<%BANNER%>

A New Method for the Modeling of Elemental Segregation Behavior and Partitioning in Single Crystal Nickel Base Superalloys


PAGE 1

A NEW METHOD FOR THE MODELING OF ELEMENTAL SEGREGATION BEHAVIOR AND PARTITIONING IN SINGLE CRYSTAL NICKEL BASE SUPERALLOYS By ERIC CHRISTOPHER CALDWELL A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2004

PAGE 2

Copyright 2004 by Eric Christopher Caldwell

PAGE 3

This work is dedicated to my family a nd friends who have been with me through good times and bad. And for those who travel in ha rms way, there is a light at the end of the tunnel. Godspeed!

PAGE 4

Nothing of value is free from Starship Troopers by Robert A. Heinlein

PAGE 5

v ACKNOWLEDGMENTS The author would like to thank and to acknowledge the support of Dr. Gerhard Fuchs for providing the way and the means, Dr Reza Abbaschian and Dr. Robert DeHoff for support and consultation, and my fam ily and friends for their support and understanding, especially Dr Daniel Villanueva for making me realize that I was in the wrong career. Additional thanks go to Wayne Ac ree and the staff of the Major Analytical Instrument Center (MAIC) at the Univers ity of Florida, and oddly enough, the United States Navy for giving me the backbone, c ourage and dedication to see the job done. This material is based on work suppor ted by the National Sc ience Foundation under Grant No. 0072671.

PAGE 6

vi TABLE OF CONTENTS page ACKNOWLEDGMENTS...................................................................................................v LIST OF TABLES.............................................................................................................ix LIST OF FIGURES...........................................................................................................xi ABSTRACT.....................................................................................................................xi x CHAPTER 1 INTRODUCTION........................................................................................................1 2 LITERATURE SEARCH.............................................................................................9 2.1. Evolution of Nickel Based Superalloys.................................................................9 2.1.1. The Matrix..........................................................................................10 2.1.2. Casting and Specialized Processing Techniques.......................................14 3 MATERIALS AND EXPERIMENTAL PROCEDURE...........................................19 3.1. Materials..............................................................................................................19 3.2. Metallography......................................................................................................21 3.3. Scanning Electron Microscopy/B ackscatter Electron Microscopy.....................24 3.3.1. Electron Microprobe Analysis...................................................................26 3.3.2. Verification of Applicability of Analysis..................................................28 4 EXPERIMENTAL RESULTS...................................................................................29 4.1. Primary Dendrite Arm Spacing...........................................................................29 4.2. Electron Microprobe Analysis.............................................................................30 4.3. Elemental Segregation and Partitioning..............................................................32 4.3.1. Cobalt Partitioning.....................................................................................38 4.3.2. Chromium Partitioning..............................................................................39 4.3.3. Rhenium Partitioning.................................................................................43 4.3.4. Tungsten partitioning.................................................................................46 4.3.5. Tungsten Partitioning with an Addition of Molybdenum.........................47 4.3.6. Molybdenum Partitioning..........................................................................51 4.3.7. Ruthenium Partitioning.............................................................................51

PAGE 7

vii 4.3.8. Palladium Partitioning...............................................................................52 4.3.9. Tungsten and Molybdenum Partitioning Interactions...............................55 4.3.10. Tantalum and Aluminum Partitioning Interactions.................................57 4.3.11. Tantalum and Aluminum Partitioning Interactions with an Addition of Titanium...........................................................................................................60 4.4. Segregation Behavior...........................................................................................64 4.4.1. Cobalt Segregation Behavior.....................................................................70 4.4.2. Chromium Segregation Behavior..............................................................71 4.4.3. Rhenium Segregation Behavior.................................................................75 4.4.4. Tungsten Segregation Behavior................................................................78 4.4.5. Tungsten Segregation Behavior with an Addition of Molybdenum.........79 4.4.6. Molybdenum Segregation Behavior..........................................................80 4.4.7. Ruthenium Segregation Behavior..............................................................80 4.4.8. Palladium Segregation Behavior...............................................................83 4.4.9. Tungsten and Molybdenum Segreg ation Behavior Interactions...............83 4.4.10. Tantalum and Aluminum Segreg ation Behavior Interactions.................87 4.4.11. Tantalum and Aluminum Segregati on Behavior with an Addition of Titanium...........................................................................................................88 4.5. Scheil Analysis and Comparison.........................................................................92 4.6. Verification of Applicability of Analysis............................................................96 5 DISCUSSION.............................................................................................................98 5.1. Primary Dendrite Arm Spacing.........................................................................100 5.2. Partitioning Coefficient and Segregation...........................................................101 5.2.1. Comparison of k and Techniques for Examining Segregation...........101 5.2.2. Cobalt Effects..........................................................................................105 5.2.3. Chromium Effects...................................................................................107 5.2.4. Rhenium Effects......................................................................................109 5.2.5. Tungsten Effects......................................................................................111 5.2.6. Tungsten Effects with an Addition of Molybdenum...............................113 5.2.7. Molybdenum Effects...............................................................................114 5.2.8. Ruthenium Effects...................................................................................115 5.2.9. Palladium Effects.....................................................................................117 5.2.10. Tungsten and Molybdenum Effects.......................................................118 5.2.11. Tantalum and Aluminum Effects..........................................................120 5.2.11.1 Effect of increased tantal um with decreased aluminum...............120 5.2.11.2. Effect of decreased tantalum and increased aluminum...............121 5.2.12. Tantalum and Aluminum Effects with an Addition of Titanium..........123 5.2.12.1. Effect of decreased tantalum with titanium.................................123 5.2.12.2. Effect of decreased aluminum with titanium..............................125 5.3. Scheil Analysis..................................................................................................127 5.3.1. Analysis of LMSX-3...............................................................................128 5.3.2. Analysis of CMSX-4...............................................................................128 6 CONCLUSIONS......................................................................................................133

PAGE 8

viii 7 FUTURE WORK......................................................................................................138 7.1. Solidification Front Curves from EMPA...........................................................138 7.2. Other Elemental Interaction...............................................................................139 APPENDIX A SAMPLE BACKSCATTERED ELECTRON IMAGES.........................................141 B ELECTRON MICROPROBE ANALYSIS SCHEDULES AND SUMMARY OF PROCEDURE USED...............................................................................................160 C AVERAGE ELECTRON MICROPROBE ANALYSES RESULTS......................163 D SCHEIL ANALYSIS GRAPHS FOR LMSX-3.......................................................182 E SCHEIL ANALYSIS DATA AND GRAPHS FOR CMSX-4.................................195 F SCHEIL ANALYSIS GRAPHS FOR LMSX-3.......................................................204 G SCHEIL ANALYSIS DATA AND GRAPHS FOR CMSX-4.................................217 LIST OF REFERENCES.................................................................................................226 BIOGRAPHICAL SKETCH...........................................................................................230

PAGE 9

ix LIST OF TABLES Table page 3-1 Compositions of the 18 model alloys in weight percent (wt%)...............................22 3-2 Composition of CMSX-4 in wt%.4,6........................................................................28 4-1 PDAS measurements from EMPA and from hand calculations..............................31 4-2 Showing weight percentages of each respective element in each alloy from the dendrite core and the interdendritic re gion, and the calculated k value for both techniques A (in orange ), and B (in blue)................................................................35 4-3 Comparison of values calculated by kB and .........................................................73 4-4 Comparison of kB and for CMSX-4....................................................................97 5-1 i for the eighteen model alloys and CMSX -4 listed in order from lowest to highest....................................................................................................................105 6-1 Elemental segregation effects for each combination of alloy compared................136 7-1 Recommended alloying variati ons to investigate in wt%......................................139 7-2 Recommended alloying va riations based on at%...................................................140 C-1 Average EMPA data for LMSX-1.........................................................................164 C-2 Average EMPA data for LMSX-2.........................................................................165 C-3 Average EMPA data for LMSX-3.........................................................................166 C-4 Average EMPA data for LMSX-4.........................................................................167 C-5 Average EMPA data for LMSX-5.........................................................................168 C-6 Average EMPA data for LMSX-6.........................................................................169 C-7 Average EMPA data for LMSX-7.........................................................................170 C-8 Average EMPA data for LMSX-8.........................................................................171

PAGE 10

x C-9 Average EMPA data for LMSX-9.........................................................................172 C-10 Average EMPA data for LMSX-10.......................................................................173 C-11 Average EMPA data for LMSX-11.......................................................................174 C-12 Average EMPA data for LMSX-12.......................................................................175 C-13 Average EMPA data for LMSX-13.......................................................................176 C-14 Average EMPA data for LMSX-14.......................................................................177 C-15 Average EMPA data for LMSX-15.......................................................................178 C-16 Average EMPA data for LMSX-16.......................................................................179 C-17 Average EMPA data for LMSX-17.......................................................................180 C-18 Average EMPA data for LMSX-18.......................................................................181 E-1 Scheil curve data for CMSX-4...............................................................................201 F-1 EMPA data for LMSX-3 Scheil analysis...............................................................209 G-1 Scheil curve data for CMSX-4...............................................................................223

PAGE 11

xi LIST OF FIGURES Figure page 2-1 The matrix from model alloy LMSX-15. Image taken at 10kx. matrix and precipitates are labeled.............................................................................................10 2-2 Al-Ni phase diagram. The AlNi3 field is visible at 85 87 wt% Ni.......................11 2-3 FCC matrix shown above left and L12 ordered phase of Ni3Al (Ni shown in black) above right.6.............................................................................................................11 2-4 Ni-Al-X ternary phase diagram. The Ni3Al phase fields are shown in the phase diagram with the various other additions, indicating large regions of solubility.....14 2-5 The improvements in alloy elongation and rupture strength for the same alloys (M252 and Waspalloy) for vacuum melt and air melt..................................................15 2-6 DS casting operation is shown on the le ft and SX casting operations are shown on the right. The primary difference is the use of a constricto r or single crystal selector.....................................................................................................................17 3-1 BSE image of LMSX-1 taken at 100x equivalent....................................................25 3-2 BSE image of LMSX-13 taken at 100x equivalent..................................................25 3-3 BSE photo of LMSX-1 taken at 100x equi valent. Yellow line i ndicates location of the line scan preformed............................................................................................27 4-1 BSE image of LMSX-13. Black lines added to image were where PDAS measurements were taken.........................................................................................30 4-2 k values for LMSX-1 for techniques A (o range) and B (blue). The green line is at k = 1........................................................................................................................4 0 4-3 k values for LMSX-13 for techniques A (orange) and B (blue). The green line is at k = 1....................................................................................................................40 4-4 k values for LMSX-18 for techniques A (orange) and B (blue). The green line is at k = 1....................................................................................................................41 4-5 k values for LMSX-8 for techniques A (o range) and B (blue). The green line is at k = 1. The difference is noted by a circle...............................................................41

PAGE 12

xii 4-6 Mo segregation plot for LMSX-7 a nd -8. White points were used in kB analysis. Second order trendlines are al so shown for both alloys...........................................42 4-7 Al segregation plot for LMSX-1 and 18 shown for comparison. White points were used in kB analysis. Second order trendlines are also shown for all alloys............42 4-8 Partitioning effects due to increasing Co concentration for elements showing a preference to segregate to the dendritic region........................................................44 4-9 Partitioning effects due to increasing Co concentration for elements showing a preference to segregate to th e interdendritic region.................................................44 4-10 Partitioning effects due to increasing Cr concentration for elements showing a preference to segregate to the dendritic region........................................................45 4-11 Partitioning effects due to increasing Cr concentration for elements showing a preference to segregate to th e interdendritic region.................................................45 4-12 Partitioning effects due to increasing Re concentration for elements showing a preference to segregate to the dendritic region........................................................48 4-13 Partitioning effects due to increasing Re concentration for elements showing a preference to segregate to th e interdendritic region.................................................48 4-14 Partitioning effects due to increasing W concentration for element segregating to the dendritic region...................................................................................................49 4-15 Partitioning effects due to increasing W concentration for element segregating to the interdendritic region...........................................................................................49 4-16 Partitioning effects due to decreasing W concentration with the addition of 1 at% Mo for element segregating to the dendritic region.................................................50 4-17 Partitioning effects due to decreasing W concentration with the addition of 1 at% Mo for element segregating to the interdendritic region..........................................50 4-18 Partitioning effects due to the addition of 1 at% Mo for element segregating to the dendritic region........................................................................................................53 4-19 Partitioning effects due to the addition of 1 at% Mo for element segregating to the interdendritic region.................................................................................................53 4-20 Partitioning effects due to Ru addition for element segregating to the dendritic region........................................................................................................................5 4 4-21 Partitioning effects due to Ru addition fo r element segregating to the interdendritic region........................................................................................................................5 4

PAGE 13

xiii 4-22 Partitioning effects due to Pd addition for element segregating to the dendritic region........................................................................................................................5 6 4-23 Partitioning effects due to Pd addition for element segregating to the interdendritic region........................................................................................................................5 6 4-24 Partitioning trends for elements in LMSX -1 and-7. Difference in the two alloys is that LMSX-7 contains 3.1 wt% W and an addition of 1.6 wt% Mo........................58 4-25 Partitioning trends for elements in LMSX-6 and -8. Difference in the alloys is that LMSX-6 contains 8.6 wt% W, 0 wt% M o, and LMSX-8 contains 5.85 wt% W, 1.6 wt% Mo....................................................................................................................58 4-26 Partitioning trends for elements between in LMSX-1 and-12. Difference in the two alloys is that LMSX-12 contai ns 11.2 wt% Ta and 5.0 wt% Al..............................61 4-27 Partitioning trends for elements between in LMSX-1 and-13. Elements segregating to the dendritic region show n. Difference in the two alloys is that LMSX-13 contains 6.00 wt% Ta and 6.15 wt% Al...................................................................61 4-28 Partitioning trends for elements between in LMSX-1 and-13. Elements segregating to the interdendritic region shown. Difference in the two alloys is that LMSX-13 contains 6.00 wt% Ta and 6.15 wt% Al...................................................................62 4-29 Partitioning trends for elements be tween in LMSX-12 and-13. Elements segregating to the de ndritic region shown................................................................62 4-30 Partitioning trends for elements be tween in LMSX-12 and-13. Elements segregating to the interd endritic region shown........................................................63 4-31 Partitioning trends for elements between in LMSX-1 and-14. Elements segregating to the dendritic region show n. Difference in the two alloys is that LMSX-14 contains 6.00 wt% Ta and an addition of 0.80 wt% Ti............................................65 4-32 Partitioning trends for elements between in LMSX-1 and-14. Elements segregating to the interdendritic region shown. Difference in the two alloys is that LMSX-14 contains 6.00 wt% Ta and an addition of 0.80 wt% Ti............................................65 4-33 Partitioning trends for elements between in LMSX-1 and-15. Elements segregating to the dendritic region show n. Difference in the two alloys is that LMSX-15 contains 5.10 wt% Al and an addition of 0.80 wt% Ti............................................66 4-34 Partitioning trends for elements between in LMSX-1 and-15. Elements segregating to the interdendritic region shown. Difference in the two alloys is that LMSX-15 contains 5.10 wt% Al and an addition of 0.80 wt% Ti............................................66 4-35 Partitioning trends for elements be tween in LMSX-14 and-15. Elements segregating to the de ndritic region shown................................................................67

PAGE 14

xiv 4-36 Partitioning trends for elements be tween in LMSX-14 and-15. Elements segregating to the interd endritic region shown........................................................67 4-37 Red lines indicated soli dification/segregation gradie nts between dendrite cores within the interdendritic region for an elemen t that segregates to the dendrite cores. The dendrites are represented in yellow...................................................................69 4-38 Elemental segregation plots based on due to increasing Co content from 4 wt% to 12.2 wt%...................................................................................................................75 4-39 Elemental segregation plots based on due to increasing Cr content from 2.1 wt% to 6.15 wt%..............................................................................................................76 4-40 Elemental segregation plots based on due to increasing Re content from 0 wt% to 8.9 wt%.....................................................................................................................78 4-41 Elemental segregation plots based on due to increasing W content from 5.85 wt% to 8.6 wt%................................................................................................................79 4-42 Elemental segregation plots based on due to increasing W content from 3.1 wt% to 5.85 wt% with an addition of 1.6 wt% Mo to the alloys......................................82 4-43 Element segregation plots based on due to increasing Mo content from 0 wt% to 1.6 wt%.....................................................................................................................82 4-44 Element segregation plots based on due to increasing Ru content from 0 wt% to 3.2 wt%.....................................................................................................................84 4-45 Elemental segregation plots based on due to increasing Pd content from 0 wt% to 1.7 wt%.....................................................................................................................84 4-46 Elemental segregation plots based on due to decreasing W to 3.1 wt% and adding 1.6 wt % Mo.............................................................................................................86 4-47 Elemental segregation plot based on due to decreasing W to 5.85 wt% and adding 1.6 wt% Mo..................................................................................................86 4-48 Elemental segregation plots based on due to increasing Ta to 11.2 wt% and decreasing Al to 5 wt%............................................................................................89 4-49 Elemental segregation plots based on due to decreasing Ta to 6.0 wt% and increasing Al to 6.15 wt%........................................................................................89 4-50 Elemental segregation plots based on due to changing Ta and Al concentrations. Compilation of Figures 4-48 and 4-49.....................................................................90 4-51 Elemental segregation plots based on due to decreasing Ta to 6.0 wt% and a Ti addition of 0.80 wt%................................................................................................93

PAGE 15

xv 4-52 Elemental segregation plots based on due to decreasing Al to 5.10 wt% and a Ti addition of 0.80 wt%................................................................................................93 4-53 Elemental segregation plots based on due to changing Ta and Al concentrations with a Ti addition. Compilation of figures 4-51 and 4-52......................................94 4-54 Scheil curve comparison for Cr done by two different techniques..........................94 4-55 Scheil curve comparison for Re done by two different techniques..........................95 4-56 Scheil curve comparison for Ta done by two different techniques..........................95 5-1 Ni segregation plot for LMSX-9, -10, -1, and -11. Trendlines were added to show degree of segregation of Ni observed as the Re content was increased.................103 5-2 Ta segregation plot for LMSX-9, -10, 1, and -11. Trendlines were added to show degree of segregation of Ni observed as the Re content was increased.................103 5-3 Example showing data for k and from two idealized elemental segregation profiles based on a normalized PDAS. Th e equations for each trendline are indicated on the graph............................................................................................104 5-4 LMSX-3 Scheil curves for Fu ll and Short techniques for Cr.................................130 5-5 LMSX-3 Scheil curves for Fu ll and Short techniques for Al.................................130 5-6 Scheil curves for Re from CMSX-4 done using the techniques described in this study.......................................................................................................................131 5-7 Scheil curves for Re from CMSX-4 from literature.43...........................................131 5-8 Scheil curves for Ta from CMSX-4 done using the techniques described in this study.......................................................................................................................131 5-9 Scheil curves for Ta from CMSX-4 from literature.43...........................................131 5-10 Scheil curves for Ti from CMSX-4 done using the techniques described in this study.......................................................................................................................132 5-11 Scheil curves for Ti from CMSX-4 from literature.43............................................132 5-12 Scheil curves for W from CMSX-4 done using the techniques described in this study.......................................................................................................................132 5-13 Scheil curves for W from CMSX-4 from literature.43............................................132 A-1 BSE image of LMSX-1 at 100x.............................................................................142 A-2 BSE image of LMSX-1 at 100x.............................................................................142

PAGE 16

xvi A-3 BSE image of LMSX-2 at 100x.............................................................................143 A-4 BSE image of LMSX-2 at 100x.............................................................................143 A-5 BSE image of LMSX-3 at 100x.............................................................................144 A-6 BSE image of LMSX-3 at 100x.............................................................................144 A-7 BSE image of LMSX-4 at 100x.............................................................................145 A-8 BSE image of LMSX-4 at 100x.............................................................................145 A-9 BSE image of LMSX-5 at 100x.............................................................................146 A-10 BSE image of LMSX-5 at 100x.............................................................................146 A-11 BSE image of LMSX-6 at 100x.............................................................................147 A-12 BSE image of LMSX-6 at 100x.............................................................................147 A-13 BSE image of LMSX-7 at 100x.............................................................................148 A-14 BSE image of LMSX-7 at 100x.............................................................................148 A-15 BSE image of LMSX-8 at 100x.............................................................................149 A-16 BSE image of LMSX-8 at 100x.............................................................................149 A-17 BSE image of LMSX-9 at 100x.............................................................................150 A-18 BSE image of LMSX-9 at 100x.............................................................................150 A-19 BSE image of LMSX-10 at 100x...........................................................................151 A-20 BSE image of LMSX-10 at 100x...........................................................................151 A-21 BSE image of LMSX-11 at 100x...........................................................................152 A-22 BSE image of LMSX-11 at 100x...........................................................................152 A-23 BSE image of LMSX-12 at 100x...........................................................................153 A-24 BSE image of LMSX-12 at 100x...........................................................................153 A-25 BSE image of LMSX-13 at 100x...........................................................................154 A-26 BSE image of LMSX-13 at 100x...........................................................................154 A-27 BSE image of LMSX-14 at 100x...........................................................................155

PAGE 17

xvii A-28 BSE image of LMSX-14 at 100x...........................................................................155 A-29 BSE image of LMSX-15 at 100x...........................................................................156 A-30 BSE image of LMSX-15 at 100x...........................................................................156 A-31 BSE image of LMSX-16 at 100x...........................................................................157 A-32 BSE image of LMSX-16 at 100x...........................................................................157 A-33 BSE image of LMSX-17 at 100x...........................................................................158 A-34 BSE image of LMSX-17 at 100x...........................................................................158 A-35 BSE image of LMSX-18 at 100x...........................................................................159 A-36 BSE image of LMSX-18 at 100x...........................................................................159 E-1 Scheil curve for Ni from CMSX-4.........................................................................196 E-2 Scheil curve for Cr from CMSX-4.........................................................................196 E-3 Scheil curve for Co from CMSX-4........................................................................197 E-4 Scheil curve for Mo from CMSX-4.......................................................................197 E-5 Scheil curve for W in CMSX-4..............................................................................198 E-6 Scheil curve for Re in CMSX-4.............................................................................198 E-7 Scheil curve for Ta from CMSX-4.........................................................................199 E-8 Scheil curve for Al from CMSX-4.........................................................................199 E-9 Scheil curve for Ti from CMSX-4.........................................................................200 F-1 Scheil curves comparing full and short techniques for Ni in LMSX-3..................205 F-2 Scheil curves comparing full and short techniques for Cr in LMSX-3..................205 F-3 Scheil curves for both full and sh ort techniques for Co in LMSX-3.....................206 F-4 Scheil curves for both full and sh ort techniques for W in LMSX-3......................206 F-5 Scheil curves for both long and shor t techniques for Re in LMSX-3....................207 F-6 Scheil curves for both long and shor t techniques for Ta in LMSX-3....................207 F-7 Scheil curves for both full and short techniques for Al in LMSX-3......................208

PAGE 18

xviii G-1 Scheil curve for Ni from CMSX-4.........................................................................218 G-2 Scheil curve for Cr from CMSX-4.........................................................................218 G-3 Scheil curve for Co from CMSX-4........................................................................219 G-4 Scheil curve for Mo from CMSX-4.......................................................................219 G-5 Scheil curve for W in CMSX-4..............................................................................220 G-6 Scheil curve for Re in CMSX-4.............................................................................220 G-7 Scheil curve for Ta from CMSX-4.........................................................................221 G-8 Scheil curve for Al from CMSX-4.........................................................................221 G-9 Scheil curve for Ti from CMSX-4.........................................................................222

PAGE 19

xix Abstract of Thesis Presen ted to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree Masters of Science A NEW METHOD FOR THE MODELING OF ELEMENTAL SEGREGATION BEHAVIOR AND PARTITIONING IN SINGLE CRYSTAL NICKEL BASE SUPERALLOYS By Eric Christopher Caldwell August 2004 Chair: Gerhard Fuchs Major Department: Materials Science and Engineering Ni-base superalloys are commonly used in very extreme environments where high temperature strength, good corro sion/oxidization resistance, a nd microstructural stability are required. These superalloys are made up of twelve to fifteen different elemental additions including, but not limite d to, Cr, Co, Mo, W, Re, Ta, Al, Ti, Ru, and Pd. The combinations of these elements make cas ting of a superalloy difficult and undesirable phases (the Topologically Close Packed, or TCP phases) may form in the microstructure during casting or service. TCP phases form due to localized concentra tions of specific elements. To prevent the formation of these undesirable phases and to maximize the alloys properties, solutioning heat treatments are required. Many of the solutioning heat treatment for third generation superalloys (2 at% Re) are very l ong. The length of time has to be sufficient to remove the elemental segregation th at exists within the microstructure.

PAGE 20

xx The elemental segregation exists upon casti ng due to alloying elements partitioning to a specific phase ( or ) or region (dendrite core or interdendritic region). A partitioning coefficient, k, is used to descri be the partitioning behavior of the alloying elements. k was observed to exhibit a diffe rent partitioning behavior than was indicated by electron microprobe line scans. A new term based on the curvature of the segregation plot, was used to qualify the direction of each elements partitioning (dendr ite core or interdendritic region), and to quantify some degree of relative segregati on between all the alloying elements in each alloy. The values for were then plotted against vary ing elemental relationships and conclusions about the segregat ion behavior were drawn.

PAGE 21

1 CHAPTER 1 INTRODUCTION The need for new materials is ever present and has been a driving force in technological evolution. The ga s turbine engine is a prime example of this. Due to the extreme operating conditions within the engine, most materials as well as the processes used to fabricate components are insufficient. Historically the first true application of gas turbine technology was the first jet aircraft of World War II. These aircraft we re revolutionary at the time, but severely limited operationally and cost prohibitive due to materials issues. The ME-262, the first jet powered airplane, was power ed by a Junkers Jumo 004B (F igure 1-1) turbojet engine, generating about 2,000 pounds of thrust. Howeve r, the engine could only run for around forty hours before it had to be replaced. Th is short service life was largely due to the Figure 1-1: Junkers Jumo 004A turbojet engine

PAGE 22

2 forged steels used in the engine. After World War II, th e jet age began, and with it the quest for higher powered and mo re reliable turbojet engines. One of the key limiting components of the tu rbojet engine (or more simply here, turbine) are the blades and vanes within the h ot section. The hot section is as the name implies: the hot part of the engine A turbojet operates under the thermodynamic Brayton cycle. The efficiency of a Brayton cycle is determined by the temperature of the first stage of the turbine. Th e higher the temperature of the fi rst stage, the more efficient and higher power the turbojet can become. Si nce more power is desired and the limiting components are in the region of the turbine se ction, these components had to be designed better and new materials used to reach the higher temperatures required to increase efficiency. The Junkers Jumo 004B blades were made of forged mild steel (SAE 1010) that had an aluminum coating for oxidization protection.3 It should be noted that the use of steel over other metals was due to availability of steel compared to other scarce strategic materials. Besides being exposed to the hi ghest temperatures within the engine, the blades and vanes are also exposed to a ve ry corrosive environment and at high stress levels. This lead the early metallurgists to select the Co-based and Ni-based metals for turbine applications, which are now called superalloys (Figure 1-2). Many of the early improvements to superall oys came from both processing and by alloying. The concept of investment casting was taken from the dental industry. With this innovation came problems such as inclusions from the mold, but investment casting was cheaper and easier to manufacture than fo rged components. The advent of vacuum induction melting (VIM) by F. N. Darmara in the 1950s reduced the problem of

PAGE 23

3 Figure 1-2: The change of temperature capab ilities for superalloys at the approximate time the alloy was introduced.4 inclusions to wrought processes.5 VIM made casting an even more viable alternative because purer alloys could be made with fewer inclusions. As an added benefit, additions of more reactive additions for solid soluti on strengthening (i.e., W, Nb, and later Ta)4 could be used due to the vacuum atmosphere in the processing stage. Therefore better strength and creep resistance, and ultimately higher temperature capability, were realized in the resulting alloys. One of the first superalloys was Ni-20Cr, a simple solid solution strengthened alloy. To increase the strength of this all oy, metallurgists began to add other alloying elements, like Mo and C, to the Ni-Cr base alloy. The demand for higher temperature use was still present, and since Cr depressed th e Ni melting point, other alloying elements such as Al had to be utilized. The Ni-Al al loys worked well with the VIM process due to the reactivity of Al with the atmosphere and the need to keep Al in solution. There were two potential precip itate strengthening phases that could be used for the nickel-aluminum alloys: -NiAl, and -Ni3Al. Initially, the Ni-bas e alloys were single

PAGE 24

4 phase due to the FCC lattice which provided g ood creep resistance. It was later found that a matrix with ( is an order phase with an L12 type structure) precipitates produced higher strength materials and allo wed operational temperatures to increase further. The phase forms as a cuboidal precipitate but the shape of the precipitate is governed by the misfit strains betwee n the precipitates and the matrix.6 Negative misfit produces small cubes, and positive misfit produces spheres. A significant portion of the strengthening of the alloys is from the phase, the interface, and single coherent with the matrix. The aluminum also result ed in the formation of a thin Al2O3 coating on the surface which reduced the problems of co rrosion in the hot sections. The resulting alloys were the first generation superalloys. Al l of the elements that had previously been added to the matrix when steels and other meta ls were used (i.e., Cr, W, Nb, Ti, Ta, etc.), were all added to these new alloys. The resu lting Ni-based alloys could be used up to about 85% of their homologous temperature.4 The entire time alloy development was in progress, the processing advances were also occurring. Due to the high temperatures, turbine blades must al so withstand creep; a slow time-temperature-stress dependant type of deformation. Inve stigation found that creep life could be extended by reducing th e number of transverse grain boundaries within the component. The number of tr ansverse grains was reduced with the development of directiona l solidification in 1960.6 Directional solidification (DS) itself was further developed by controlling the with drawal rate of the casting, and therefore controlling the solidific ation front to yield only high angle boundaries (HAB) and low angle boundaries (LAB)7 along the direction of grain growth.

PAGE 25

5 DS work was not the last of the advancem ents in processing. The ultimate goal of DS was the complete elimination of grain boundaries from the cast component, to produce a single crystal. This was accomplis hed with the addition of a grain selector.8 This grain selector almost completely elim inates the HABs and LABs from the casting and produces a single crystal (SX). SX technology further in creased the operating temperatures and operational lifetimes of components within a turbine. The next key innovation was the addition of rhenium to the alloy. With the addition of 1 atomic percent (at%) Re, ther e was a substantial boost in the mechanical properties of the cast alloys. These alloys containing 1 at% Re became known as second generation superalloys. It is often said that Nece ssity is the mother of inven tion, and the desire for better operational capabilities of turbines was stil l the quest. Around the mid 1990s another 1 at% of Re was added to the superalloys.9 These were given the moniker of third generation superalloys due to their Re addition, which resulted in a further increase in the properties of the alloy. Throughout these all oy and process improvements, engineers and designers took advantage of the increased te mperature capabilities of the blade and vane alloys. Due to the increased temperature capab ilities of the materials, engine design has taken off more. The F-119 turbojet engine is currently the state of the art and generates 35000 pounds of thrust (Figure 3).10 A very large increase when compared to that of the early Jumo 004B (an increase of about 18 x in only 50 years). Due to the increased additions of many high density refractory elements (nearly 20% of the weight was due to less than 10% of the additions), a relatively minor problem began to becomes more significant. Unde sirable phases began to form in the

PAGE 26

6 Figure 1-3: A modern day turb ojet engine. This is the F-119 engine developed by Pratt & Whitney for the F-22 Raptor and the F-35 Joint Strike fighter. microstructure along specific orientations. These phases are called topologically close packed (TCP) phases. While they did form in the earlier generation superalloys, TCP has become more of a problem in the third gene ration superalloys. TCPs form at relatively high temperature, over extended time, consists primarily of the heavy refractory elements, and form within the microstructure of components in service. There are cases of TCP forming upon casting (i.e. CMSX-10), but these TCP phases can be put back into solution by solutioning heat treatments. Some of these solutioning heat treatments are exceedingly long and take over fifty hours11 to complete. TCP are composed of many of the refractory elements added to the alloy for strengthening, and the presence of the TCP therefore depletes the microstructure of th e key solid solution strengthening elements. Also, TCP are inherently brittle and are reported to be comm on failure initiation sites in failed components.4 TCP are needlelike in shape when viewed in the transverse di rection and disk like when observed from the proper longitudina l orientation. Some of the common TCP phases are , r, p, and Laves phases.12 Although relatively little is understood about TCP formation, an understanding of the elemen tal partitioning during solidification could

PAGE 27

7 aid in TCP prediction, alloy developmen t, and develop better heat treatment requirements. Earlier analysis involved the use of a segregation partitioning coefficient, k. This partitioning coefficient relates the difference in the amount of an element present between the dendrite core and the interdendr itic region and has been defined as13 itic Interdendr i Dendrite ix x k, ,' (equation 1-1) where xi, dendrite is the composition in the dendrite core (in wt%) for element i, and xi, interdendritic is the composition of element i within th e interdendritic region (in wt%). Other work has utilized partitioning coefficients by performing a Scheil analysis on the data collected. It is the goal of this investigation to fu rther examine the elemental partitioning that takes place during the solidification of a supera lloy. To do this a different technique was used to collect the data in the effort to determine how composition effects elemental segregation. This different technique was then compared against prior work done, and was re-examined to identify any new trends. Two additional checks were also done. The first was Scheil-type analysis that was preformed on one of the model alloys to s ee how the data collecti on technique in this study compared to that typically preformed in industry. The second check done in this investigation was then preformed on a co mmon, commercial superalloy to determine how the analysis used in this study compares to what is reported in open literature. Using the compositional data collected, this new analys is technique which used the curvature of compositional profile of the elemental segregation from dendrite core to dendrite core. This was be done in hope s of developing a better understanding of

PAGE 28

8 elemental segregation in a s uperalloy on solidification in or der to develop more castable alloys with reduced heat treatment requireme nts, and create new and better alloys for future use.

PAGE 29

9 CHAPTER 2 LITERATURE SEARCH Ni-base superalloys are some of the most complex metal alloys used, and are used in very extreme, if not hostile environments The metallurgy of superalloys begins with the microstructure that results from th e elemental additions, and then casting and processing. The processing of these advanced alloys has to be carefully controlled and the steps understood to produ ce the optimal balance of pr operties and to avoid the formation deleterious phases and an i nhomogeneous microstructure. There are inhomogentities in the elemental distribution that occur on casting of the advanced superalloys due to elemental partitioning and segregation. This section will provide an overview of this history and present current ideas regarding the phenomena of segregation in third gene ration Ni-base superalloys. 2.1. Evolution of Nickel Based Superalloys The development of Ni-base superalloys begins nearly 100 years ago. A simple wrought Ni-20Cr alloy was used for electri cal heating elements. They have grown tremendously from this humble beginning and have spread in their use from heating elements, to corrosion resistant alloys, and to high temperature applications. A specific high temperature application for Ni-base alloys is the hot section components of aircraft turbine engines, and industrial gas turbine (IGT) engines. The Ni alloys developed for use in these components need to have excel lent strength, creep re sistance, and fatigue resistance at high temperature, and also be resistant to oxidation and hot corrosion. The

PAGE 30

10 development of these alloys requires unique alloying additions and special casting and processing techniques. 2.1.1. The Matrix The ability for Ni-based superalloys to tolerate high levels of alloying without forming microstructural instabil ities, and to form the unique microstructure produces a material with unique properties. The material is composed of two phases, a matrix with precipitates spread throughout, with a coherent interface between the phases (Figure 2-1). Figure 2-2 is the Al-Ni phase diagram show ing the specific composition range of interest for the formation of these alloys.14 The matrix is a FCC structure and the is an L12 type ordered structure (Figure 2-3) The FCC structure exhibits the highest degree of packing with numerous sl ip systems which typically results in a material that maintains arrangement for c onstituent atoms to maintain tensile, creep rupture, and fatigue strengt h, at temperatures close to the homologous temperature. Figure 2-1: The matrix from model alloy LMSX-15. Image taken at 10kx. matrix and precipitates are labeled. matrix precipitate

PAGE 31

11 The FCC lattice also has a large range of solubili ty for other elements that can be used to improve the properties of the alloy. The precipitate has nearly the same lattice parameter as the matrix making the matrix and precipitate coherent. Figure 2-2: Al-Ni phase diagram. The AlNi3 field is visible at 85 87 wt% Ni. Figure 2-3: FCC matrix shown above left and L12 ordered phase of Ni3Al (Ni shown in black) above right.6 The benefits of the FCC or matrix were originally discovered in steels and were found to have the ability to be heavily alloyed. The base element for high temperature alloys was shifted from Fe to Ni and Co becau se they had the ability to be alloyed to a greater extent and the microstructure could be formed. Cr and Al were some of the

PAGE 32

12 earliest additions to this base material. They acted as solid solution strengtheners, increased environmental resistance, and incr eased the high temperature properties of the alloys. The addition of Cr to the matrix incr eased the alloys resist ance to hot corrosion, and Al increased its resistance to high temperature oxidation.4,6 The high strength of the superalloys come s from solid soluti on strengthening, precipitation hardening, a nd the misfit between the and its coherent ordered precipitated, . When alloying elements are ad ded, the lattice parameters for the and both change slightly due to the alloying elem ents being larger or smaller than the one they are substituting for (Hume-Rothery criteri a for solid solution strengthening). The misfit is the difference in lattice parameters between the matrix and the precipitate. Misfit influences the shape of the precipitate. At low misf it strains (0.0 0.2 %), the precipitates are spherical. At sligh tly higher misfit stra ins (0.5-1.0 %), the precipitates are cuboidal. Finally, when the mi sfit is even higher (> 1.25 %), the precipitates are plate-like. It is the formation of the cuboidal and the very fine (secondary) (which is formed on ageing) that prevents dislocation bypass and forces the dislocations to cut through the ordered particle forming a superdislocation. The volume fraction is also important because it influences alloy strength4. Alloys that have a very high volume fraction ( 70% and greater) exhibit high strengt h, but very limited ductility, and the opposite is true for the low volume fraction alloys. It is the combination of the volume fraction, misfit, and coherency of the precipitate that bring about th e high strengths of superalloys. There are many different elemental additi ons used to improve the properties of superalloys. Among the additions are Co, Cr, Mo, W, Re, Ta, Ti, Ru, and Pd (which has

PAGE 33

13 become of recent interest). Many of these elements are soluble in the Ni3Al system (Figure 2-4).30 Each addition has various contributions it provides to the superalloy as a whole, and summarized below Cobalt Added to reduce or offset the solvus temperatur e without causing incipient melting4,6,15, is reported to increase the mi crostructural stability of the alloy9,15, reduces stacking fault energy ( SFE), and provides some solid solution strengthening.6 Co has been reported to pa rtition to the dendrite core.16,17,18 Chromium : Added to increase the surface stability and prevent/minimize hot corrosion4,6, reduces the solvus temperature19, reduces the anti-phase boundary energy ( APB) of the phase. Cr has been to partition to the dendrite core16,17,18 and is a known component of TCP phases.4,6 Molybdenum : Added to increase solid solution strengthening of the matrix6,18, lower the alloy density (Mo is less dense than other elements like W), adjust the volume fraction.20 Mo has been reported to partition to the dendrite core16,18,21, and is a known component of TCP phases.4,6,12 Tungsten : Added because it is a potent solid solution st rengthener in Ni-base alloys16,18, and W increases the inci pient melting point of the alloy. W partitions to the dendrite core and is a known component of TCP phases.6,12 W has also been reported to increase the susceptibil ity of the alloy to hot corrosion. Rhenium : is the element that defines the diffe rence in superalloy generations. It is a strong solid solution strengthener22, and increases the high temperature creep properties.18 Re is an element found in TCP phases23 and partitions to the dendrite core.17,19,25 Tantalum : like Re is a strong so lid solution strengthener.18,25 Ta is also added to improve castability26, increase the volume fraction15, decreases the susceptibility to incipient melting27, increase the anti-ph ase boundary energy ( APB) of the , and is one of the formers. Ta has been reported to partition to the interdendritic region.16,18,22 Aluminum : is the primary former.4,6 Al is also added to increase surface stability and high temperat ure oxidation resistance4,6, and Al improves the castability of the alloy. Al has been re ported to partition to the interdendritic region.16,18,22 Titanium : another former.4,6 Ti is less dense than Ta, it increases the volume fraction15, increase the anti-ph ase boundary energy ( APB) of the , and strengthens the phase.4,6,16 Ti has been reported to par tition to the interdendritic region.16,18

PAGE 34

14 Ruthenium : is reported to increase the microstructural stability28 and act as a solid solution strengthener. Ru has been re ported to partition to the dendrite core.16,29 Palladium : is an element of recent investiga tion. Pd is added to improve the surface stability of th e alloy and act as a solid solution strengthener. Pd has been reported to partition to the dendrite core.16,29 There are other trace elements (i.e. Hf, and B) that are added as well as many deleterious elements (i.e. Cd, Hg, O, and N) that have to be removed by meticulous quality control and specializ ed processing procedures. Figure 2-4: Ni-Al-X ternar y phase diagram. The Ni3Al phase fields are shown in the phase diagram with the various other additions, indicating large regions of solubility. 2.1.2. Casting and Specialized Processing Techniques The original superalloys we re cast using investment cas ting techniques from dental prosthesis.6 Investment casting involves the pouring of the molten alloy into a preformed shell mold and then breaking the she ll mold away from the components after the alloy has solidified and coole d. This left behind grains of various sizes throughout the alloy due to different localized cooling rates. In some instan ces, inclusions were left in

PAGE 35

15 the casting from the shell, impurities in the metal melted, or some of the alloying elements oxidizing before the all oy solidifies (i.e. 2 Al + 3/2 O2 Al2O3). For the properties of the superalloys to increase, these problems had to be overcome. Vacuum induction melting (VIM) overcame these problems. Developed in the 1950s by Falih N. Darmara6, VIM removed the atmosphere to keep the reactive elements (i.e. Al and Ti) from oxidizing and leaving inclusions in the cast alloys, and aided in removing of some of the deleterious tramp elements from the alloys. VIM also allowed for closer control of the elemen tal additions. The mechanical properties increased after VAR was used. (Figure 2-5).4 Figure 2-5: The improvements in alloy elonga tion and rupture strength for the same alloys (M-252 and Waspalloy) for vacuum melt and air melt. Superalloy properties were increased with the advent of VIM and VAR, but another advancement had to achieved to continue to increase the useful temperatures and mechanical properties as turbine inlet temperat ures continued to rise. The presence of transverse grain boundaries was reduced with th e use of directional solidification (DS). The DS process was initially developed in the 1960s by F. VerSnyder and colleges working at Pratt & Whitney.6 The process used was then further improved upon by G. Chadley working at TRW.7 The improvement involved a controlled withdrawal of the casting from the furnace. The grains nucleate on the chill plate and grow into the melt,

PAGE 36

16 but the solidification interface does not change location relative to the outside of the furnace. The solidification interfaces only move s relative to the component as it is being cast. By controlling the w ithdrawal rate, which controlle d the solidification front, the only grains formed in the casting are onl y high angle boundaries (HAB) and low angle boundaries (LAB). The removal of transverse grain boundari es dramatically increased the creep properties of the alloys. The next goal wa s the elimination of grain boundaries from the alloy entirely. B. Piearch modified the mo lds being used for DS. He added a grain selector to the lower part of the casting. Th is grain selector was designed to let only on grain orientation through. This is typically the <001> orientation due to its high creep rupture properties. When the alloy was now cast, it was a single crystal (SX) with no longitudinal or transverse grains. Figure 2-631 shows the configura tion for DS casting techniques and Figure 2-731 shows the configuration for SX casting techniques. As the superalloys were being cast, they began to develop a problem. A metastable phase would develop in the microstructure ov er time while the alloy was in-service or on casting due to the high refractory element c ontent. These phases are the topologically close packed (TCP) phases and they deplete th e matrix of alloying elements when they are formed from the constituent alloying elements.12 TCP are thought to be fracture initiation sites due to their shape and brit tle behavior. Methods like PHACOMP were developed to create alloys that had stable mi crostructures that were stable (i.e., were not

PAGE 37

17 Figure 2-6: DS casting oper ation is shown on the left and SX casting operations are shown on the right. The primary differen ce is the use of a c onstrictor or single crystal selector. prone to form TCP phases). As more and mo re refractory elements were added to the alloy, the frequency of TCP formation increa sed. TCP formation was noted in some of the early superalloys during service life, but in alloys like CMSX-10, TCP phases form on casting due to the high refractory element content. Solutioning heat treatments are done to remove the TCP phases from the as-cas t alloys but these heat treatments are very long (upwards of 50 hours), at high temp erature (CMSX-10 is solution heat treated at temperatures above 1350C).16 There are several different TCP phases found in superalloys. Among these are , p, r, and the Laves phases. and p are composed predominately of Ni Cr, and Re, and to a lesser extent Co, W, and Mo.12 When a SX component is cast, a solidificati on front is formed as the dendrites grow into the melt. The dendrites reject certai n elements back into the liquid depending up how the elements partition. This rejection is the origin of the segr egation of the alloying elements within the microstructure. With the elements not being homogeneously distributed in the alloy, solutioning heat treatments must be preformed.

PAGE 38

18 Solutioning heat treatments (solutioning fo r short) are done at temperatures above the solvus temperatures and below the solidus temperature and at times sufficient to have the elements become evenly distribute d. The difference in these two temperatures ( solvus and solidus temp eratures) is called the window. In general, alloys that have less segregation are more easily solutioned. There are several benefits to developing a better understanding of the segregation of the constituent elements in a nickel base superalloy. By understanding which elements segregate more strongly, solution heat treatme nts can be developed that are potentially shorter and at lower temperature. The deve lopment of new alloys would also benefit from this understanding, by using elements th at have been shown to reduce segregation, and therefore, reduce TCP formation.

PAGE 39

19 CHAPTER 3 MATERIALS AND EXPERIMENTAL PROCEDURE In this chapter, the materials and proc edure that were used in this study are described along with the various t echniques used to analyze them. 3.1. Materials The materials used are based on a thir d generation Ni-based superalloy. The baseline alloy (LMSX-1); has a composition in weight percent (wt% ) of Ni-bal, Cr-4.15, Co-12.2, W-5.85, Re-5.9, Ta-8.6 Al5.5, Hf-0.1. The baseline composition is related to CMSX-10 and Ren N6, both being third gene ration superalloys. From this LMSX-1 baseline alloy, 17 other model alloys were de signed to evaluate the effect of typical alloying additions on the solid ification behavior and prope rties of Ni-base superalloy single crystals (Table 3-1). The elemen tal additions and the compositional ranges selected were based on industrial experience, material development history, and current industrial trends. The 17 model alloys each had one to two vari ations from the baseline alloy so that the influence of each type of addition could be examined. LMSX-2 and -3 were added to study the influence of cobalt on stability, solvus and solid solution strengthening. LMSX-2 contained a moderate level of Co (8 w/o) and LMSX-3 contained a low level (4 w/o Co). Note that LMSX-1 has 12 wt% Co which is similar to the Co concentration in Ren N625, and LMSX-3 has 4 wt% Co for comparison to CMSX-10.9 Ren N6 was developed by GE, and CMSX-10 was developed by Cannon-Muskegon. These manufacturers have different id eas as to the effects of Co.9,25,31 LMSX-4 and -5 have

PAGE 40

20 variations in the amount of chromium present in these a lloys. These alloys were developed to examine the effect of Cr content on microstructure stability, solvus temperature, and surface stability. LMSX-4 has a high Cr level (6.15 w/o) and LMSX-5 contains a low level (2.1 w/o) of Cr. LMSX-6 has a high level of tungsten (8.6 w/o) to investigate tungstens effect on stability and solid solution strengthening. LMSX-7 and 8 both have a 1 a/o (1.6 w/o) addition of molybdenum, to de termine the effect of Mo additions on stability and solid solution st rengthening. LMSX-7 substituted 1 atomic percent (at%) Mo for 1 at% W, so the alloy contained a reduced amount of tungsten (3.1 w/o). LMSX-9, -10, and -11 all have varyi ng amounts of rhenium. LMSX-9 contains no rhenium (0 w/o). LMSX-10 contains a lo w level of rhenium (1 at% or 2.95 wt%). LMSX-11 has the largest amount of rhenium of all the alloys (3at% or 8.7 w/o). These alloys are intended to cover wh at is essentially the first th ree generations of superalloy (LMSX-9, -10, and -1) to determine the effect of the Re on stability of first, second, and third generation superalloys. The high Re c ontent in LMSX-11 was added to investigate the stability of alloys with large Re a dditions. In LMSX-12, -13, -14, and -15, the amounts of the formers, Al and Ta, were varied from alloy to alloy and titanium was substituted in the latter two. LMSX-12 and -13 have changes in the amounts of Ta and Al to determine the effect of Ta/Al ratio va riations on solvus and solidus temperatures, elemental solidifica tion segregation, and size and shape. In LMSX-14 and -15, Ti was substituted for Ta (in LMSX-14) or Al (LMSX15) to determine if Ti affected the alloys solidus, solvus, segregation, and strength. Th e alloys LMSX-12, -13, -14, and -15 were all intended to have a constant volume fraction. To begin examination of the fourth generation superalloys, LMSX-16 and -17 both have additions of ruthenium (1.6 and 3.2

PAGE 41

21 w/o respectively). It has been reported th at Ru additions affect stability and solid solution strengthening28 and these two alloy were added to investigate that claim. LMSX-18 has a 1 a/o addition of palladium ( 1.7 w/o). Pd, a member of the precious metal group (i.e. Re, Ru, Pd, Pt, Au) was also included in this study since it has also been reported to affect microstructural st ability, strength, and surface stability.32,33 The alloys were cast in si ngle crystal bars at Precisi on Cast Components Airfoils (PCC Airfoils, Minerva, OH). A commercial directional solidification furnace was used with high gradient investment casting techniques to cast the a lloys in a [001] orientation. An inchworm type grain selector was used to produce single cr ystal samples. The withdrawal rate was initially set at 6 in (15.24 cm) per hour until the grain selector was reached. After that point, the rate was ch anged to 8 in (20.32 cm) per hour. The bars were cast in cylinders with a diameter of 1.25 cm and a length of 20 cm. One mold was processed for each alloy, and each mold contai ned nineteen bars. Af ter casting, the [001] orientation was verified by Laue backscattered x-ray technique s. For the purpose of this investigation, samples with defects such as freckles, slivers, high angle boundaries (HAB), and low angle boundaries (LAB) were not used. 3.2. Metallography After receipt of the bars, specimens were sectioned for metallographic evaluation. A LECO CM-20 cut-off wheel, using a LEC O 3025 blade (rated for HRC 45-60) was used to perform all sectioning of the bars. The bar was cut in the middle, and starting from the cut mid-section ends, another cut was made to leave behind a small disk 1.25 cm in diameter and 0.5 cm thick. This disk was then sectioned in half to produce two semi-circular specimens for micr ostructural characterization.

PAGE 42

22Table 3-1: Compositions of the 18 model alloys in weight percent (wt%). Highlighted regions indicate change s made from baselin e. Compositions of Ren N6 and CMSX-10 shown for comparison. Alloy ID Ni Cr Co Mo W Ta Re Al Ti Hf Ru Pd Comments LMSX-1 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 Baseline 61.95 5.00 13.00 2.00 3.00 2.00 13.00 0.05 Atomic % Composition LMSX-2 Bal 4.10 8.00 5.85 8.60 5.90 5.55 0.10 Reduced Co (8 at%) LMSX-3 Bal 4.10 4.00 5.85 8.60 5.90 5.55 0.10 Minimum Co (4 at%) LMSX-4 Bal 6.15 12.20 5.85 8.60 5.90 5.55 0.10 High Cr (7 at%) LMSX-5 Bal 2.10 12.20 5.85 8.60 5.90 5.55 0.10 Low Cr (3 at%) LMSX-6 Bal 4.10 12.20 8.60 8.60 5.90 5.55 0.10 High W (3 at%) LMSX-7 Bal 4.10 12.20 1.60 3.10 8.60 5.90 5.55 0.10 Low W (1 at%) + 1 at% Mo LMSX-8 Bal 4.10 12.20 1.60 5.85 8.60 5.90 5.55 0.10 +1 at% Mo LMSX-9 Bal 4.10 12.20 5.85 8.60 0.00 5.55 0.10 0 at% Re LMSX-10 Bal 4.10 12.20 5.85 8.60 2.95 5.55 0.10 1 at% Re LMSX-11 Bal 4.10 12.20 5.85 8.60 8.70 5.55 0.10 3 at% Re LMSX-12 Bal 4.10 12.20 5.85 11.20 5.90 5.00 0.10 High Ta (4at%), Low Al (12 at%) LMSX-13 Bal 4.10 12.20 5.85 6.00 5.90 6.15 0.10 Low Ta (2 at%), High Al (14 at%) LMSX-14 Bal 4.10 12.20 5.85 6.00 5.90 5.65 0.80 0.10 Low Ta (2 at%) + 1at %Ti LMSX-15 Bal 4.10 12.20 5.85 8.60 5.90 5.10 0.80 0.10 Low Al (12 at%) + 1 at% Ti LMSX-16 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 1.60 +1 at% Ru LMSX-17 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 3.20 +2 at% Ru LMSX-18 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 1.70 +1 at% Pd CMSX-10 Bal 3.00 4.00 0.60 6.00 8.00 6.00 5.75 0.10 Rene N6 Bal 4.50 12.50 1.10 5.75 7.50 6.00 5.35 0.15

PAGE 43

23 Once the specimens were cut, they were m ounted using a LECO PR-10 mounting press. The specimens were mounted in 3.175 cm ( 1.25 inch) mounts using di allyl phthalate and labeled as LMSXX as cast where X indicated the specifi c alloy identification number. With the metallographic specimens mounte d, they were then leveled, ground, and polished to a mirror-like finish. The leve ling of the specimens was done using a LECO BG-20 belt grinder with a water cooled 240 grit belt. The edges of the specimen mounts were first chamfered to ease handlin g and lessen hydroplaning during polishing. Leveling was done until there was no diallyl phthalate covering the specimen and there were no raised spots obvious on the sample. All of the grinding and polishing was done using a LECO VP-20 Vari/Pol, operated at 300 rpm, and water was used to lubri cate and cool the specimen. Standard metallographic practices for grinding and po lishing were used to prepare the specimen33, and a Branson 1200 ultrasonic sink was used for ultrasonic cleaning of the specimens between polishing steps. Two techniques were evaluated for grindi ng and polishing. The first technique was considered the standard technique, which ha s been typically used by the University of Florida Materials Science and Engineering De partment, and the second was an advanced technique initially develope d by Struers Inc and further modified for this study. The standard technique was done on LMSX1, -2, -3, -4, -5, -9, -10, -11, -16, -17, and -18. Grinding was done using wet-dry al umina grinding disks beginning with 240 grit, followed with 320, 400, 600, and finally 800 grit. This was followed with two rough polishing steps. Rough polishing was done using 20.32 cm (8 in) billiard cloths with first 15 m and then 5 m alumina suspended in water. Fine polishing was done using LECO

PAGE 44

24 Micron cloths with first 1 m and then 0.3 m alumina suspended in water. All specimens were polished to a mirror-like fini sh and examined optic ally for scratches. The advanced technique was done on LMSX -6, -7, -8, -12, -13, -14, and -15. The grinding steps were done using Struers MD-Piano 600 and MD-Piano 1200 grit magnetic grinding disks. The particulate was imbedded into the disk itself and only needed to be dressed between specimens to maintain the proper grit size. Rough polishing was done using a Struers MD-Mol magne tic disk with the appropria te MD-mol solution. This solution was water based and needed either l ittle or no extra water for lubrication. The final polishing was done in the same manne r as the standard technique. Again, all specimens were polished to a mirror-like fini sh and examined optic ally for scratches. Although no specimen was done using both t echniques, the final requirement was the same: a mirror-like finish without scratches. This was easily attainable with both techniques given sufficient time. The adva nced technique, using the magnetic disks, offered reduced grinding and polishing times, less mess, fewer steps, and a decreased chance of cross contamination between grit sizes. The advanced technique has the setback of increased time if a step is not done properly due to the large changes in grit sizes used. If done correctly, specimen preparation time was reduced from 45 min to 20 min. 3.3. Scanning Electron Microscopy/ Backscatter Electron Microscopy Electron microscopy was first done usi ng a JOEL SEM 6400. The instrument was operated with an accelerating voltage of 15 keV and a working distance of 15 mm. The instrument was primarily operated in the b ackscattered mode. Using the backscattered electron (BSE) imaging, 20 images were taken of each specimen in the ascast condition.

PAGE 45

25 The images were taken in a grid like manne r of four-by-five. The images were 1 mm apart in the y direction and 2 mm apart in the x directio n. These images were taken to calculate the primary dendrite arm spacing (PDAS). Figures 3-1 and 3-2 are representative of the BSE images taken to determine the PDAS. Appendix A contains additional images from this portion of this investigation. Figure 3-1: BSE image of LMSX -1 taken at 100x equivalent. Figure 3-2: BSE image of LMSX -13 taken at 100x equivalent X Y X Y

PAGE 46

26 3.3.1. Electron Microprobe Analysis The remainder of this investigation of the segregation behavior of these alloys was done using electron microprobe analysis (E MPA). The instrument used for this examination was a JOEL 733 Superprobe. The instrument was operated with an accelerating voltage was 15 keV, a take -off angle of 40, a spot size of 1 m and a beam current 20 nA. Each point in the EM PA was measured by wavelength dispersive spectroscopy (WDS) and measur ed for 10 seconds per point. Specific calibration for Ni, Cr, Co, Mo, W, Re, Ta, Al, Ti, Ru, Pd, and Hf were all used as references. To expedited the sca nning times, as many different crystals as possible were used while maintaining the best line (K L or M ) to scan. A LiF crystal was used to measure intensities for Ni, Cr, and Co. The compositional analysis for these elements was based on the K lines. To measure intens ities for W, Re, Ta, Hf, and Al, a TAP crystal was used. To determin e the chemical analysis of these elements, the K line for Al was measured, and the L lines were used for all the others on this crystal. Finally, a PET crystal was used to measure intensities for Ru, Mo, and Ti, with chemical composition based on the K line for Ti and the L lines for Ru and Mo. A small computer routine for the microprobe had to be used to perform the line scans, along with some of the proper settings. Due to the ag e of the equipment, some of the line scan routines had to be varied to detect specific elements. These routines are found in Appendix B. A problem occurred with measuring some of the trace elements due to the age of the software. The trace elements of Mo in LMSX-7 and -8, Ti in LMSX -14 and -15, and

PAGE 47

27 the Ru in LMSX-16 all required a specific step to be added to this routine to properly measure the peak. Line scans were used to measure co mposition and segregation within the microstructure. A line of 30 points was s canned running between two dendrite cores through the interdendritic region. Care was taken to avoid any secondary and tertiary dendrite arms. Image 3-3 contains an exampl e of one of the line scans examined. The typical length of each line scan was 300 m. Three scans were done on each specimen and all the data was entered by hand, again due to the age of the equipment. A total of 90 points were scanned for each specimen. This technique is a variation of that used by Pollock et. al.34 The technique to measure/quantify solidif ication segregation was developed by M. N. Gungor36 and is commonly found to be the indus try standard. This technique involves a grid of point scans across the specimen, all equally spaced. To check the validity of the new method of using line scans, the grid me thod was used on LMSX-3. The PDAS of Figure 3-3: BSE photo of LMSX-1 taken at 100x equivalent. Yellow line indicates location of the line scan preformed.

PAGE 48

28 LMSX-3 was measured at 253.4 m and a slightly larger spacing of 265.0 m was used for the spacings between points in the line scans. Fifteen line scans of fifteen points were used with the larger spacings used for a total of 225 points scanned.11 This atomic percent and normalized weight percent data we re then entered into a spreadsheet by hand for analysis. 3.3.2. Verification of App licability of Analysis To provide an independent check of this investigation, a piece of as-cast CMSX-4 was sectioned, mounted, and polished (using th e standard technique) to an optically verified mirror like finish. CMXS-4 was used due to availability of the as-cast sample. The composition of CMXS-4 is listed in Ta ble 3-2. The EMPA was preformed in a similar fashion to that described above to see if the techniques described above were applicable to current production alloys and to broaden the possible spectrum of further understanding of trends f ound in this experiment. Table 3-2: Composition of CMSX-4 in wt%.4,6 Alloy ID Ni Cr Co Mo W Ta Re Al Ti Hf CMXS-4 Bal 6.5 9.0 0.6 6.0 6.5 3.0 5.6 1.0 0.10

PAGE 49

29 CHAPTER 4 EXPERIMENTAL RESULTS For clarity, the results of this investigation are broken down into three parts. First, the primary dendrite arm spacing (PDAS) will be discussed. Then the observations of the electron microprobe analysis are evaluated. Finally, the two electron microprobe analysis techniques will be compared and evaluative. 4.1. Primary Dendrite Arm Spacing Twenty 100x images (or fields of view) ta ken of each of the 18 model alloys were used to calculate the primary dendrite arm spacing (PDAS). Due to the natural variabilities in dendrite arm spacings, from 6 to 8 measurements were taken from each field of view, but the number was held consiste nt for all fields for that alloy. Figure 4-1 is one of the 100x BSE images from LMSX-12. The black lines drawn on the image are examples of the lines used to measure the PDAS. This procedure was repeated for all twenty fields of view, and then the final values were tabulated. To make measuring easier, the micron bar on the image was meas ured and used as a standard. It was measured at 5.4 cm and indicated 500 m long. This allowed a machinists scale to be used to make all the measurements directly fr om the field of view and then ratioed back to the actual size. The average, standa rd deviation, and median values were all calculated. Table 4-1 contains the results from these calculations. This was done to develop an understanding of the accuracy in calculating the PDAS from the EMPA line scans.

PAGE 50

30 All of the measured PDAS standard deviat ions were relatively large, and all but two of the PDAS measurements fell to within one standard deviation of the mean. The exceptions were LMSX-10 and -17. Of the rema ining sixteen alloys, six of the measured PDAS were very close (about 20 m difference) to those calculat ed from the line scans. Another eight of the measurements were within about 50 m of one another. The only alloys that exhibite d a variation in PDAS greater than 70 m (other than LMSX-10 and17) were LMSX-1 and -2. LMSX-1 had the hi ghest standard devia tion for PDAS of the eighteen alloys. Figure 4-1: BSE image of LM SX-13. Black lines added to image were where PDAS measurements were taken. 4.2. Electron Microprobe Analysis To quantify and characterize the inho mogeneties and segr egation in the microstructure that occur during solidifi cation, a lengthy analysis was preformed to develop a better understanding of the elemental interactions an d solidification behavior. The electron microprobe analysis (EMPA) resu lts are broken down into three sections. The first section contains the results of the lin e scan technique and how they relate to the

PAGE 51

31 Table 4-1: PDAS measurements from EMPA and from hand calculations. Standard deviation is shown for hand calcula tions. All measurements are in m. LMSX1 2 3 4 5 6 7 8 9 EMPA 287.66 267.39 250.94 259.61262.91 225.52307.24 262.31367.90 Measured 374.33 343.00 253.47 294.35310.84 281.65331.78 320.62 381.86 St Dev 104.1 98.7 64.3 84.0 87.1 97.5 80.7 74.1 84.5 LMSX10 11 12 13 14 15 16 17 18 EMPA 271.41 223.59 275.72 257.35226.80 290.93247.51 174.70258.09 Measured 360.23 258.52 325.85 280.03281.48 286.40284.51 268.91271.53 St Dev 116.1 61.0 79.5 79.8 72.4 78.2 61.7 79.9 70.1 elemental segregation and partitioning for the eighteen model alloys. The next section contains the results from the grid scan of LMSX-3. Finally, the da ta from the line scans from CMSX-4 are presented. The data was measured in atomic percent (at%) and then converted to normalized weight percent (wt%) and recorded. Within these eighteen model alloys, a total of fifteen relationships were observed. Eight of these relationships could be directly related to the variation of a single elemental addition. The remaining seven show the interac tions that appear to be present from alloy to alloy based on the variation of only two el ements (i.e. Ta and Al both varied from baseline). The relationships observed that re late to elemental variations are as follows: Cobalt. By comparing LMSX-1, -2, and -3. Chromium. By comparing LMSX-1, -5, and -5. Rhenium. By comparing LMSX-1, -9, -10, and -11. Ruthenium. By comparing LMSX-1, -16, and -17. Tungsten. By comparing LMSX-1 and 6. Molybdenum. By comparing LMSX-1 and -8 Palladium. By comparing LMSX-1 and -18. Tungsten with a Molybdenum addition. By comparing LMSX-7 and -8. The remaining relationships that were observed were examined to qualify the interactions that might be present in the systems where two elemental additions were varied. These systems are listed as follows:

PAGE 52

32 Variation of Tantalum and Aluminum from the baseline. LMSX-1, -12, and LMSX-1, -13. Variation between Tantalum and Aluminum. LMSX-12 and -13. Variation of Tantalum and Aluminum fr om the baseline with an addition of Titanium. LMSX-1, -14, and LMSX-1, -15. Variation between Tantalum and Aluminum with an addition of Titanium. LMSX14 and -15. Variation between decreasing Tungsten a nd increasing Molybde num. LMSX-1, -7 and -6, -8. As noted previously, all final data from the line scans is presented in normalized weight percent (wt%). 4.3. Elemental Segregation and Partitioning Three line scans from dendrite core to dendrite core through the interdendritic region were preformed on one specimen from each of the model alloys. The composition of each point along the line in each alloy was determined. The average values for each element for the three line scans for each speci men were calculated. Appendix C contains the average EMPA results for the eighteen model alloys. Nearly all the elements in all the alloys exhibit some degree of segreg ation; however the degree and direction (dendritic or interdendritic) of the segregation varied. A partitioning coefficient (k) was calculated from the average values of each element from the set of line scans from each alloy The partitioning coefficient parameter is indicative of the degree of segregation during solidification and tendency for an elemen t to segregate to either the dendrite core or the interdendritic re gion and how much upon casting. k is defined as itic Interdendr i Dendrite ix x k, ,' (Equation 1-1)

PAGE 53

33 where xi, dendrite is the composition (in wt%) at the dendrite core and xi, interdendritic is the composition (in wt%) roughly equidi stant between both dendrite cores.11, 16,36-40 The points chosen for the determination of the segregation partition coefficient came from either end of the line scan (i.e. the dendrite core). The interdendr itic value was chosen from either of the midpoint of this average scan, with one exception. When the minimum or maximum compositional level did not occur at the midpoint, this interdendritic value was taken from a trendline. If the mid points did not lie reasonably ne ar the trendline, the next point on the line was c hosen. This was done to avoid the possibility that the midpoints chosen would not indi cate the actual degree of segregation as shown by the trendlines of the actual data was as indicated. Table 4-2 contains the k values calculated from this method. Data listed as kA is the data collected by F. Fela.16 The partitioning coefficients calculated in th is study are reported as kB. A k less the unity indicates a tendency of this element to segregate to the interdendritic region; whereas a k greater than unity indicates segregation to the dendrite core.11,16,36-38 Graphs were then developed to show the variations of k as the composition was varied in this investiga tion. Figures 4-2, 4-3, and 4-4 graphically illustrates how kA and kB compared to one another for LMSX-1, -13, and -18 as examples. From the comparisons, it can be seen that although the segregati on behavior in both studies indicate similar direc tions of segregation, the magnit udes varied particularly for Re. The magnitude difference can be attribut ed to differences in the location used to measure composition within the specimen bei ng locally different from one another. However, it is clear that the segregation trends represented by k largely holds true for

PAGE 54

34 both kA and kB. The formers, Ni, Al, Ta, and Ti, all segregated to the interdendritic region, and the solid solution strengtheners, Cr, Co, W, and Re segregated to the dendritic region. Although the segregation be havior was similar in both studies, there was a discrepancy in the segregation behavi or of Mo in LMSX-8 (+ 1 at% Mo). kA indicated that Mo segregated to the dendritic region, whereas kB indicated Mo segregated to the interdendritic region. Fi gure 4-5 contains the graph that compares the results of both kA and kB. Figure 4-6 is the graph for LM SX-8 that was used to identify the points for the k partitioning analysis. The points chosen for the k analysis are shown as large open circles on the graphs. In addition, a second order trend line was plotted to aid in visualizing the segregation behavior. For comparison, a similar graph for Al from LMSX-1 and -18 is shown with the sa me data points used for calculation of k labeled as in Figure 4-7.

PAGE 55

35Table 4-2 Showing weight percentages of each respective element in each alloy from the dendrite core and the interdendritic reg ion, and the calculated k value for both tec hniques A (in orange), and B (in blue). Alloy Ni Cr Co Mo W Re Ta Al Ti Ru Pd Dendritic 56.044.0713.04 6.8310.494.864.33 Interdendritic 61.763.9311.40 4.313.3810.085.74 k'B 0.91 1.04 1.14 1.58 3.10 0.48 0.75 LMSX-1 k'A 0.93 1.11 1.12 1.79 3.060 0.490 0.74 Dendritic 59.964.279.04 6.7310.855.024.67 Interdendritic 63.853.567.64 4.293.5710.386.39 k'B 0.94 1.20 1.18 1.57 3.04 0.48 0.73 LMSX-2 k'A 0.91 1.64 1.29 1.93 5.940 0.430 0.71 Dendritic 64.903.914.33 6.7110.794.984.46 Interdendritic 69.003.663.52 3.582.2211.356.33 k'B 0.94 1.07 1.23 1.87 4.86 0.44 0.70 LMSX-3 k'A 0.95 1.07 1.13 1.78 3.110 0.500 0.76 Dendritic 54.876.3513.37 6.679.724.264.46 Interdendritic 59.166.0711.19 4.383.169.295.48 k'B 0.93 1.05 1.19 1.52 3.08 0.46 0.81 LMSX-4 k'A 0.93 1.16 1.10 1.70 3.020 0.480 0.80 Dendritic 60.752.5913.37 5.799.293.694.51 Interdendritic 64.882.6512.87 3.543.596.865.79 k'B 0.94 0.98 1.04 1.64 2.59 0.54 0.78 LMSX-5 k'A 0.94 1.18 1.14 1.68 3.050 0.520 0.76 Dendritic 57.174.6713.97 8.449.173.434.56 Interdendritic 61.764.5412.01 4.473.418.466.61 k'B 0.926 1.029 1.163 1.888 2.689 0.405 0.690 LMSX-6 k'A 0.89 1.41 1.21 2.00 4.590 0.390 0.68

PAGE 56

36Table 4-2 (Cont.) showing weight percentage s of each respective element in each alloy from the dendr ite core and the interdendr itic region, and the calculated k value A (in blue), and B (in orange). Alloy Ni Cr Co Mo W Re Ta Al Ti Ru Pd Dendritic 60.3 4.7413.651.612.888.64 3.974.72 Interdendritic 62.48 4.2912.891.822.043.67 7.375.65 k'B 0.97 1.10 1.06 0.88 1.41 2.35 0.54 0.84 LMSX7 k'A 0.95 1.20 1.22 1.08 1.36 3.300 0.500 0.79 Dendritic 57.75 4.4413.711.545.558.59 3.914.71 Interdendritic 61.5 4.312.971.883.813.47 7.755.56 k'B 0.94 1.03 1.06 0.82 1.46 2.48 0.50 0.85 LMSX8 k'A 0.88 1.79 1.45 1.48 2.00 5.660 0.380 0.64 Dendritic 64.35 3.7912.82 7.390 5.624.70 Interdendritic 63.79 3.7911.59 4.570 9.255.45 k'B 1.01 1.00 1.11 1.62 0.00 0.61 0.86 LMSX9 k'A 1.02 1.37 1.25 1.76 0.000 0.570 0.90 Dendritic 60.31 3.8313.53 6.915.69 5.324.60 Interdendritic 62.62 3.5911.38 4.321.67 10.655.53 k'B 0.96 1.07 1.19 1.60 3.41 0.50 0.83 LMSX10 k'A 0.97 1.01 1.14 1.62 3.280 0.500 0.85 Dendritic 54.30 4.6313.62 4.8213.81 3.294.40 Interdendritic 62.62 3.6110.92 2.792.06 9.796.80 k'B 0.87 1.28 1.25 1.73 6.70 0.34 0.65 LMSX11 k'A 0.88 1.13 1.18 1.83 3.74 0.40 0.69 Dendritic 57.53 4.4113.89 5.978.85 5.264.36 Interdendritic 61.26 3.9012.03 3.803.31 9.765.68 k'B 0.94 1.13 1.15 1.57 2.67 0.54 0.77 LMSX12 k'A 0.95 1.17 1.12 1.62 3.37 0.53 0.80

PAGE 57

37Table 4-2(Cont.) showing weight percentage s of each respective element in each alloy fr om the dendrite core and the interdendri tic region, and the calculated k value A (in blue), and B (in orange). Alloy Ni Cr Co Mo W Re Ta Al Ti Ru Pd Dendritic 59.494.1413.36 5.699.972.185.07 Interdendritic 67.134.6311.14 2.751.706.427.37 k'B 0.89 0.89 1.20 2.07 5.86 0.34 0.69 LMSX-13 k'A 0.89 1.10 1.18 2.08 2.86 0.39 0.73 Dendritic 61.754.7213.97 5.257.301.934.120.48 Interdendritic 66.523.9612.66 2.872.344.385.701.15 k'B 0.93 1.19 1.10 1.83 3.12 0.44 0.72 0.42 LMSX-14 k'A 0.88 1.55 1.32 2.65 10.49 0.34 0.68 0.29 Dendritic 58.234.3213.82 5.729.663.584.190.42 Interdendritic 63.993.7811.32 2.992.408.045.941.13 k'B 0.91 1.14 1.22 1.91 4.03 0.45 0.71 0.37 LMSX-15 k'A 0.91 1.26 1.22 1.91 3.94 0.46 0.72 0.44 Dendritic 57.374.5214.51 5.119.353.554.59 1.63 Interdendritic 61.414.0412.17 3.363.167.534.52 1.38 k'B 0.93 1.12 1.19 1.52 2.96 0.47 1.02 1.18 LMSX-16 k'A 0.92 1.11 1.16 1.78 3.99 0.47 0.74 1.15 Dendritic 55.414.2413.69 5.779.663.524.52 3.59 Interdendritic 61.493.6810.97 3.101.6810.116.34 3.11 k'B 0.90 1.15 1.25 1.86 5.75 0.35 0.71 1.15 LMSX-17 k'A 0.90 1.32 1.24 2.01 6.33 0.38 0.71 1.08 Dendritic 57.234.1313.86 6.0610.123.844.41 0.80 Interdendritic 61.843.7111.22 2.912.238.746.47 2.95 k'B 0.93 1.11 1.24 2.08 4.54 0.44 0.68 0.27 LMSX-18 k'A 0.94 1.03 1.07 1.69 2.63 0.62 0.80 0.33

PAGE 58

38 With kB exhibiting the same trend as kA, the composition effect s and some of the elemental interactions were plotted. When examining the effect of elemental variations, all the compositional effects were compared dire ctly to the baseline alloy LMSX-1. Note that kB is calculated using equation 1-1, however the data used in this calculation was obtained from data collection me thod described in this paper. 4.3.1. Cobalt Partitioning The effects of cobalt variations (LMSX-1, -2 and -3; 12.2 wt% Co, 8.0 wt% Co, and 4.0 wt% Co respectively) on the kB values were all of the elements in the alloy were plotted against increasing Co content. From th is graph (Figure 4-8), it can be seen that increasing Co content decreased the segregation of the elements that partition to the dendrite core. The largest decrease in segr egation occurs with Re followed by W, Co itself, and finally Cr. The effect on Cr is a very small decrease in segregation over the range of 4 wt% to 12.2 wt% Co. Whereas the e ffect of Re decreased markedly as the Co level is increased to the 8 wt% Co, and then remains constant with further increasing Co. It should be noted that the in crease in Co content in these alloys results in a decreased segregation of Co itself, but only slightly. When looking at the elements that segregat e to the interdendritic region (Figure 49), increasing the Co content also decreased the segregation of Al and Ta, but slightly increased the segregation of Ni. The decrease in partitioning for Al with increasing Co content greater than that for Ta, but the Ta fo llows the same trend as Re does in that the degree of segregation is decr eased to the 8 wt% Co point and then becomes essentially constant. As was stated, the segregation of Ni increased with increasing Co, but Ni is the only element that was observed to exhibit increased segregation when increasing Co content.

PAGE 59

39 4.3.2. Chromium Partitioning The alloys with varying chromium conten t were the second group examined. This series of alloys consists of LMSX -5, -1, and -4 (2.1 wt% Cr (3 at%), 4.1 wt% Cr (5 at%), and 6.15 wt% Cr (7 at%) respectively). The e ffects of this addition on the elements in the alloy (Ni, Cr, Co, W, Re, Ta, and Al) was ex amined and characterized. Increasing the Cr concentration increased the segregation of Re, Co, and Cr. The increase in Re segregation, being the most consistent and pr onounced when compared to that of Co and Cr. Co partitioning increased as Cr cont ent was increased, and the Cr partitioning did increase slightly. In the ba seline alloy, LMSX-1, and the hi gh Cr content alloy, LMSX-4, Cr was observed to partition to the dendrite co re. But in the low Cr alloy (LMSX-5), Cr was observed to segregate to th e interdendritic region. W had a different response to this change in concentration; as Cr content increased, the W partitioning decreased. The partitioning coefficient for Co at the 2.1 wt% Cr was the lowest found in this investigation indicating that Co partitioned the least in this alloy. Figure 4-10 shows the effect graphically of increasing Cr con centration on the segregation of elements partitioning to the dendritic region.

PAGE 60

40 k' Comparison for LMSX-10 0.5 1 1.5 2 2.5 3 3.5 NiCrCoWReTaAlk' Technique A Technique B Figure 4-2: k values for LMSX-1 for techniques A (orange ) and B (blue). The green line is at k = 1. k' Comparison for LMSX-130 1 2 3 4 5 6 7 NiCrCoWReTaAlk' Technique A Technique B Figure 4-3: k values for LMSX-13 for t echniques A (orange) and B (blue). The green line is at k = 1

PAGE 61

41 k' Comparison for LMSX-180 1 2 3 4 5 6 7 8 NiCrCoWReTaAlPdk' Technique A Technique B Figure 4-4: k values for LMSX-18 for t echniques A (orange) and B (blue). The green line is at k = 1. k' Comparison for LMSX-80.00 1.00 2.00 3.00 4.00 5.00 6.00 NiCrCoMoWReTaAlk' Technique A Technique B Difference Figure 4-5: k values for LMSX-8 for techniques A (orange ) and B (blue). The green line is at k = 1. The difference is noted by a circle.

PAGE 62

42 Plot of Molybdenum Segregation in LMSX-7 and -8 with Normalized PDAS0.00 0.50 1.00 1.50 2.00 2.50 00.20.40.60.81 Normalized PDASwt% Mo LMSX-7 LMSX-8 Figure 4-6: Mo segregation pl ot for LMSX-7 and -8. White points were used in kB analysis. Second order trendlines are also shown for both alloys. Plot of Aluminum Segregation in LMSX-1 and -18 with Normalized PDAS 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 00.20.40.60.81 Normalized PDASwt% Al LMSX-1 LMSX-18 Figure 4-7: Al segregation plot for LMSX-1 and -18 shown for comparison. White points were used in kB analysis. Second order tre ndlines are also shown for all alloys.

PAGE 63

43 The effect of increasing Cr on elements that partition to the interdendritic region is shown in Figure 4-9. The partitioning behavior of Ni, Al, and Ta due to varying the Cr concentration was not consistent. Ta showed a linear increase in partitioning as the Cr. The partitioning of Ni did not appear to be affected by the change in Co content. The graph in Figure 4-11 shows a decrease in the pa rtitioning coefficient, but the variation are small and may be due to experimental data scatter. The effect of Cr content on the partitioning of Al was still different than that of Ni and Ta. Al partitioning decreased as Cr content increased. 4.3.3. Rhenium Partitioning Alloys LMSX-9, -10, -1 and -11 were used to evaluate the changes in partitioning due to increasing Re content. LMSX-9 is a first generation superalloy with 0 wt% Re, LMSX-10 is a second generation superalloy with 1 at% Re ( 3 wt%), LMSX-1 is the baseline and is a third genera tion superalloy with 2 at% Re ( 6 wt%), and LMSX-11 is a model alloy with 3 at% Re ( 9 wt%) and was added to examine the effect of a large Re additions on alloy stability. Figure 4-12 contains the kB curves for elements segregating to the dendritic region, and Figure 4-13 contains the kB curve for elements that segregate to the interdendritic region. Of the elements segregating to the dendrite cores, Re shows the largest increase in partitioning due to the increase in Re concen tration. The partitioning coefficient for Re in LMSX-11 (8.95 wt% Re) was the largest k va lue observed in this experiment. Cr and Co also exhibit increasing se gregation levels when the Re content was increased up to the 5.95 wt% Re (LMSX-1) concentration. At the highest Re concentration, the Co showed a slightly greater propensity to partition to the dendrite core.

PAGE 64

44 Partitioning Effect with Varying Co0.000 1.000 2.000 3.000 4.000 5.000 6.000 2468101214wt% Cok' Cr Co W Re Figure 4-8: Partitioni ng effects due to increasing Co c oncentration for elements showing a preference to segregate to the dendritic region. Partitioning Effect with Varying Co0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000 2468101214wt% Cok' Ni Ta Al Figure 4-9: Partitioni ng effects due to increasing Co c oncentration for elements showing a preference to segregate to the interdendritic region.

PAGE 65

45 Partitioning Effect with Varying Cr0.000 0.500 1.000 1.500 2.000 2.500 3.000 3.500 1234567wt% Crk' Cr Co W Re Figure 4-10: Partitioning effects due to incr easing Cr concentration for elements showing a preference to segregate to the dendritic region. Partitioning Effect with Varying Cr0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000 1234567wt% Crk' Ni Ta Al Figure 4-11: Partitioning effects due to incr easing Cr concentration for elements showing a preference to segregate to the interdendritic region.

PAGE 66

46 The Cr continued to exhibit a limited degree of segregation to the de ndritic core, and the final kB values for Cr and Co for LMSX-11 ( 8.9 wt% Re) were virtually the same. LMSX-11 contained the most se vere segregation and, theref ore the highest partitioning coefficients for Cr, Co, and Re for this investigation. Increased Re contents also resulted in an increasing segregation of Ni, Ta, and Al. Ta showed the greatest degree of segregat ion for these three elements, followed by Al, and then Ni. Ni showed a linear decrease in kB (increasing segregation) as the Re concentration was increased. Ta and Al show ed somewhat parabolic decreasing trends in k as the Re content increased. Unlike in the Re bearing alloys, Ni partitioned to the dendritic region for LMSX-9 (0 wt% Re). LMSX-11 showed the greatest amount of partitioning in Ni, Al, and Ta for this investig ation. In general, the segregation behavior of all of the elements was reduced to its lo west levels in the 0 wt% Re (LMSX-9) alloy, and the highest levels in the 8.9 wt% (LMSX-11) alloy. 4.3.4. Tungsten partitioning The effects of increasing the W concentr ation were also evaluated in this investigation by comparing LMSX-1 (5.85 wt% W) and LMSX-6 (8.9 wt% W). Figures 4-14 and 4-15 show the changes in the partiti oning coefficient for the base elements (Ni, Cr, Co, W, Re, Ta, and Al) as the concentration of W is in creased. W had a variety of effects on the elements that commonly segregat e to the dendritic regi ons (Re, W, Co, and Cr). The first effect noted was that the increas ed concentration of W, also resulted in an increased W partitioning coefficient. This was the only element with kB greater than one (i.e. elements that partitioned to the dendrit e core) that showed an increase in this segregation. Co and Cr were unchanged as the W concentration was increased.

PAGE 67

47 Somewhat unexpectedly, the increase in W content resulted in a decrease in the segregation of Re. Similar to the varied segregation behavior in the dendritic segregating elements, the elements segregated to the interdendritic re gion also showed very different responses. Raising the W levels in the alloy caused Ta a nd Al to segregate to a greater extent, with Ta exhibiting a greater degree of segregation th an Al. In a pattern similar to that shown by Re for this series, the partitioning of Ni decreased (kB approaching one) with increasing W content. 4.3.5. Tungsten Partitioning with an Addition of Molybdenum LMSX-7 and -8 both had a 1 at% Mo additi on to evaluate the effects of Mo on the segregation behavior of the alloys. In addition, the W concentration in LMSX-7 was decreased to 3.1 wt% (1 at%). Re, W, Cr, a nd Co all segregated to the dendrite core regions of the as-cast structure (Figure 416). As the W concentration was decreased from 5.85 wt% to 3.1 wt%, Re showed the larges t decrease in segrega tion of the elements in this alloy. The segregation behavior of W itself was also decrease slightly. The partitioning behavior of Co was unaffected by the decrease in W concentration. The degree of Cr segregation increased as the W concentration decreased. Mo, Ni, and Ta all exhibited a decreased degree of segregation as the W concentration was decreased. The change in W had no obvious effect on the Al segregation behavior. The lowest kB values for W and Re (indicating the least amou nt of segregation) in this investigation were found in LMSX-7. Figure 4-17 clearly illustrates the eff ect of decreasing W concentration the segregation be havior of Ni, Ta, Mo, and Al.

PAGE 68

48 Partitioning Effect with Varying Re0.000 1.000 2.000 3.000 4.000 5.000 6.000 7.000 8.000 012345678910wt% Rek' Cr Co W Re Figure 4-12: Partitioning effects due to incr easing Re concentration for elements showing a preference to segregate to the dendritic region. Partitioning Effect with Varying Re0.000 0.200 0.400 0.600 0.800 1.000 1.200 012345678910wt% Rek' Ni Ta Al Figure 4-13: Partitioning effects due to incr easing Re concentration for elements showing a preference to segregate to the interdendritic region.

PAGE 69

49 Partitioning Effects with Varying W0.000 0.500 1.000 1.500 2.000 2.500 3.000 3.500 55.566.577.588.599.5wt% Wk' Cr Co W Re Figure 4-14: Partitioning effects due to increasing W concentration for element segregating to the dendritic region. Partitioning Effects with Varying W0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000 55.566.577.588.599.5wt% Wk' Ni Ta Al Figure 4-15: Partitioning effects due to increasing W concentration for element segregating to the in terdendritic region.

PAGE 70

50 Partitioning Effects with Varying W (Mo added)0.00 0.50 1.00 1.50 2.00 2.50 3.00 22.533.544.555.566.57wt% Wk' Cr Co W Re Figure 4-16: Partitioning effects due to decr easing W concentration with the addition of 1 at% Mo for element segrega ting to the dendritic region. Partitioning Effect with Varying W (Mo added)0.00 0.20 0.40 0.60 0.80 1.00 1.20 22.533.544.555.566.57 wt%k' Ni Mo Ta Al Figure 4-17: Partitioning effects due to decr easing W concentration with the addition of 1 at% Mo for element segregating to the interdendritic region.

PAGE 71

51 4.3.6. Molybdenum Partitioning By examining the segregation behavior of the baseline (LMSX-1) and LMSX-8 alloys, the effect of a si ngle addition of Mo could be observed. The elemental segregation behavior of elements that partit ion to the dendritic regions is shown in Figure 4-18 and Figure 4-19 illustrates the segreg ation behavior of elements that partition to the interdendritic region. The addition of 1 at% Mo decreased the overall segregation of nearly every elem ent in the alloy. kRe decreased the most substantially followed by kW, and finally kCo. Cr partitioning was virtually unaff ected by the addition of Mo to this alloy. The elements that exhibited partitioning coefficients (k) less than one, also exhibited a similar segregation behavior w ith the addition of 1 at% (1.6 wt%) Mo. The segregation of Al was observ ed to decrease to the grea test degree followed by Ni and finally Ta. Mo was observed to partition to the interdendritic regions, and partitioned more strongly than Al and less than Ta. 4.3.7. Ruthenium Partitioning Ruthenium has become an alloying addition of great interest and is currently being added to the newer superalloys28,39,, which are called fourth ge neration superalloys. To investigate the effect of R u, two alloys were included in the alloy design matrix (see Table 3-1). The first was LMSX-16, which was the baseline LMSX-1 alloy with an addition of 1 at% Ru (1.6 wt%). The sec ond alloy, LMSX-17, contained 2 at% Ru (3.2 wt%). The addition of 1 at% Ru had no affect on Re segregation. However, when the Ru content was increased to 2 at%, Re begins to partition more dramatically. The remaining elements with kB greater than one (i.e. partition to the dendrite core) al l show essentially linear trends (Figure 4-20) for all three Ru concentrations (LMSX-1 (0 at% Ru), LMSX-

PAGE 72

52 16 (1 at% Ru), and LMSX-17 (2 at% Ru)). Cr segregated to a lesser degree than Re for all of the alloys in this study, and showed a linear increase in segregation as the Ru concentration increased. The kB values for Co and W both increased by a similar amount with the increase in Ru content. With the increase in Ru, Ru itself showed a decrease in its segregat ion behavior. The kB for Co in LMSX-17 was the largest value found for Co in this investiga tion, indicating that Ru strongly influences the segregation behavior of Co. Of the elements segregati ng to the interdendritic re gion in LMSX-1, -16, and -17, Ta showed the greatest degree of segregati on followed by Al and finally Ni (Figure 421). The segregation of Ta does not change until the Ru content was greater than 1.6 wt% (1 at%). When the Ru concentration was increased above 1 at%, Ta began to segregate to the interdendritic region more s ubstantially than at lower Ru concentrations. Al followed a similar pattern to Ta, but not as strongly. It should al so be noted that Al segregation behavior seemed to be reversed in the 1 at% Ru alloy since Al was observed to segregate to the dendritic region in LMSX-16. Ni was the only element that was relatively unaffected by the addition or Ru, and exhibited only a slight trend towards increased segregation with the increasing Ru content. 4.3.8. Palladium Partitioning The effect of Pd, a precious metal group element, was examined using LMSX-18 (1 at% Pd). Of the elements that exhibited tend encies to segregate to the dendrite cores, Re was affected the most by the Pd addition, a nd then followed by W (Figure 4-22). Both Re and W showed increased segregation as Pd was introduced into the alloy. Although Cr and Co partitioning both increased with th e increasing Pd content, it was not to the extent of the increase observed in W and Re.

PAGE 73

53 Partitioning Effect with Varying Mo0.000 0.500 1.000 1.500 2.000 2.500 3.000 3.500 00.20.40.60.811.21.41.61.8 wt% Mok' Cr Co W Re Figure 4-18: Partitioning effects due to the addition of 1 at% Mo for element segregating to the dendritic region. Partitioning Effects with Varying Mo0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000 00.20.40.60.811.21.41.61.8 wt% Mok' Ni Ta Al Mo Figure 4-19: Partitioning effects due to the addition of 1 at% Mo for element segregating to the interdendritic region.

PAGE 74

54 Partitioning Effect with Varying Ru0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000 00.511.522.533.5 wt% Ruk' Ni Ta Al Figure 4-20: Partitioning effects due to Ru addition for element segregating to the dendritic region. Partitioning Effect with Varying Ru0.000 1.000 2.000 3.000 4.000 5.000 6.000 7.000 00.511.522.533.5 wt% Ruk' Cr Co W Re Ru Figure 4-21: Partitioning effects due to Ru addition for element segregating to the interdendritic region.

PAGE 75

55 The presence of Pd in the alloy (LMSX-18) caused a decrease in segregation of Ni to the interdendritic regions (Figure 4-23). Segregation for Al and Ta both increased due to the addition of 1.7 wt% (1 at%) Pd, and th eir increases were similar in magnitude. From the kB values calculated, Pd itself segregated heavily to the interdendritic region. 4.3.9. Tungsten and Molybdenum Partitioning Interactions Although the segregation beha viors of alloys with an increasing W content (LMSX-1 and -6), with an addition of Mo (LMSX-1 and -8), and with decreasing W content with an addition of Mo (LMSX-7 and -8) were discussed, the segregation behavior due to substituting Mo for W was evaluated (LMSX-1 and -7, and LMSX-6 and -8) for interactions and consistency. These gr aphs from this evaluation are presented in See Figure 4-24. The first alloys compared were betw een LMSX-1 (5.85 wt% W, 0 Wt% Mo) and LMSX-7 (3.1 wt% W, 1.6 wt% Mo). The segr egation behavior for those elements whose partitioning coefficient, kB, value is greater than one are Re, W, Cr, and Co. The substitution of 1 at% Mo for 1 at% W caused a decrease in the segregations of Re, W, and Co. The decrease in segregation for Re was the most significant followed by W and finally Co, which showed only a slight decreas e in segregation. Cr segregation increased slightly due to this alloy m odification. All of the elemen ts that segregated to the interdendritic region exhibited a decrease in pa rtitioning due to the decrease in W content and the Mo addition. The partitioning of Al was reduced to the grea test degree, followed by Ni. The degree of segregation observed fo r Mo was intermediate to Al and Ni, but since it is only one point no further observati on can be made. The segregation of Ta was also decreased, but not to the extent of Ni.

PAGE 76

56 Partitioning Effects due to Pd Addition0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 00.20.40.60.811.21.41.61.8 wt% Pdk' Ni Ta Al Pd Figure 4-22: Partitioning effects due to Pd addition for element segregating to the dendritic region. Partitioning Effects due to Pd Addition0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 00.20.40.60.811.21.41.61.8 wt% Pdk' Cr Co W Re Figure 4-23 Partitioning effects due to Pd addition for element segregating to the interdendritic region.

PAGE 77

57 To verify the trends shown in decrea sing W content with an addition of Mo, LMSX-6 (8.6 wt% W, 0 wt% Mo) and -8 (5.85 wt% W, 1.6 wt% Mo) were compared. All of the trends noted in the LMSX-1 and -7 comparison were present in the evaluation of LMSX-6 and -8 (Figure 4-25), but the magnitudes had changed. The segregation behavior of Re was still obser ved to decrease with decreasi ng W content, but at a lower rate than the alloys with a lower concen tration of W. W exhibited more initial segregation due to the increased W content of LMSX-6, but d ecreased to nearly the same kB values for both LMSX-7 and -8 indica ting an increased segregation at high W concentrations. Ta and Ni both exhibited great er decreases in segreg ation behavior when the W content was reduced from 8.6 to 5.85 wt% and 1.6 wt% Mo was added. However, Ta and Ni were both initially more segr egated in LMSX-6 than LMSX-1. The segregation behavior of Co was observed to decrease more, but like Ni and Ta, was to a greater extent segregated in LMSX-6 than LMSX-1. Cr and Al segregation did not indicate any change due to d ecreasing W from a high content to an intermediate content combined with adding Mo. When comparing the degree of segregation in these four alloys (LMSX-1, -6, -7 and -8), LMSX-8 e xhibited the least amount of segregation. 4.3.10. Tantalum and Aluminum Pa rtitioning Interactions The next group of interactions observed co me from those alloys that had varying amounts of both Ta and Al (LMSX-12 and -13). LMSX-12 is a modified baseline alloy with 4 at% Ta (11.2 wt%, termed high Ta) a nd 12 at% Al (5 wt%, termed low Al). LMSX-13 contained a reduced Ta content (2 at%, 6 wt% termed low Ta) and an increased Al concentration (14 at%, 6.15 wt% termed high Al). Comparing the elements of these alloys to one another as well as the baseline (LMS X-1) was done to characterize

PAGE 78

58 Partitioning Interactions due to Decreasing W and a Mo Addition0.000 0.500 1.000 1.500 2.000 2.500 3.000 68 Alloy (LMSX-X)k' Cr Co W Re Ni Ta Al Mo Figure 4-24: Partitioning trends for elemen ts in LMSX-1 and-7. Difference in the two alloys is that LMSX-7 contains 3.1 wt% W and an addition of 1.6 wt% Mo. Partitioning Interactions Due to Decreased W and a Mo Addition0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 17 Alloy (LMSX-X)k' Cr Co W Re Ni Ta Al Mo Figure 4-25: Partitioning trends for elements in LMSX-6 and -8. Difference in the alloys is that LMSX-6 contains 8.6 wt% W, 0 wt% Mo, and LMSX-8 contains 5.85 wt% W, 1.6 wt% Mo.

PAGE 79

59 the interactions. Recall that all of these alloys have similar volume fractions of , so the alloy modifications are only intended to alter the composition of the phases. The increase in Ta to 11.2 wt% coupled with a decrease in Al to 5 wt% (LMSX-1 to LMSX-12) resulted in a variet y of effects on the elements in the alloys (Figure 4-26). Increased Ta and decreased Al contents cause d a decrease in the se gregation of Re, but Re remained the most segregated element present in this alloy. Ta showed the second greatest decrease in segregation which is surp rising since the amount of Ta was increased by 1 at% ( 3 wt%). The only other el ement that showed some effect due to this change was Cr, whose partitioning increased. The ot her elements in the system, W, Co, Ni, and Al did not show any significant change in se gregation due to the modification in alloy chemistry. To continue to evaluate the role of the formers, another combination of alloys was used to begin to examine partitioning interactions (LMSX-1 and -13). The difference in chemistry for these two lies in LMSX-13 which contains a reduced quantity of Ta (from 8.9 wt% down to 6 wt%) and an increase in Al (f rom 5.55 wt% up to 6.15 wt%). The overall trend for this alloy modifi cation was an increase in segregation for all elements except for Cr which began to segregat e to the interdendritic region. The largest increase in segregation of the elements that exhibited dendritic se gregation, was in the segregation for Re, which nearly doubled. Th e next greatest increase in segregation was observed in W. Co was the only element that did not appear to be affected by the change in alloy chemistry (Figure 4-28). Ta also exhi bited a significant increase in segregation of those elements that had a kB less than one. However, the segregation of Ta was significantly lower in magnitude in comparison to Re. Al segregation also increased to a

PAGE 80

60 lesser extent than Ta. Ni exhi bited a slight increase in part itioning due to this change in chemistry (Figure 4-29). LMSX-12 was also compared directly to LMSX-13 to further characterize these alloy modification effects (Fi gures 4-30 and 4-31). Not su rprisingly, the trends reported for the LMSX-1 to LMSX-13 interactions we re to be observed when examining LMSX12 and LMSX-13. Re segregation increased ag ain, and by a factor of more than two. W segregation also increased, but not to the degree of Re. Ag ain, Co partitioning appeared unaffected by these alloy modifications. The segregation to the in terdendritic region increased to the largest degree for Ta. Al se gregation did increase, but not to the extent of Ta, and the degree of Ni increased the least. 4.3.11. Tantalum and Aluminum Partitioning Interactions with an Addition of Titanium Ta and Al are not the only formers in Ni-base superalloys. Ti is also considered to be a former. The baseline alloy, LMSX -1, was modified again with Ti additions for either Ta or Al, to c ontinue to look at the effects of the formers. LMSX-14 is LMSX-1 with an addition of 0.80 wt% (1 at%) Ti and a decrease in Ta from 8.9 wt% (3 at%) down to 6.0 wt% (2 at%) This change in alloy chemistry changed the segregation of W a nd Cr causing them both to segregate more to the dendrite core, with W segregating more strongly than Cr. Re and Co segregation patterns had no observable change in this comparison (Figur e 31). Ta and Al both showed about the same increase in partitioning to the interdendritic region from the baseline to this modified chemistry. Ti itself exhibited the strongest segregation to the interdendritic region. The partitioning behavior of Ni decreased slightly due to these alloy modifications (Figure 32).

PAGE 81

61 Partitioning Interactions Due to Increasing Ta and Decreasing Al0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 112 Alloy (LMSX-X)k' Cr Co W Re Ni Ta Al Figure 4-26: Partitioning trends for elemen ts between in LMSX-1 and-12. Difference in the two alloys is that LMSX-12 contains 11.2 wt% Ta and 5.0 wt% Al. Partitioning Interactions Due to Decreasing Ta and Increasing Al0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 113 Alloy (LMSX-X)k' Cr Co W Re Figure 4-27: Partitioning trends for elem ents between in LMSX-1 and-13. Elements segregating to the dendritic region shown. Difference in the two alloys is that LMSX-13 contains 6.00 wt% Ta and 6.15 wt% Al.

PAGE 82

62 Partitioning Interactions due to Decreasing Ta and Increasing Al0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 113 Alloy (LMSX-X)k' Ni Ta Al Figure 4-28: Partitioning trends for elem ents between in LMSX-1 and-13. Elements segregating to the interde ndritic region shown. Difference in the two alloys is that LMSX-13 contains 6.00 wt% Ta and 6.15 wt% Al. Partitioning Interactions due to Variations in Ta and Al0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 1213 Alloy (LMSX-X)k' Cr Co W Re Figure 4-29: Partitioning trends for elem ents between in LMSX-12 and-13. Elements segregating to the dend ritic region shown.

PAGE 83

63 Partitioning Interactions due to Varying Ta and Al0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 1213 Alloy (LMSX-X)k' Ni Ta Al Figure 4-30: Partitioning trends for elem ents between in LMSX-12 and-13. Elements segregating to the inte rdendritic region shown. The effect of substituting Ti for Al was evaluated with LMSX-1 and -15, in which the formers were again modified (Figure 33 and 34). LMSX-15 is a variant of LMSX14 in that it contains the same addition of 1 at% (0.80 wt%) Ti, but LMSX-15 also had a reduction in Al from 5.10 wt % (13 at%) Al down to 5.0 wt% (12 at%). Of elements segregating to the dendrite, Re again showed the largest increase in segregation due to the alloy modification, followed by W. Cr segregation also incr eased, but only slightly, and Co showed even less of a change than Cr due to this alloy modification. Ta and Al both showed the same degree of increase in segrega tion with the substituti on of Ti for Al. Ni appeared to be unaffected by this modificat ion in alloy chemistry. Ti itself again segregated to the interdendritic regio n, more strongly than any other element. Using the combination of LMSX-14 and LMSX-15, it is now possible to observe the interactions between Ta and Al with the Ti add ition being constant. When

PAGE 84

64 comparing, LMSX-14 and -15, Re showed a la rge increase in segregation due to the increased Al content, decreased Ta content, and the Ti addition. W and Co exhibited an increase in kB of similar magnitude due to the change in Ta and Al concentrations with Ti in the matrix. The segregation of Cr ha d no appreciable change with the modification in alloy chemistry. Ti showed a greater degree of segregation than any other addition that partitioned to the interdendritic region. The kB for Ti in LMSX-15 was slightly lower than that of LMSX-14 indicating an increa se in partitioning with increasing Ta and decreasing Al contents. Ni a nd Al both exhibited similar in creases in segregation with alloy modifications. Ta showed no change in segregation due to these changes in base alloy chemistry. 4.4. Segregation Behavior The use of partitioning coefficients to describe the segregation of elements in an ascast alloy is useful to un derstand castability, defect fo rmation, and heat treatment requirements. However, the magnitude of se gregation obtained from the calculation of the partitioning coefficient may not be indica tive of the degree of segregation that is occurring. Also, in an element that show s a relatively wide scatter and no visible partitioning preference, (i.e. Cr in this expe riment) the actual partitioning, dendritic or interdendritic, that is occurring may not be accurate in all cases. The line scans used in this study, deve lop a graphical representation of the compositional variations that occur, due to segregation after so lidification and some degree of back diffusion have occurred. Fi gure 4-37 depicts this segregation between dendrites as a surface that has a varying composition depending on the distance from the dendrite itself. The curved lines between the dendrite cores is an id ealized representation

PAGE 85

65 Partitioning Interaction due to D ecreasing Ta with a Ti Addition0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 114 Alloy (LMSX-X)k' Cr Co W Re Figure 4-31: Partitioning trends for elem ents between in LMSX-1 and-14. Elements segregating to the dendritic region shown. Difference in the two alloys is that LMSX-14 contains 6.00 wt% Ta and an addition of 0.80 wt% Ti. Partitioning Interaction due to D ecreasing Ta with a Ti Addition0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 114 Alloy (LMSX-X)k' Ni Ta Al Ti Figure 4-32: Partitioning trends for elem ents between in LMSX-1 and-14. Elements segregating to the interde ndritic region shown. Difference in the two alloys is that LMSX-14 contains 6.00 wt% Ta and an addition of 0.80 wt% Ti.

PAGE 86

66 Partitioning Interaction Due to Decreasing Al and a Ti Addition0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 115 Alloy (LMSX-X)k' Cr Co W Re Figure 4-33: Partitioning trends for elem ents between in LMSX-1 and-15. Elements segregating to the dendritic region shown. Difference in the two alloys is that LMSX-15 contains 5.10 wt% Al and an addition of 0.80 wt% Ti. Partitioning Interaction Due to Decreasing Al and a Ti Addition0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 115 Alloy (LMSX-X)k' Ni Ta Al Ti Figure 4-34: Partitioning trends for elemen ts between in LMSX-1 and-15. Elements segregating to the interde ndritic region shown. Difference in the two alloys is that LMSX-15 contains 5.10 wt% Al and an addition of 0.80 wt% Ti.

PAGE 87

67 Partitioning Interactions Due to Varying Ta and Al with an Addition of Ti0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 1415 Alloy (LMSX-X)k' Cr Co W Re Figure 4-35: Partitioning trends for elem ents between in LMSX-14 and-15. Elements segregating to the de ndritic region shown. Partitioning Interactions Due to Varying Ta and Al with an Addition of Ti0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 1415 Alloy (LMSX-X)k' Ni Ta Al Ti Figure 4-36: Partitioning trends for elem ents between in LMSX-14 and-15. Elements segregating to the inte rdendritic region shown.

PAGE 88

68 of solidification, back diffusion, and segrega tion of an element that segregates to the dendrite core. Note that the composition of th e interdendritic region is depleted in the element while the core is enriched. Also it should be noted that the solidification/segregation lines are represented by curves. The use of curves was based on the observation of the general trends of the data points determined by EMPA. For each set of EMPA data points, a s econd order trendline was determined and then the equation that descri bes the trendline was determined. This was done for a normalized primary dendrite arm spacing (PDAS). Using this second order equation, the curvature for the trendline was determined. Curvature is defined as the amount by whic h a curve, surface, or other manifold deviates from a straight line.42 Mathematically, curvature, or comes from the second derivative of an equation, or more explicitly, 42 2 / 3 2 2 21 x y x y. equation (4-1) But this can be simplified to just the second derivative as previously mentioned due to the desire to determine the maximum value for the given equation. Thus, putting this in terms of the trendline equations, it is simply 2 a (where a is from a x2 + b x + c from the trendline equation) because th e only point of concern is at the apex which can be considered x = 0. It should be noted that care should be taken with the calculation of the curvature, The sign of is determine by the line scan it self. Since the line scans in this experiment were done from dendrite core to dendrite core thr ough the interdendritic region, one combination of positive and negative curvature values is achieved. If the

PAGE 89

69 scan were done from the interdendritic re gion, through the dendrite core, and back into the interdendritic region, another combination of positive and negative s are returned which are the opposite sign of th e first example. By doing the scans dendrite core to dendrite core, the resultant signs reflect those do ne by the previous k analysis in this and other studies. Figure 4-37: Red lines indicated solidificat ion/segregation gradie nts between dendrite cores within the interdendritic region for an element that segregates to the dendrite cores. The dendrites are represented in yellow. With the trendline equations determined, the could be calculated. was used to explain the segregation behavior in the various alloys. The curvature, values were calculated and then plotte d against the following: Cobalt. By comparing LMSX-1, -2, and -3. Chromium. By comparing LMSX-1, -5, and -5. Rhenium. By comparing LMSX-1, -9, -10, and -11. Ruthenium. By comparing LMSX-1, -16, and -17. Tungsten. By comparing LMSX-1 and 6. Molybdenum. By comparing LMSX-1 and -8

PAGE 90

70 Palladium. By comparing LMSX-1 and -18. Tungsten with a Molybdenum addition. By comparing LMSX-7 and -8. Variation of Tantalum and Aluminum from the baseline. LMSX-1, -12, and LMSX-1, -13. Variation between Tantalum and Aluminum. LMSX-12 and -13. Variation of Tantalum and Aluminum fr om the baseline with an addition of Titanium. LMSX-1, -14, and LMSX-1, -15. Variation between Tantalum and Aluminum with an addition of Titanium. LMSX14 and -15. V Variation between decreasing Tungsten and increasing Mo lybdenum. LMSX-1, -7 and -6, -8 Table 4-3 contains the values and the kB values for comparison purposes. Similar to previous results, the trend of k gr eater than unity indicated segregation to the dendrite core, along with greater than zero was consis tent for partitioning to the dendritic regions for the eighteen model alloys.11,35 Similarly, the trend of k less than unity and less than zero was also consistent with previous results for the eighteen model alloys, indicating consistency in dete rmining overall segregation path to the interdendritic regions. Although most results for these comparisons were similar, there was some disagreement in the elements that showed only a weak segregation preference between the dendritic and interdendritic region. 4.4.1. Cobalt Segregation Behavior The value was calculated for each element in each of LMSX-1, -2, and -3 and then plotted against increasing Co concentration. Figure 4-38 shows the extent of change of resulting from this compositional variation. Cr, Ni, W, and Re all partitioned to the dendritic region, and Al, Ni, a nd Ta all segregated to the interdendritic region. The

PAGE 91

71 elements W, Re, Ta, and Al all show a decrea se in their segregation as the Co content was increased. Co and Ni segregated slight ly more. Cr segregation did not change significantly. Re segregates more than a ny of the elements in these alloys over all concentrations of Co, and exhibited a maximum in segr egation at 4 wt% Co. Re segregation decreased slightly wi th the addition of 4 wt% Co to the alloy (for a total of 8 wt% Co). With 12.2 wt% Co present in the alloy, the Re dropped to the lowest level in this study. Ta showed the next greatest effect due to increasi ng Co content. The increase in Co from 4 wt% to 8 wt% showed little effect on Ta, but the segregation began to decrease (become less negative) when the Co concentration was in creased to 12.2 wt%. Ni showed the third greatest segregation be havior in this seri es of alloys. The increase in Co concentration caused an initia l increase in partitioni ng of Ni when Co was increased from 4 wt% to 8 wt%. The remaini ng increase in Co had no further effect on the segregation of Ni. W showed a linear de crease in segregation as the Co content was increased from 4 wt% to 12.2 wt%. The segr egation of Co followed a more expected trend of increasing as the concentration of it increased in the system from 4 wt% to 8 wt% Co, but did not change beyond the 8wt% Co concentration. Co in LMSX-3 was the lowest value for Co found in this part of this investigation. The partitioning of Al was the opposite of the trend observed by Co. There was no change in Al segregation from 4 wt% Co to 8 wt% Co, and then the partitioning decreased with further additions of Co. 4.4.2. Chromium Segregation Behavior LMSX-4, -1, and -5 were used to evaluate the segregation behavior of the elements in the alloys with varying Cr contents. LMSX-5 contained 2.1 wt% Cr and LMSX-4 contained 6.15 wt% Cr. This analysis is pres ented from the low Cr content alloy to the

PAGE 92

72 high content alloy (Figure 4-39). When the analysis was preformed, Re was observed to exhibit the greatest degree of segregation and it partitioned to the dendritic region. The low and baseline levels of Cr had little e ffect on the segregation behavior, but the addition of 4.15 wt% Cr to the high Cr (L MSX-4, 6.15 wt% Cr) brought about a decrease in Re segregation. Ta segregated to the interdendritic region and was the second most strongly segregated element. As Cr was adde d, the partitioning of Ta increased and then remained relatively constant. The addition of Cr brought about a decrease in the third most heavily partitioned element, Ni, which se gregated to the interdendritic region. As the Cr content was increased, the partitioning of Ni decreased in a linear manner. W partitioned to the dendritic region and its segregation decreased linearly as the Cr content increased. Co and Cr both segregated to th e dendrite cores, and bot h showed only slight increases in segregation due to increasing Cr content. However, Co did segregate more strongly than Cr over the entire range of compositions evaluated. Cr exhibited a complete change in segregation. In high Cr alloy (LMSX-4, 6.15 wt% Cr) and the baseline, Cr was observed to segregate to th e dendritic regions. Whereas in low Cr content alloys (LMSX-5, 2.1 wt% Cr) was obser ved to segregate to the interdendritic region. The increasing the Cr content caused Al to segregate to a slightly less, and Al segregated to the interdendritic region. Cr in LMSX-5 was almost zero indicating no preference in segregation.

PAGE 93

73Table 4-3: Comparison of values calculated by kB and Alloy Method Ni Cr Co Mo W Re Ta Al Ti Ru Pd -32.910.7510.02 16.5547.80 -44.98-9.12 1 k'B 0.91 1.04 1.14 1.58 3.10 0.48 0.75 -31.312.3911.60 19.5855.81 -44.98-12.59 2 k'B 0.94 1.20 1.18 1.57 3.04 0.48 0.73 -27.810.885.29 22.3657.96 -45.69-13.01 3 k'B 0.94 1.07 1.23 1.87 4.86 0.44 0.70 -21.361.829.59 13.9040.77 -35.69-8.98 4 k'B 0.93 1.05 1.19 1.52 3.08 0.46 0.81 -35.63-0.209.59 17.6447.36 -27.00-9.12 5 k'B 0.94 0.98 1.04 1.64 2.59 0.54 0.78 -41.481.7114.39 29.2049.66 -38.49-14.91 6 k'B 0.93 1.03 1.16 1.89 2.69 0.41 0.69 -15.250.189.31-2.635.2939.58 -28.92-7.55 7 k'B 0.97 1.10 1.06 0.88 1.41 2.35 0.54 0.84 -25.391.0610.64-1.3912.7539.99 -28.65-9.11 8 k'B 0.94 1.03 1.06 0.82 1.46 2.48 0.50 0.85 1.26-2.275.49 17.990.00 -25.92-4.15 9 k'B 1.01 1.00 1.11 1.62 0.00 0.61 0.86 -16.922.3514.02 22.2331.82 -45.59-7.82 10 k'B 0.96 1.07 1.19 1.60 3.41 0.50 0.83 -65.365.7116.86 15.5186.65 -42.52-16.80 11 k'B 0.87 1.28 1.25 1.73 6.70 0.34 0.65 -28.802.8113.11 16.9147.08 -40.80-10.27 12 k'B 0.94 1.13 1.15 1.57 2.67 0.54 0.77

PAGE 94

74Table 4-3 (cont.): Comparison of values calculated by kB and Alloy Method Ni Cr Co Mo W Re Ta Al Ti Ru Pd -50.02 -1.8911.24 22.5459.26 -25.75-15.32 13 k'B 0.89 0.89 1.20 2.07 5.86 0.34 0.69 -41.27 0.6410.70 22.4143.09 -18.99-11.04-5.59 14 k'B 0.93 1.19 1.10 1.83 3.12 0.44 0.72 0.42 -30.16 2.0713.03 19.6346.81 -30.01-9.43-7.14 15 k'B 0.91 1.14 1.22 1.91 4.03 0.45 0.71 0.37 -33.63 1.6211.37 16.0146.51 -31.27-11.31 0.84 16 k'B 0.93 1.12 1.19 1.52 2.96 0.47 1.02 1.18 -49.64 5.4517.68 20.6264.85 -46.59-15.08 2.75 17 k'B 0.90 1.15 1.25 1.86 5.75 0.35 0.71 1.15 -30.19 3.2818.05 22.0457.72 -36.08-15.76 -19.12 18 k'B 0.93 1.11 1.24 2.08 4.54 0.44 0.68 0.27

PAGE 95

75 4.4.3. Rhenium Segregation Behavior Re is the element that defines the different generations of superalloys and this part of the investigation deals with the effects of segregation due to increasing Re content from 0 wt% Re (LMSX-9, a first generation model superalloy), to 3 wt% Re (LMSXS10, a second generation model superalloy), a nd finally reaching 6 wt% Re (LMSX-1), a third generation model superalloy. To begin to understand the effect of larger quantities or Re on an alloy, an additional 3 wt% Re was added in LMSX-11. This discussion will be related in terms of increas ing Re content from 0 wt% to 8.9 wt%. See Figure 4-40 for graphical representation of the presented information. Normalized Partitioning due to Co-60.00 -40.00 -20.00 0.00 20.00 40.00 60.00 80.002468101214w/o Co Ni Cr Co W Re Ta Al Figure 4-38: Elemental se gregation plots based on due to increasing Co content from 4 wt% to 12.2 wt%.

PAGE 96

76 Normalized Partitioning due to Cr-50.00 -40.00 -30.00 -20.00 -10.00 0.00 10.00 20.00 30.00 40.00 50.00 60.001234567w/o Cr Ni Cr Co W Re Ta Al Figure 4-39: Elemental se gregation plots based on due to increasing Cr content from 2.1 wt% to 6.15 wt%. Re was the most segregated element in the alloys examined in this series, and the degree of segregation increased as more Re wa s added to the system. Re segregated to the dendritic region, and the for Re in LMSX-11 was the larg est observed in this study. Ta, which partitioned to the interdendritic region exhibited an initial increase in segregation when 1 at% Re was added to the system. Af ter this point, the se gregation varied, but remained relatively constant and did not incr ease further. Ni was found to segregate to the dendrite core in LMSX-9 (0 wt% Re), and then began to partition to the interdendritic region, with increasing Re content. The fina l addition of Re (to 8.9 wt%) caused a large increase in the segregat ion behavior of Ni, and Ni became more negative than that of Ta indicating even more Ni segregation was occu rring than Ta. W showed less segregation than Ni, and it segregated to the dendritic re gion. The increase in Re did not affect the segregation behavior of W signi ficantly. The overall behavior of W was nearly constant,

PAGE 97

77 although a slight decrease in segregation was obs erved. Co initially showed very little segregation in LMSX-9, but the addition of 1 at% Re increased its partitioning to the dendritic core. Further additi ons of Re brought about a slight increase in segregation in Co. Al segregated to the interdendritic re gion, and the segregation behavior for Al did not change from the 0, 1, and 2 at% Re concen trations. The addition of the final 1 at% Re caused the segregation to increase slight ly. Cr was observed to segregate to the interdendritic region in LMSX9, but after Re was added, it began to segregate to the dendritic region. As the Re content was in creased, a slow, linear increase in the segregation of Cr was observed. LMSX-11 contained four of the strongest segregating elements in this entire investigation. Ni and Al were the most heav ily segregated to the interdendritic region, and Re were the most heavily segregated to the dendritic core followed by either W and Co, both of which were observed to have th e same degree of segregation. However, minimums in the segregation behavior of se veral elements were observed in the low Re alloys. Al was the lowest in LMSX-9, and Re was at its lowest in LMSX-10.

PAGE 98

78 Normalized Partitioning due to Re-80 -60 -40 -20 0 20 40 60 80 100012345678910w/o Re Ni Cr Co W Re Ta Al Figure 4-40: Elemental se gregation plots based on due to increasing Re content from 0 wt% to 8.9 wt%. 4.4.4. Tungsten Segregation Behavior W was studied at two levels: the baselin e LMSX-1 (5.85 wt% W) and an increased level of W in LMSX-6 (8.6 wt% W). The fi rst observation was th at by increasing the W concentration, all of the elements in the alloys (Ni, Cr, Co, W, Re, Ta, and Al) segregated more strongly (Figure 4-41). Re, W, Co, and Cr all segregated to the dendrite core. The degree of segregation was also in this order with Re being the most heavily partitioned, and Cr being the least partitioned. Ta, Ni, a nd Al all partitioned to the interdendritic region. At the low W level (5.85 wt%), Ta se gregated the most strongly, followed by Ni and then Al. When segregation was examined at the high W level (8.6 wt%), Ni and Ta switched making Ni the most heavily partitioned element segregating to the interdendritic region. In LMSX-6, W was found to segregate more strongly than in any other alloy in this study.

PAGE 99

79 Normalized Partitioning varying W-60.00 -40.00 -20.00 0.00 20.00 40.00 60.0055.566.577.588.599.5w/o W Ni Cr Co W Re Ta Al Figure 4-41: Elemental se gregation plots based on due to increasing W content from 5.85 wt% to 8.6 wt%. 4.4.5. Tungsten Segregation Behavior wi th an Addition of Molybdenum With the addition of 1 at% Mo, LMSX-7 and -8 could be compared to examine the effects of partitioning with a variation in W. The difference in these to alloys is the reduced W content of LMSX-7 to 3.1 wt% from 5.85 wt%. Increasing the W content had little eff ect on the two most heavily segregated elements (Figure 4-42). Re, the most heavily segregated of all, remained segregated to the dendrite core regions. Ta, the second most heavily segregated element, still segregated to the interdendritic region. Ni was still segregating to the interdendritic regions and partitioned more strongly as W was added. The increase in Ni with increasing W was the largest observed in this set of alloys. Initially, Co partitioned more than W itself to the dendritic region. Bu t after increasing th e W concentration, W segregated more strongly than Co. Al segreg ated to the interdendr itic region. As the W

PAGE 100

80 content was increased, Al began to partition to a slightly greater degree, but not to the extent of the other elements with the excep tion of Re and Ta. Cr showed only a small increase in its behavior of partitioning to the dendritic region, as W was added. Mo, which partitioned to the interdendritic regi on, exhibited less segregation as more W was added to the system. The lowest degree of W segregation, W, in this study was observed in LMSX-7. 4.4.6. Molybdenum Segregation Behavior Using the baseline LMSX-1 (0 wt% Mo) and comparing it to LMSX-8 (1.6 wt% Mo), the segregation behavior of Mo coul d be ascertained. Of the elements that segregated to the dendrite core region, Re se gregated the most, followed by W, then Co, and finally Cr (Figure 4-43). The elements th at segregated to the interdendritic region were Ta, Ni, Al, and Mo (in order from greates t degree of segregation to least). Re was the most heavily segregated, and Ta was the second most segregated. The addition of Mo caused both Re and Ta to segregate less, and by about the same amount. This change in chemistry also led to a decrease in the segreg ation Ni and to a lesser degree, W. Al and Cr had no observable change in segregation be havior due to the a ddition of 1 at% Mo. The segregation of Co increased slig htly with the addition of Mo. 4.4.7. Ruthenium Segregation Behavior LMSX-16 and -17 both contained an addi tion of 1 and 2 (1.6 and 3.2) at% (wt%) Ru respectively. Analyses were done on the EM PA data to determine the effect of an addition of Ru on the partitioning of all elemen ts contained in these alloys, and compared The elements that segregated to the dendritic region (in order of gr eatest to least) were Re, W, Co, Cr, and Ru (Figure 4-44). All th e other elements (Ni, Ta, and Al) partitioned to the interdendritic region. The initial addition of 1 at % Ru only showed an effect on the

PAGE 101

81 segregation behaviors of Ni, Ta, and Al. The addition of 1 at% Ru caused Ni to segregate more, and the Ta to segregate less, making Ni the most severely segregated element that partitioned to the interdendritic region. Al segregated only slight more than it had prior to the addition of 1 at% Ru. The addition of a second 1 at% Ru (for a total of 3.2 wt%) ca used a significant increase in the segregation be havior of Re. Ni and Ta also exhibited an increased partitioning behavior. The segregation beha viors of Ni and Ta changed by about the same amount. Although W did segregate more th an Co at both the 1 and 2 at% Ru levels, against the baseline alloy LMSX-1 (0 at%, 0 wt% Ru). the segregation of Co increased more than that of W with the Ru addi tions. The 3.2 wt% Ru caused a continued segregation of Al to the interdendri tic region at the about same rate. Cr also increased at the 3.2 wt% Ru concentration from its leve l at the 1.6 wt% Ru. Ru itself began to partition more as its concentration was in creased, but it showed the least amount of segregation of all the elements contained in the alloy. Ta was observed to exhibit a maximum degree of segregation in LMSX-17.

PAGE 102

82 Normalized Partitioning due to W with Mo Addition-40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 30.0 40.0 50.022.533.544.555.566.5wt% W Ni Cr Co W Re Ta Al Mo Figure 4-42: Elemental se gregation plots based on due to increasing W content from 3.1 wt% to 5.85 wt% with an addition of 1.6 wt% Mo to the alloys. Normalized Partitioning due to Mo-50.00 -40.00 -30.00 -20.00 -10.00 0.00 10.00 20.00 30.00 40.00 50.00 60.0000.20.40.60.811.21.41.61.8w/o Mo Ni Cr Co W Re Ta Al Mo Figure 4-43: Element segregation plots based on due to increasing Mo content from 0 wt% to 1.6 wt%.

PAGE 103

83 4.4.8. Palladium Segregation Behavior LMSX-18 was a model alloy with an additional 1 at% (1.7 wt%) Pd. When compared to LMSX-1, the segregation effect s due to this addition may be examined (Figure 4-45). Re, W, Co, and Cr all segregated to the dendrit ic region (and in that order from the most strongly segregated to the leas t), and Ta, Ni, Pd, and finally Al segregated to the interdendritic region (aga in in the order of the highest to lowest partitioning). Re showed the largest increase in segregati on behavior due the addition of Pd. The segregation behavior of Al al so increased with the Pd addi tion. W and Co segregated more strongly with the addition of Pd and the segregation of both elements increased by about the same amount with the Pd addition. Cr increased very slight ly over the range of the addition. The addition of Pd had no affect on the segregation behavior of Ta and Ni. Pd itself was observed to segregate to the interden dritic region to a sli ghtly greater degree than Al. Of all the values of Co observed in these alloys, the maximum value of segregation was observed in LMSX-18. 4.4.9. Tungsten and Molybdenum Segre gation Behavior Interactions The segregation behavior of a decrease in W content and a Mo addition can be examined to develop a qualitative understand ing of elemental interactions that exist between Mo and W. The combinations of LMSX-1, -7 and LMSX-6, -8 were examined to determine the presence of elemental inte ractions and verify th e consistency between these two studies. LMSX-1 and -7 were the first two alloys compared to analyze the effects of a decrease in W (5.85 wt% in LMSX-1 and 3.1 wt% in LMSX-7) and an addition of 1.6 wt% Mo in LMSX-7. When the W conten t was decreased, and as Mo was added, the

PAGE 104

84 Normalized Ru Partitioning-60.0 -40.0 -20.0 0.0 20.0 40.0 60.0 80.000.511.522.533.5w/o Ru Ni Cr Co W Re Ta Al Ru Figure 4-44: Element segregation plots based on due to increasing Ru content from 0 wt% to 3.2 wt%. Normalized Partitioning due to Pd-60.0 -40.0 -20.0 0.0 20.0 40.0 60.0 80.000.20.40.60.811.21.41.61.8w/o Pd Ni Cr Co W Re Ta Al Pd Figure 4-45: Elemental se gregation plots based on due to increasing Pd content from 0 wt% to 1.7 wt%.

PAGE 105

85 segregation behavior of all th e elements (Ni, Cr, Co, W, Re, Ta, and Al) all decreased (Figure 4-46). Re was the most heavily segregated of the elements that partitioned to the dendritic region. The substitution of Mo for W resulted in a decrease in the segregation behavior of Re. This change in alloy chemistry also caused a decrease in the segregation behavior of W. In the baseline alloy (LMS X-1), W segregated more strongly than Co, but when Mo was substituted for W, W segreg ated less than Co, and both segregated to the dendrite core region. Cr decrease very slightly due to the decrease in W and addition of Mo. All of the elements that partitioned to th e interdendritic region segregated less strongly in LMSX-7 than in LMSX-1. Ta wa s the most strongly segregated element that went into the interdendritic region, followed by Ni, and th en by Al. The degree of segregation of Ni decreased more than any other element, when Mo was substituted for W. Al exhibited the smallest decrease in the degree of segregati on with a decreased W content and a Mo addition. LMSX-6 (8.6 wt% W, 0 wt% Mo) and -8 (5.85 wt% W, 1.6 wt% Mo) were compared to verify the trends with Mo subs tituted for W (Figure 447). The segregation behavior of all the elements (Ni, Cr, Co, W, Re, Ta, and Al) all continued to show a decreased segregation due to the substitution of Mo for W. Ni was observed to be more strongly segregated of the elements that segr egated to the interdendritic region, followed by Ta, without the Mo addition (LMSX-6), but when Mo was substituted for W, the degree of segregation for Ni decreased. Ta was then slightly more segregated than Ni in LMSX-8. However, Ta was observed to be mo re strongly segregated in LMSX-8 than in LMSX-6.

PAGE 106

86 Normalized Partitioning Effects due to a Decrease in Tungsten and an Addition of Molybdenum-50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 30.0 40.0 50.0 60.017Alloy Ni Cr Co W Re Ta Al Mo Figure 4-46: Elemental se gregation plots based on due to decreasing W to 3.1 wt% and adding 1.6 wt % Mo. Normalized Partitioning Effects due to Decrease in W and an Addition of Molybdenum-60.00 -40.00 -20.00 0.00 20.00 40.00 60.00 68 Alloy (LMSX-X) Ni Cr Co W Re Ta Al Mo Figure 4-47: Elemental se gregation plot based on due to decreasing W to 5.85 wt% and adding 1.6 wt% Mo.

PAGE 107

87 4.4.10. Tantalum and Aluminum Segre gation Behavior Interactions The former interactions were observed in three different combinations. The first was comparing LMSX-1 to LMSX-12. These alloys utilized an increase in the Ta concentration from 8.6 wt% to 11.2 wt%, coupled with a decrease in Al from 5.55 wt% to 5.00 wt%. The second comparison was LMSX-1 to LMSX-13. Here, the Ta was decreased to 6 wt% and the Al was increas ed to 6.15 wt%. The last comparison examined in this section was that of LM SX-12 to LMSX-13, in which the effect of varying Ta and Al can readily be seen. When comparing LMSX-1 to LMSX-12, the e ffects of substituting Ta for Al on the segregation behavior was determined. Re, W, Co, and Cr segregated to the dendritic region, and the magnitudes of their segregation co efficients were also in that order (from greatest to least). The segregat ion of Co increased slightly, but all the other elements that segregated to the dendrite core (Re, W, and Cr) had no observable effects in their segregation behaviors due to the substitution of Al for Ta. Ta, Ni, and then Al were shown to partition to the inte rdendritic region, with Ta exhibiting the greatest magnitude, and Al the smallest, and the segregation of Ta and Al increased (Ta more than Al). Ni exhibited a slight decrease in segregation from the substitution of Al for Ta. See Figure 4-48. The next comparison involved the substitution of Al for Ta using LMSX-1 and -13 (Figure 4-49). The segregation behavior of Re increased when Al was substituted for Ta, but Re still exhibited the most severe segr egation to the dendritic region. W had the same trend, but segregated less strongly than Re in both instances. Co still partitioned to the dendritic region, and showed only a very sl ight increase in segregation due to this

PAGE 108

88 change in chemistry. The substitution of Al for Ta resulted in the segregation of Cr changing from the dendritic re gion in LMSX-1, to the interd endritic region in LMSX-13. Ta, Ni, and Al all segregated to the inte rdendritic region, but to varying degrees. The magnitude of from the baseline alloy (from greates t to least) was Ta, Ni, and Al. But after the alloy was modified, this order ch anged. Ni and Ta switched, and Ni became the most heavily segregated of the three el ements. The segregation behavior of Ni increased more than any other element in this series. The segregation behavior of Al also increased, but not to the extent of Ni. The degree of segregation of Ta actually decreased. The final comparison was between LMSX12 and LMSX-13 (Figure 4-50). Due to the general linearity of the trends in the comparison betw een LMSX-1 and LMSX-12, the trends shown in this graph appear almost iden tical. All the trends are also duplicated. The only change was a slight decrease in th e segregation behavior of Cr from LMSX-12 to LMSX-13. 4.4.11. Tantalum and Aluminum Segregatio n Behavior with an Addition of Titanium Keeping with the same methodology as the pr evious section, in teractions between the alloys LMSX-1, -14 and -15 could be ex amined to determine the effect of other formers on the segregation behavior. LMSX -14 differs from LMSX-1 by a reduction in Ta from 8.6 wt% to 6.0 wt% and an additi on of 0.80 wt% Ti. The difference between LMSX-1 and -15 is LMSX-15 has 5.10 wt% Al and an addition of 0.80 wt% Ti. These alloys were compared in this way, and th en a final comparison between LMSX-14 and 15 was done.

PAGE 109

89 Normalized Partitioning due to an Increase in Tantalum and a Decrease in Aluminum-50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 30.0 40.0 50.0 60.0112Alloy Ni Cr Co W Re Ta Al Figure 4-48: Elemental segregation plots based on due to increasing Ta to 11.2 wt% and decreasing Al to 5 wt%. Normalized partitioning due to a Decrease in Tantalum and an Increase in Aluminum-60.0 -40.0 -20.0 0.0 20.0 40.0 60.0 80.0113Alloy Ni Cr Co W Re Ta Al Figure 4-49: Elemental segregation plots based on due to decreasing Ta to 6.0 wt% and increasing Al to 6.15 wt%.

PAGE 110

90 Normalized partitioning due to Varying bothTa and Al-60.0 -40.0 -20.0 0.0 20.0 40.0 60.0 80.01213Alloy Ni Cr Co W Re Ta Al Figure 4-50: Elemental se gregation plots based on due to changing Ta and Al concentrations. Compilati on of Figures 4-48 and 4-49. The effect of adding Ti for Ta was ex amined by determining the segregation behaviors of LMSX-1 and -14 (Figure 4-51) As in previous results, the following elements segregated to the dendritic region : Re, W, Co, and Cr. The elements that segregated to the interdendritic re gion were Ta, Ni, Al, and Ti. The alloy modification caused a decrease in partitioning for Re (which segregated the most strongly), and increased the segregati on of W. The substitution of Ti for Ta also resulted in a slight increase in the segreg ation behavior of Co, and no observable change for Cr. For LMSX-1, Ta was the most segregated of the formers, but in LMSX-14 Ni was the most strongly segregat ing element. The value of for Ni was also more than that of Ta in LMSX-1. Essentially decreased for Ni (more negative) and increased for Ta (closer to zero). The segregati on of Al also increased slightly.

PAGE 111

91 The effect of substituting Ti for Al (LMSX-1 and -15) on the segregation behavior was slightly clearer than the previous compar ison (Figure 4-52). Re, W, Co, and Cr all segregated to the dendrite core regions. Re was the most segregated, followed by W, Co, and finally Cr. The elements segregating to th e interdendritic were Ta, Ni, Al, and Ti. The alloy modification (i.e. substituting Ti for Al) brought about a decrease in the segregation behavior of Re, a nd an increase in the degree of segregation of W, Co, and Cr, to about the same extent. Al did not change between these alloys. Ni decreased slightly indicating a slight increase in segregation, and Ta increased to the same value as Ni (both for LMSX-15). The partitioning of Ta decreased with this s ubstitution of Ti for Al. Finally, the effect of varyi ng Ta and Al at constant Ti was evaluated by examining alloys LMSX-14 and -15. All of the elements continued to segreg ate to the respective regions as specified in the two prior compar isons (Figure 4-53). Substituting Ta for Al resulted in the degree of Re segregation, and a decrease in segregation of W. Co and Cr both exhibited increased segregation, with Co exhibiting slightly great er segregation than Cr. As in most alloys, Re showed the greatest degree of segregation. Ni was generally the more segregated of the elements in the interdendritic region, but in LMSX-15, the degree of segregation fo r Ni and Ta were about the same. Ni exhibited a decrease in segregation (increase in when is negative), and Ta exhibited an increase in segregation (decrease in when is negative). A slight reduction in the partitioning of Al was observed in LMSX15, in comparison to LMSX-14. Finally, Ti partitioned to a greater degree in LMSX15 than in LMSX-14. Of all of the Ta values

PAGE 112

92 calculated in this inve stigation, the values de termined for Ta in LMSX-14 indicated the least amount of Ta segregation observed in this alloy series. 4.5. Scheil Analysis and Comparison To further check the validity of this an alysis, a Scheil analys is was done according to the method described by M. N. Gungor.36 For clarity, the Gungor methodology is identified in the following as Full analysis and the work in this study is identified as Short analysis. The LMSX-3 specimen was us ed for this test. Appendix D contains all pertinent data and graphs from this ev aluation. The full Sche il equation was not determined; however the general shapes of the curves were compared to examine the effectiveness of a much faster method of collecting the data. The Short analysis compares very well agai nst the Full analysis for Ni, Cr, Co and Al, (Figure 4-54 is shown for Cr) with the cu rves having the same shape, slope, and lying very close, if not on one another. The curv es for W and Re (Figure 4-55 is shown for Re) are also similar, but they do begin to diverg e or have a slightly greater slope than the curve for the other elements. The only curv e that exhibited a si gnificant difference was for Ta (Figure 4-56). Although there was one curve of seven that differed, the advantage of this is the time required to perform the entire test. The Full analysis required 12 hours to perform, and the Short analysis (which was the techniqu e use to evaluate segregation in all prior sections) took 5 hours.

PAGE 113

93 Normalized Partitiioning due to Decreasing Ta with an Addition of Ti-50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 30.0 40.0 50.0 60.0114Alloy Ni Cr Co W Re Ta Al Ti Figure 4-51: Elemental se gregation plots based on due to decreasing Ta to 6.0 wt% and a Ti addition of 0.80 wt%. Normalized Partitioning due to a Decrease in Al and an Addition of Ti-50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 30.0 40.0 50.0 60.0115Alloy Ni Cr Co W Re Ta Al Ti Figure 4-52: Elemental se gregation plots based on due to decreasing Al to 5.10 wt% and a Ti addition of 0.80 wt%.

PAGE 114

94 Normalized partitioning of Varying Amounts of Tantalum and Aluminum with an Addition of Titanium-50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 30.0 40.0 50.0 60.01415Alloy Ni Cr Co W Re Ta Al Ti Figure 4-53: Elemental se gregation plots based on due to changing Ta and Al concentrations with a Ti addition. Compilation of figures 4-51 and 4-52. LMSX-3 Cr Scheil Comparison0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.10.20.30.40.50.60.70.80.91 vol%wt% Cr Full Short Figure 4-54: Scheil curve comparison fo r Cr done by two different techniques.

PAGE 115

95 LMSX-3 Re Scheil Analysis0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 00.10.20.30.40.50.60.70.80.91 vol%wt% Re Full Short Figure 4-55: Scheil curve comparison fo r Re done by two different techniques. LMSX-3 Ta Scheil Analysis0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 00.10.20.30.40.50.60.70.80.91 vol%wt% Ta Full Short Figure 4-56: Scheil curve comparison fo r Ta done by two different techniques.

PAGE 116

96 4.6. Verification of Applicability of Analysis The analysis described in this investiga tion was done on an as-cast specimen of CMSX-4 to compare values returned for both k and Results for this portion of the study are in Table 4-4. When comparing the values for and k for CMSX-4, there is perfect agreement in the direction of elemental pa rtitioning. Values of kB greater than unity indicate partitioning of elements to the dendritic core regions. Values of greater than zero indicate this also. For va lues of k less than unity, there is segregation to the interdendritic region. When is used, segregation to the interdendritic region will be less than zero. All of the elemen ts in CMSX-4 show agreement between the two techniques. The magnitudes of segregation were somewhat different for the trace elements Mo and Ti in CMSX-4. Again this use of is based on the start and stop poi nts. The convention used in this experiment was to start and stop at de ndrite cores. Using the dendrite cores as starting and stopping points has dend ritic segregation occurring if is greater than zero. If the interdendritic region is use d, dendritic segregation occurs if is less than zero. To continue with the verification, Scheil curves were prepared for CMSX-4 so that they could be compared with similar curves44 for CMSX-4. The partitioning direction for these curves was based on the k results found in Table 4-4. The data and Scheil curves for CMSX-4 are contained in Appendix D.

PAGE 117

97 Table 4-4: Comp arison of kB and for CMSX-4. Ni Cr Co Mo W Re Ta Al Ti Dendritic 63.08 6.2510.520.696.064.433.47 5.150.69 Interdendritic 65.57 7.379.220.723.551.296.20 6.711.45 k'B 0.96 0.85 1.14 0.96 1.71 3.43 0.56 0.77 0.48 -6.86 -5.01 4.39 -0.76 14.13 16.00 -11.81 -6.20 -3.90

PAGE 118

98 CHAPTER 5 DISCUSSION There is a significant amount of literature on the effect of composition on the properties (i.e. creep, fatigue, strengthening, etc.) of supera lloys. However, due to the complexity of the system, with twelve to fifteen alloying elements in a typical superalloys4-6,30,36, a significant amount still remain s unknown. Elemental interactions and the complex problems w ith segregation and diffusion are prevalent throughout the superalloy system. As noted above, superalloys are made up of twelve to fifteen different elements added to nickel, which is the most common base element. The typical additions to the base element are Al, Cr, Co, W, Re, Ti and Ta. There are other additions that are relatively low levels and have been ignored for the purposes of discussion (i.e. Hf and B). Ni and Al, when present together in the appropriate amount form the matrix. This occurs in the vicinity of Ni15Al in the Al-Ni binary diagram14, but commonly, a superalloy only contains about 55 60 wt% Ni and about 4 -6 wt % Al. The remaining 40 45 wt% is made up of all the other alloying elements, and each element has a different melting temperature. Elements su ch as Re, W, and Ta all have very high melting temperature, are very dense, and diffuse slowly, but Cr, Co, and Ti have relatively low melting temperatures have lower densities, and di ffuse at different rates. These differences cause the elements to be distributed unevenly throughout the alloy during solidification, and in some extreme circ umstances, an undesirable phase if formed due to localized enrichment. If the pattern s for the segregation of the elements used in these alloys are known, improved alloys compositions can be developed.

PAGE 119

99 Heat treatments are often used to reduce or eliminate se gregation from the as-cast microstructure. An alloy that is less segr egated (more homogeneous) requires less time to heat treat (solution) to re duce segregation. The purpose of heat treatments is to evenly disperse all of the elements in the alloy and develop an optimized microstructure so that more uniform and better properties will be obser ved in the alloy. This local enrichment of elements forming in the as-cast structure can also lead to deleterious phases such as , and laves phases. To eliminate segregati on in the alloy, the elements must diffuse through the matrix until they are well disp ersed. Diffusion is a thermally activated process; higher temperature equals shorter time, but some incipient melting may occur. However, lower temperature heat treatments require longer times, and the alloy may still be segregated, unless sufficient time is allo wed. Shorter and lower temperature heat treatments are desired by industry since the heat treatment costs will be reduced. The temperature is governed by the difference between the solvus and solidus temperatures, or the heat treatment window. Third generation superalloys (2 at% Re) are currently used in a variety of applications. These are some of the most h eavily alloyed superalloys and contain nearly 15 wt% of the refractory elements, Re, Ta, and W. With the addition of these refractory elements, segregation can cause problems dur ing casting. CMSX-10 is a third generation superalloy used to make airfoils for some of the highest temperature applications. The chemistry of CMSX-10 is listed at the bottom of Table 3-1. Due to the alloy chemistry, the solvus is very high (over 1350C), and the solidus is only 30C higher.16 Since these dense refractory elements diffuse slowl y, the total time for solution heat treatment for an alloy like CMSX-10 can be nearly 50 hours. This makes heat treating very

PAGE 120

100 difficult, and expensive. Because of these l ong and expensive heat treatments, the desire to understand how the elements partition b ecomes important because it could lead to shorter heat treatment times. The baseline alloy LMSX-1 was developed to have an approximate volume fraction of 55 60% and have good microstruc tural stability (not form topologically close packed (TCP) phases on casting or thr oughout service life). The chemistry of LMSX-1 is based on two commercial third ge neration alloys, CMSX-10 and Ren N6. The other seventeen alloys were developed to examine the effect of the additions on strength, stability, solvus, etc. The composition of LMSX-1 and the other seventeen model alloys is contained in Table 3-1. Currently, partitioning is determined by ratioing the composition of an element between the dendrite core region and the interdendritic region11,16,37-39 (equation 1-1). This calculation produces what is knows as the partitioning coefficient k. k readily indicates if an element segregat es to the dendrite core (k > 1. 00) or to the interdendritic region (k < 1.00), but k does not provide an estimate of the inte ractions between the elements in the alloy. To begin to ev aluate the interactions, the curvature was used of the compositions along a line scan in this study. The minimum or maximum point on the line scan curves was the position was determined, and represents the maximum degree of segregation along the line scan. 5.1. Primary Dendrite Arm Spacing The primary dendrite arm spacing (PDAS) was calculated for the eighteen model alloys (Table 4-1). The expected di stance between the de ndrite cores was 300 mm. The values calculated by the twenty fiel ds of view returned ranged from 253.5 m

PAGE 121

101 (LMSX-3), to 381.9 m (LMSX-9). The PDAS was also calculated from the line scans using the average of the three scans done. The PDAS values from the lines scans ranged from 174.7 m (LMSX-17) to 367.9 m (LMSX-9). The information on PDAS is included in this study for reference only, a nd both methods yielding similar results. When comparing both methods of measur ing the PDAS, the only measurements that were greater than one standard devi ation from the mean were those for LMSX-10 and -17. Six of the measurements were within 20 m of one another (LMSX-3, -9, -11, -13, -15, and -18). Of the remain ing ten alloys, eight were with 50 m of one another. The only two alloys that had a difference of greater than 70 m were LMSX-1 and -2. The standard deviations for the PDAS m easurements were larg e (typically around 70 m) and this is probably due to the heterogeneous nature of the solidif ication structure and differences in solidification rates in local regions of that specimen. 5.2. Partitioning Coefficient and Segregation This section describes the reasoning a nd methods for determining the partitioning coefficients and then continues on to eval uate the eleven alloy systems examined. 5.2.1. Comparison of k and Techniques for Examining Segregation The idea for the use of a different an alytical technique for explaining the segregation, stemmed from the an alysis of the very different behaviors observed in the line scans for Ni and Ta in LMSX-9, -10, 1, and -11 (Figure 5-1 and 5-2). When the partitioning coefficient k was calculated from the EMPA data, the raw data for Ni exhibited a greater degree of segregation in LMSX-11 than Ta, but Ta was more heavily segregated in LMSX-9, -10, an -1. The kNi and kTa did not indicate this trend

PAGE 122

102 (Table 4-2). The curvature of the trendline, was then used to better describe the segregation behavior of the partitioni ng of the elements in the system. The following is an example to illustrate the difference in k and Assume the segregation of two elemental additions, to a Ni-base superalloy, A (7.5 wt%) and B (2.5 wt%), is measured using a line scan. The da ta from the line scans behaves in a parabolic manner similar to the elements described in this study (Figure 5-3). k would be calculated in accordance with equation 1-1, a nd would be equal to 4 for both elemental additions and both segregate strongly to the de ndrite core. A more scientific method of determining the partitioning would be by comp aring the extreme values to the expected value (C/C0). Given that the average value in Figure 5-3 (A: 7.50, B: 2.50), a similar result also occurs. Both elements would have the same value for segregation of 1.6. However, when the data from the line scan is examined, element A segregates more strongly than element B. The trendlin es were determined for element A (38.571 x2 39.857 x + 13.286) and element B (12.857 x2 13.286 x + 4.4286), and from these, the was calculated to be 77.14 and 25.17 for elements A and B respectively. Those values of indicate that the elements do still segregat e to the dendrite core, and also which element segregates more strongly based on th e elements compositional gradient. The data generated in this study was combin ed with literature reports to perform a similar comparison of real data. Th e k data acquired in this study (kB) was compared to the k data compiled by F. Fela (kA) (Table 4-2), and compared to trends found in literature4. The technique used in this study ag reed well with prio r and some published work (when alloys of similar elemental compos itions are examined). This indicated that

PAGE 123

103 Plot or Ni Segregation Due to Varying Re Content with Normalized PDAS50.00 52.00 54.00 56.00 58.00 60.00 62.00 64.00 66.00 68.00 70.00 00.10.20.30.40.50.60.70.80.91 Normalized PDASwt% Ni LMSX-1 LMSX-9 LMSX-10 LMSX-11 Figure 5-1: Ni segregation pl ot for LMSX-9, -10, -1, and -11. Trendlines were added to show degree of segregation of Ni obs erved as the Re content was increased. Plot of Ta Segregation Due to Varying Re Content with Normalized PDAS0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 00.10.20.30.40.50.60.70.80.91 Normalized PDASwt% Ta LMSX-1 LMSX-9 LMSX-10 LMSX-11 Figure 5-2: Ta segregation plot for LMSX-9, -10, -1, and -1 1. Trendlines were added to show degree of segregation of Ni obs erved as the Re content was increased.

PAGE 124

104 k' ComparisonElement A: y = 38.571x2 39.857x + 13.286 Element B: y = 12.857x2 13.286x + 4.42860 2 4 6 8 10 12 14 00.10.20.30.40.50.60.70.80.91 Normalized PDASwt% element A B Poly. (A) Poly. (B) Figure 5-3: Example sh owing data for k and from two idealized elemental segregation profiles based on a normalized PDAS. Th e equations for each trendline are indicated on the graph. the technique of using line scans did not offset the data collected a ppreciably and did not produce erroneous results. The data was next compared to the kB data and trends were compared. The trends for kB and were nearly identical (Table 4-3) The only differences occurred in the elements that exhibited only a slight segregation preference. Therefore, the data that was obtained, fit the kB data, and agreed with kA data from a previous study. kB and values are listed in Table 4-3. The use of has two additional benefits. Since the composition is based on 100%, all of the trendline constants sum up to 100. When the second derivative is taken, the curvatures should sum to zero (or close to zero). This indicates ther e are no errors in the

PAGE 125

105 data used for the analysis; i 0, where i is one of the el ements in the alloy. This requirement for the s to sum to zero is due a function of the mathematics used. Additionally, overall effects of alloy segregation can be identified visually (from the graphs as indicated by the overall changes in of in the appropriate graphs) or mathematically ( ij, where i is one of the elements in alloy j). Whichever ij is at a minimum for a set of alloys being comp ared, that alloy exhib its the least overall amount of segregation of those alloys comp ared. The complete list of all of the mathematical sums of k are listed in Table 51. The alloys in Table 5-1 are listed in order of lowest i to highest i Table 5-1: i for the eighteen model alloys and CM SX-4 listed in order from lowest to highest. Alloy i Alloy i Alloy i LMSX-9 57.07 LMSX-16 152.57 LMSX-18 202.24 CMSX-4 69.07 LMSX-14 153.72 LMSX-17 222.65 LMSX-7 108.71 LMSX-15 158.29 LMSX-11 249.41 LMSX-8 128.99 LMSX-12 159.78 LMSX-4 132.11 LMSX-3 173.00 LMSX-10 140.75 LMSX-2 178.25 LMSX-5 147.01 LMSX-13 186.02 LMSX-1 150.88 LMSX-6 189.83 5.2.2. Cobalt Effects The effect of Co addition on solidification and segregation were examined using LMSX-1 (12.2 wt% Co), -2 (8 wt% Co), and -3 (4 wt% Co). LMSX-1 is based on the chemistry of Ren N6 (12.5 wt% Co), and LMSX-3 is based on CMSX-10 (4 wt% Co). All three of the alloys were examined in the as-cast condition to investigate each elements segregation pattern and then compar ed against the varying Cr concentration to evaluate the effects.

PAGE 126

106 Figures 4-10 and 4-11 contain the kB graphs for Cr, and Figure 4-38 contains the graph for the Co additions. Both sets of data and graphs show similar trends. In all cases, as the amount of Co is increased in th e alloy, the elemental pa rtitioning decreased. kRe, kW, kCo, and kCr were all greater then one i ndicating that these elements partitioned to the dendrite core. The k curves indicate a large decrease in the partitioning of Re due to the addition of 8 wt% Co, and then there is no further change as the Co content is increased. The k curve for W indicated a decrease in segregation as the Co content was increased to 8 wt% Co, but to a lesser degree than Re, and kW did not change further with increasing Co content. kCo and kCr exhibited little change due to increasing Co concentrations. The partitioning coefficients for Ni, Ta, and Al were all less then 1.00, and therefore these elemen ts were observed to segregate to the interdendritic region. kTa increased from the 4 wt% Co to 8 wt% Co concentration, and then did not change further as more Co was added to the alloy. kAl also increased, but from the 4 wt% Co to the 12.2 wt% Co cont ent alloy, and at a constant rate. The partitioning coefficient for Ni, kNi, decreased slightly at Co cont ents greater than 8 wt%. The value trends were similar to the kB trends. Re decreased slowly from the 4 wt% Co to the 8 wt% Co concentration, a nd then decreased more rapidly as Co concentration was increased to the 12.2 wt%. W exhibited a constant decreasing trend as the Co content was increased 4 wt% Co to 12.2 wt% Co. The Co increased as the Co content was increased from 4 wt% up to 8 wt%, and then remained constant up to 12.2 wt% Co. This increase in Co segregati on can be explained due to the amount of increasing amounts of Co in the Ni matrix. Cr did not exhibit any change due to increasing Co concentrations. The curvature va lues indicated that Re, W, Cr, and Cr all

PAGE 127

107 segregated to the dendrite cores. The Ta and Al were not visibly affected when the Co concentration was increased from 4 wt% to 8 wt%. However, when the Co content was increased further, both Ta and Al decreased (became less negative). Ni segregation increased ( Ni decreased, became more negative) from 4 wt% Co to 8 wt% Co. As the Co content was further increased, Ni increased slightly, but still exhibited more segregation then originally at 4 wt% Co. This can be attributed to Co substituting for Ni in the lattice. Overall, as the Co content was increa sed from 4 wt% to 12.2 wt%, segregation decreased in both analyses, k and (Based on Figure 4-24). Therefore, Co additions are a viable method to decrease the segregati on of the heavy elements Re, W, and Ta. In addition to this, other work on this alloy indicated similar results.16,38,43 5.2.3. Chromium Effects The effect of Cr additions on solidification and segregation were examined using LMSX-5 (2.1 wt% Cr), -1 (4.1 wt% Cr), and -4 (6.15 wt% Co). All three of the alloys were examined in the as-cast condition to investigate each elements segregation pattern and then compared against the varying Cr concentration to evaluate the effects. Figures 4-8 and 4-9 contain the kB graphs for Cr, and Fi gure 4-39 contains the graph for Cr. Both sets of data and graphs show similar trends that as the amount of Cr is increased in the alloy, the elem ental partitioning decreases. kA,Cr and kB,Cr for LMSX5 indicated different segregat ion directions, but this wa s the only observation where kA and kB did not agree. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores. The partitioning coefficient curves, k, indicated an increase in the

PAGE 128

108 partitioning of Re as the Cr content was in creased from 2.1 wt% to 4.1 wt%. When the Cr content was increased from 4.1 wt% to 6.15 wt% exhibited no further effect on the segregation of Re. kW decreased slightly as Cr conten t was increased. The segregation behavior of Co and Cr both increased as the Cr composition was increased form 2.1 wt% Cr to 6.15 wt% Cr, with Co segregating to a slightly greater degree than Cr. kTa, kAl, and kNi were all less than 1.00 (indicating segrega tion to the interdendritic region). Ta was the most heavily segregated of the elements partitioning to the interdendritic region. As the Cr content was increased, kTa continued to decrease (approach zero) indicating increasing segregation. Increa sing the Cr content from 2.1 wt% to 4.1 wt% had no affect on kAl, but as the content was furt her increased to 6.15 wt%, kAl began to increase (approach 1.00) indicating less segregation. The segregation of Ni was not affected by varying the Cr content in the alloys. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The increasing the Cr c ontent from 2.1 wt% to 4.1 wt% had no observable effect on Re, but as the Cr content was furt her increased to 6.15 wt%, the segregation of Re decreased. W exhibited a constant decreasing trend due to the increased Cr content. The degree of Co segr egation increased slight ly as the Cr content was increased in the alloy. Cr increased slightly as Cr content was increased. Cr partitioned to the interdendritic region in LMSX-5 (2.1 wt% Cr), and then was observed to partition back to th e dendrite core for higher Cr concentrations. Al also increased (became less negative) as the Cr content was increased. Ni was observed to segregate to the interdendritic regi on more severely in LMSX-5 (2.1 wt% Cr) than Ta, but as the Cr concentration was increased, Ta began to segregate more strongly than Ni. The Ni

PAGE 129

109 exhibited an increasing trend (became less negative) as the Cr content increased. The segregation behavior of Ta, Ta, increased with increasing Cr content to 4.1 wt% Cr. As the Cr concentration was increased further, Ta did not change. Overall, as the Cr content was increase d from 2.1 wt% to 6.15 wt%, segregation decreased somewhat in both analyses, k and (determined mathematically: i4 = 147, i1 = 150, and i5 = 132). Therefore, Cr addi tions are a viable method to decrease the segregation of the heavy elements Re, W, and Ta, but Cr has been identified as an element that decreases the solvus temperature, and decreases alloy stability44. Based on this information, the use of Cr to d ecrease segregation would have to be balance with other necessary properties (i.e. microstructural stab ility or strength).16 5.2.4. Rhenium Effects The effect of Re additions on solidification and segregation was examined using LMSX-9 (0 wt% Re), -10 (2.95 wt% Re), -1 (5.9 wt% Re), and -11 (8.7 wt% Re). All four of the alloys were examined in the as-cast condition to investigate each elements segregation pattern and then compared ag ainst the increasing Re concentration to evaluate the effects. Figures 4-11 and 4-12 contain the kB graphs as a function of Re content, and Figure 4-40 contains the versus Re content plot. Both sets of data and graphs show similar trends that as the am ount of Re is increased in th e alloy, the elemental partitioning increases. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores, with the exception of kCr in LMSX-9 which was observed to partition slightly to the interd endritic region. The partitioning coe fficient, k, when plotted versus

PAGE 130

110 Re content indicated an increase in the pa rtitioning of Re, as the Re content was increased. The increase in Re segregati on with increasing Re content was the most severe increase in partitioning observed in these alloys. kW was unaffected by the 1 and 2 at% additions of Re, but increased slightly with the addition of the third 1 at%. The segregation behavior of Co was unaffected by the increase in Re content. Cr, as was stated, segregated to the inte rdendritic region in LMSX-9 (kCr < 1.00), but when Re was added, Cr began to segregate slight ly to the dendr ite core, but kCr did not increase further until the final 1 at% Re was added, and then kCr increased slightly. kTa, kAl, and kNi were all less than 1.00 (indicating segregation to the interdendritic re gion), except for kNi in LMSX-9 exhibited a weak tendency to segreg ate slightly to the dendrite core. Ta, Al, and Ni all exhibited trends of increasing segregation as the Re content was increased. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). Re was the most strongly segregated element ( Re the largest) when only 1 at% was added in LMSX-10. As the Re content was increased further, Re increased in a parabolic manner. The degree of segreg ation of W decreased slightly as the concentration of Re was increased. Co increased initially with the addition of 2.95 wt% Re, but then only increased slightly mo re as the Re content was increased. Cr indicated that Cr segregated to the interdendritic regi on in LMSX-9 (0 wt% Re). With the addition of 1 at% Re, Cr began to segregate to the dendrite core, but was not affected with the further additions of Re. The addition of a third 1 at% Re caused a slight increase in Cr. With no Re present, the curvature for Ni ( Ni) indicated that Ni segregated to the dendritic region. As Re was added to the alloy, Ni began to decrease (become more negative), and therefore segregat e more to the interdendritic region. When the Re content

PAGE 131

111 was at 8.9 wt% (LMSX-11), Ni was observed to be the most heavily segregated element of those that segregated to th e interdendritic region. At lo wer Re levels, Ta was the most heavily segregated element that segregated to the interdendritic region, and was the most heavily segregated element in the model alloys LMSX-9 and -10. When the Re content was increased, Ta decreased with the first addition, and indicated no further effects due to increasing Re content. Al had no observable change due to increasing Re content until the third 1 at% Re was added (LMSX-11). With the final addition of 1 at% Re, Al decreased slightly. Overall, as the Re content was increa sed form 0 wt% to 8.9 wt%, segregation increased in both analyses, for the partit ion coefficients, k, and the curvature, (Figure 4-40). Re is a beneficial elemental addition, but increasing the Re c ontent in these alloys increased the segregation (kB and ) of each element in each alloy. When Re is considered for alloying of a superalloy, the me rits it brings must be balanced with the segregation problems that are also present. These segregation problems can lead to microstructural instabilities and extended solution heat treatments.16 5.2.5. Tungsten Effects The effects of increasing the W concentr ation on solidification and segregation were examined using LMSX-1 (5.85 wt% W) and -6 (8.6 wt% W). These alloys were examined in the as-cast conditi on to investigate each elemen ts segregation pattern as a function of W concentration to evaluate the effects. Figures 4-13 and 4-14 contain the kB graphs as a function of W content and Figure 4-41 contains the graph for W. Both sets of da ta and graphs indicate that the partitioning increases slightly as the amount of W is increased in the alloy. However,

PAGE 132

112 there was a discrepancy between kB and when examining the partitioning of Re. kRe was observed to decrease with increasing W content, while Re was observed to increase slightly with increasing W cont ent. This difference is being attributed to the scatter that is inherent when k is determ ined, and is corrected for using kRe, kW, kCo, and kCr were all greater than one, indicating that these elements segregateto the dendrite co res. As was stated, kRe exhibited a decreasi ng trend as the W content was increased. This is surprising since both W and Re segregate to the dendrite core, and both are very dense elements. kW indicated that W was segregating more as the W content was increased. kCo and kCr had no clear trend in their segregation behaviors as the W concentr ation was increased. kTa, kAl, and kNi were all less than 1.00 (indicating segregation to th e interdendritic region). Ta and Al both exhibited an increase in segregation due to the increase in W content. The segregation of Ni was observed to decrease slightly with th e increased concentration of W. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). Re was the most heavily segregated element, and when the W content was increased, Re increased slightly, indicating a s light increase in the segregation behavior of Re. The segregation of W and Co also exhibited an increasing trend as W content was increased in the alloy ( W increased more than Co). Cr segregation increased slightly due to an increase in W content. Al and Ni both became more negative (increasing segregation) as the concentration of W increased. Ta was unaffected by the increase in W. Ta was more strongl y segregated in LMSX-1 (5.85 wt% W) than Ni, but Ni became more segregated than Ta in LMSX-6 (8.6 wt% W).

PAGE 133

113 Overall, as the W content was increased from 5.85 wt% to 8.6 wt%, segregation increased slightly in both analyses, k and (Based on Figure 4-41). W, like Re, is a beneficial elemental addition for solid solu tion strengthening. But increasing W content also increases the partitioning of all the elements present in the alloy, which can lead to longer heat treatment times to remove the segr egation in these alloys. Work reported by F. Fela on this alloy indicated similar results.16 5.2.6. Tungsten Effects with an Addition of Molybdenum The effects of an increasing W concentra tion with a Mo addition on solidification and segregation were examined using LMSX -7 (3.1 wt% W, 1.6 wt% Mo) and -8 (5.85 wt% W, 1.6 wt% Mo). Both of the alloys were examined in the as-cast condition to investigate each elements segregation patte rn and then compared as a function of W concentration to evaluate the effects. Figures 4-15 and 4-16 contain the kB plots for increasing W content with a Mo addition, and Figure 4-32 contains the versus W content with a Mo. Both sets of data and graphs show similar trends that as the amount of W is increased with an addition of Mo, the elemental partitioning was observed to increase slightly. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores. Re exhibited an increasing de gree of segregation when the W content was increased. The increase in W from 3.1 wt% to 5.85 wt% caused a sm all increase in the segregation of W. The segreg ation of Co was not affected by an increase in W with an addition of Mo. Cr segregation was obser ved to decrease as the W content was increased. kTa, kAl, kMo, and kNi were all less than one, indicating segregation to the interdendritic region. The segr egation of Ta, Mo, and Ni a ll increased as the W content

PAGE 134

114 was increased with the addition of 1.6 wt% M o. The segregation of Al did not change when the W concentration was increased and Mo was added. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The variations in W content in LMSX-7 and -8 had little observable change in Re, Co, Mo, and Ta. Of the elements segrega ting to the dendritic region, W was the only element that exhibited an incr ease in segregation was increased from 3.1 wt% W to 5.85 wt% W. Ni decreased as Ni segregated more due to the increasing W content. Al also exhibited an increase in segregation when the W content was increased from 3.1 wt% to 5.85 wt% and 1.6 wt% of Mo was added. Overall, as the W content was increase d from 3.1 wt% to 5.85 wt% and 1.6 wt% with a constant Mo concentrati on, the segregation incr eased slightly in the k analysis and increased more severely in the analysis (Based Figure 4-42). The increase in segregation caused by the incr easing W content and with a Mo addition may result in extended heat treatment time. 5.2.7. Molybdenum Effects The effect of an addition of Mo on solidification and segregation were examined using LMSX-1 (0 wt% Mo), and -8 (1.6 wt% Mo). Both of theses alloys were examined in the as-cast condition to investigate each elements segregation pattern and then compared as a function of Mo concentration. Figures 4-17 and 4-18 contain the kB versus Mo content, an d Figure 4-43 contains the versus Mo content. As Mo is added to the alloy, th e partitioning decreases, and both sets of data and gra phs show similar trends.

PAGE 135

115 kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores. Re was the most severely se gregated element, and showed the greatest decrease in segregation as Mo was added. The segregation of W and Co both decreased as Mo was added also. kW was greater than kCo. The addition of Mo had no visible effect on the segregation of Cr. kTa, kAl, kMo, and kNi were all less than one, indicating segregation to the interdendr itic region. Ta segregated the most severely, followed by Mo, Al, and then Ni. The addition of Mo caused the most significant decrease in the segregation of Al to decrease the most. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). All of the elements except Cr, Co, and Al e xhibited decreasing segregation due to the addition of 1 at% Mo. Cr and Co both increased slightly indicating a slight increase in segregation with the additiona l Mo content. The addition of 1.6 wt% Mo had no affect on the segregation behavior of Al ( Al was constant). Overall, when 1.6 wt% Mo was added to th e baseline, the segregation decreased in both the k and analyses (Based from Figure 4-43). The decrease in segregation caused by the addition of Mo may result in a d ecrease in heat treatm ent time. Previous reports done by F. Fela on this alloy indicated similar results.16 This also provides some insight into why Ren N6 ha s an addition of 1.1 wt% Mo. 5.2.8. Ruthenium Effects The effect of a Ru addition on solidificat ion and segregation was examined using LMSX-1 (0 wt% Re), -16 (1.6 wt% Ru), and -1 7 (3.2 wt%). All three of the alloys were examined in the as-cast condi tion to investigate each elem ents segregation pattern and then compared against as a function of Ru concentration.

PAGE 136

116 Figures 4-19 and 4-20 contain the kB versus Ru content, and Figure 4-44 contains the versus Ru graph. Both sets of data and gr aphs show similar tre nds, and in general, the segregation behavior of the alloying elemen ts increased as Ru content is increased in the alloy. kRe, kW, kCo, kRu, and kCr were all greater than one indicating segregation to the dendrite cores. The add ition of 1 at% (1.6 wt%, LMSX-16) Ru had no affect on the segregation of Ru. However, when the second 1 at% (LMSX-17) Ru was added, Re exhibited a very large increas e in degree of segregation. W and Cr both exhibited an increase in segregation as the Ru content wa s increased from 0 wt% to 3.2 wt %. The effect of the Ru addition was more pronounced in the degree of segregation of Cr than W. Co exhibited no change in segregation as th e Ru concentration was increased from 0 wt% to 3.2 wt%. The segregation of Ru itself decreased slightly as the Ru content was increased from 1.6 wt% to 3.2 wt%. kTa, kAl, and kNi were all less than one, indicating segregation to the interdendr itic region. The segregation behavior of Ta, like Re, was unaffected by the addition of 1 at% Ru. But when the second 1 at% Ru was added to the alloy, Ta exhibited a large increase in segrega tion. The increased Ru content affected the segregation of Al when the Ru content wa s increased from 1.6 wt% to 3.2 wt%. Increased Ru content had no observable eff ect on the segregation behavior of Ni. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The addition of 1 at% ( 1.6 wt%) Ru had no affect on the for all the elements ( Ta was observed to decrease to a lower value than Ni, but this was attributed to error), except Al, which incr eased slightly. The addition of a second 1 at% Ru (for a

PAGE 137

117 total of 2 at % or 3.2 wt%), caused an incr ease in the segregation of all elements examined. Overall, Ru has no observable effect on th e segregation behavior when 1.6 wt% is added. However, increasing the Ru concentr ation further causes large increases in the segregation of the elements in the alloy (d etermined visually from Figure 4-30). Since addition of 1 at% Ru does not change the se gregation behavior, this addition may be useful in further alloy development. With 3.2 wt% Ru content, the segregation increases substantially. This could lead to extended h eat treatment times and/ or other segregation issues due to localized concentrations of elements unless the alloy is properly heat treated. Previous work by F. Fela on this alloy indicated similar results16 as well as work done by H. Harada and collegues.29 5.2.9. Palladium Effects The effect of an addition of Pd on solidification and segregation was examined using LMSX-1 (0 wt% Pd) and, -18 (1.7 wt% Pd). Both of these alloys were examined in the as-cast condition to investig ate each elements segregation pattern as a function of Pd concentration. Figures 4-21 and 4-22 contain the kB vs.Pd graphs, and Figure 4-45 contains the vs. Pd graph. Both sets of data and graphs show similar trends, and in general, as the amount of Pd is increased in the a lloy, the elemental partitioning increases. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores. The addition of 1.7 wt% Pd cau sed increases in the segregation behaviors of Re, W, Co, and Cr. Re was affected th e most by the addition of 1 at% Pd, followed by W. The segregation of Co and Cr both increas ed by about the same degree as Pd content

PAGE 138

118 was increased. kPd, kTa, kAl, and kNi were all less than one, indicating segregation to the interdendritic region. Pd itself exhibited the largest degr ee of segregation when it was added to the alloy. Ta segregated more than Al or Ni, but the degree of segregation of Al increased more than Ta due to the increased the Pd content. Due to the increase in Pd content, Ni exhibited a sli ght decrease in segregation. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The for Re, W, Co, and Cr all increa se as Pd content is increased. Re had the largest increase followed by Co, kW, and then Cr. Ta and Ni were largely unaffected by increasing Pd conten t, and Ta segregated more th an Ni. The segregation of Al increased as the Pd content wa s increased form 0 wt% to 1.7 wt%. Pd was observed to be less than Al, and greater than Ni (Pd segregated more than Al, but less than Ni). As the Pd content of the alloys was incr eased, there was an increasing degree of segregation (Based on Figure 4-45). The only el ements that exhibited significant changes were Re, Co, and Al. Heat treating alloys that contain an addition of Pd may require extra time to cause the slow diffusing elements (i.e. Re, W) to become evenly distributed throughout the microstructure. Previous work by F. Fela on this alloy indicated similar results16 as well as in published literature.29 Pd has been reported to increase the surface stability of superalloys and could possible bo lster the corrosion resistance of the base alloy. Current work has pointed to the pl atinum group metals (PGM), including Pd and Ru being effective solid soluti on strengtheners and could be us eful as alloying additions. 5.2.10. Tungsten and Molybdenum Effects The effect of substituting Mo for W on solidification and segregation was examined using two different combinations of alloys: LMSX-1 (5.8 wt% W, 0 wt% Mo),

PAGE 139

119 -7 (3.1 wt% W, 1.6 wt% Mo), and LMSX-6 (8.6 wt% W, 0 wt% Mo), -8 (5.85 wt% W, 1.6 wt% Mo). Both combinations of these a lloys were examined in the as-cast condition to investigate each elements segregation pa ttern and examined as a function of alloy content. Figure 4-24 (4-25) contains the kB graph for substituting 1 at% Mo for 1 at% W for LMSX-1 and-7 (LMSX-6 and -8). Figure 4-46 (4-47) contains the graph for substituting 1 at% Mo for 1 at% W for LMSX-1 and -7 (LMSX-6 and -8). Both sets of data and graphs show similar trends, and in general, as Mo is s ubstituted for W, the segregation in the a lloy decreases. Since the trends are identical in Figur es 4-24 and 4-25, only figure 4-24 will be discussed. kRe, kW, kCo, and kCr were all greater than on e, indicating segregation to the dendrite cores. Re, W, and Co all exhibi ted decreasing degrees of segregation when 1 at% Mo was substituted for 1 at% W, while Cr e xhibited a slight increase in the degree of segregation. kTa, kAl, kMo, and kNi were all less than one, i ndicating segregation to the interdendritic region. Ta, Al, and Ni all exhi bited decreasing segregation when 1 at% Mo was substituted for 1 at% W. Mo segreg ated more than Ni, but less than Al. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). Unlike k graphs, there were some differences in the graphs, but this is attributed to the 8.6 wt% W in LMSX-6 (Figure E-2)and will be discussed when the graphs for LMSX-1, -7 and LMSX-6, -8. The substituting of 1 at% Mo for 1 at% W caused the segregation behavior of all the elements to decrease. The substitution of 1 at% Mo for 1 at% W decreased the overall segregation in the alloys (Based on both Figures 4-24 and 4-25) possibly making heat treatment easier.

PAGE 140

120 5.2.11. Tantalum and Aluminum Effects The effects of the formers Ta and Al were investigated. The model alloys for these experiments were LMSX, -12 and -13. LMSX-1 contained 8.6 wt% (3 at%) Ta and 5.55 wt% (13at%) Al. The chemistry of LM SX-12 had an increase of 1 at% Ta (to 3 at%, or a total of 11.2 wt%) and a decrease of 1 at% Al (to 12 at%, or a total of 5.0 wt%). LMSX-13 had Ta decreased by 1 at% (to 2 at %, or 6 wt%) and Al was increased by 1 at% (to 14 at%, or 6.15 wt%). These combinati ons were chosen to maintain a constant volume fraction of 55%. 5.2.11.1 Effect of increased tantalum with decreased aluminum The effects of substituting 1 at% Ta for 1 at% Al on solidification and segregation were examined using LMSX-1 and -12. These two alloys were examined in the as-cast condition to investigate each elements segrega tion pattern as a function of alloy content. Figure 4-26 contains the kB graph for substituting 1 at% Ta for 1 at% Al, and Figure 4-46 contains the graph for substituting 1 at% Ta for 1 at% Al. The graph for kB indicates that substituting 1 at% Ta for 1 at% Al reduced the segregation but the graph for indicates a slight increase in segregation due to this alloy modification. The differences in the graphs are from the effects of Re and Ta, but the differences are slight and are considered errors from sampling. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores. kRe was the only one of these elements that exhibited a decrease in segregation due to substitution of 1 at% Ta for 1 at% Al. The change in segregation behaviors of W and Co were negligible wh en substituting 1 at% Ta for 1 at% Al. The segregation of Cr increase d slightly for this change in alloy chemistry. kTa, kAl, and kNi

PAGE 141

121 were all less than one, indicating segregation to the interdendritic region. When 1 at% Ta was substituted for 1 at% Al, the segregation of Ta decreased, as well as the segregation of Ni, but to a lesser degree. This modificat ion to the alloy chemistry had no appreciable effect on the segregation of Al. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The segregation behaviors of Ta Co, and Al increased when 1 at% Ta was substituted for 1 at% Al. The segrega tion for Re, and Ni both decreased slightly when the alloy chemistry was modified by substituting Ta for Al. This substitution had no effect on the segregati on behaviors of W and Cr. As was presented, kB indicated a decrease in segreg ation due to 1 at% Ta being substituted for 1 at% Al, but indicated that segregation increased slightly for this same change in alloy chemistry. With the increase in Ta content, it would be expected to observe an increase in the se gregation in Ta (Ta is a dense element, and has a BCC lattice), but Ta may cause the Re to become mo re dispersed within the microstructure. It is know that Ta does increase castability, and th is may partially explain this effect. To fully ascertain the effect of the substitution of 1 at% Ta for 1 at% Al, additional testing would be required on alloys that are not present in the all oy matrix (Table 3-1) (i.e. LMSX-1 baseline with the addition of 1 at% Ta). 5.2.11.2. Effect of decreased tantalum and increased aluminum The effects of substituting 1 at% Al for 1 at% Ta on solidification and segregation were examined using LMSX-1 and -13. These two alloys were examined in the as-cast condition to investigate each elements se gregation pattern as a function of alloy composition.

PAGE 142

122 Figures 4-27 and 4-28 contain the kB graphs for substituting 1 at% Al for 1 at% Ta, and Figure 4-49 contains the graph for substituting 1 at% Al for 1 at% Ta. Both sets of data and graphs show similar trends, a nd in general, as the Al is substituted for Ta, the segregation in the alloy increases. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores for all except Cr in LMSX13 which was observed to segregate to the interdendritic region. As Al was substituted for Ta, the segregation of Re increased to the greatest degree followed next by W. Co exhib ited a slight increase in segregation when Al was substituted for Ta. The segregation of Cr, as was stated, ch anged direction from the dendrite core to the interdendritic region with this alloy modification. kTa, kAl, and kNi were all less than one, indicating segr egation to the interd endritic region. The segregation of Ta, Al, and Ni all increased (i n this order) when 1 at% Al was substituted for 1 at% Ta. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The segregation of Re, W, a nd to a lesser degree, Co, all exhibited increased segregation when 1 at% Al was subs tituted for 1 at% Ta. Cr was observed to segregate to the dendrite core in LMSX-1 and then to the interdendritic region in LMSX13. The segregation of Ni and Al also exhibited increasing trends when Al was substituted for Ta. The segregation of Ta exhibited a decrease with the alloy modification, and this can be attributed to the decrease of 1 at% Ta when it was substituted for 1 at% Al. In LMSX-13, Ni was observed to segregate more than Ta; whereas, Ta was observed to segregate more severely in LMSX-1 than Ni.

PAGE 143

123 Both the kB analysis and analysis indicate that when 1 at% Al is substituted for 1 at% Ta, the overall segregation in the alloy increases. This can be observed by Figure 449. A final comparison was done between LMSX-12 and -13 to examine the full effect of substituting Ta for Al and then substituting Al for Ta. Figures 4-29 and 4-30 contain the graphs for the kB analysis, and Figure 4-50 c ontains the graph for the analysis. These graphs are nearly identical to 427, 4-28, and 4-49, and there are no additional trends to be observed. 5.2.12. Tantalum and Aluminum Effects with an Addition of Titanium Ta and Al are not the only formers examined in this investigation. Two model alloys had a small quantity of Ti (another former) added with Ta and Al reduced separately. The model alloys for these experiments were LMSX-14 and -15. The chemistry of LMSX-14 had an decrease of 1 at% Ta (to 1 at%, or a total of 6.0 wt%) and an addition of 1 at% Ti (0.80 wt%). LMSX-15 had Al decreased by 1 at% (to 12 at%) and then the addition of 1 at% Ti (0.80 wt%). These combinations were chosen to again maintain a constant volume fraction of 55%. 5.2.12.1. Effect of decreased tantalum with titanium The effect of substituting 1 at% Ti for 1 at% Ta was examined using LMSX-1 (8.6 wt% Ta, 0 wt% Ti) and -14 (6.0 wt% Ta, 0.8 wt% Ti). Both of these alloys were examined in the as-cast conditi on to investigate each elemen ts segregation pattern as a function of the alloy chemistry. Figures 4-31 and 4-32 contain the kB graphs when 1 at% Ti was substituted for 1 at% Ta, and Figure 4-51 contains the graph for the same change in alloy chemistry.

PAGE 144

124 Both sets of data and graphs show similar trends, and in general, as Ti is substituted for Ta, the elemental segregation in the alloy increased slightly. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores. The degree of segregation behavior of Re increased when Ti was substituted for Ta in this alloy chemistry. W exhibited the largest increase in segregation when 1 at% Ti was substituted for 1 at% Ta The segregation of Cr increased more significantly than did the segreg ation for Re when substituti ng 1 at% Ti for 1 at% Ta. kTi, kTa, kAl, and kNi were all less than one, indicating segregation to the interdendritic region. The segregation behavi or of Ta and Al increased by similar amounts as Ti was substituted for Ta in this change in alloy chemistry. However, the segregation of Ni decreased with the substitution of 1 at% Ti fo r 1 at% Ti. Ti itself was segregated more than Ta, Al, or Ni when it wa s added as a substitute for Ta. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The segregation behavior of Re exhibited a decrease in magnitude when 1 at% Ti was substituted for 1 at% Ta. W exhibited an increase in segregation for the substitution of 1 at% Ti for 1 at% Ta. Co exhibited a slight in crease in segregation, and Cr exhibited a slight decr ease in segregation when 1 at% Ti was substituted for 1 at% Ta. The degree of segregation of Ni and Al were observed to increase, with Ni segregating more severely than Al and Ni e xhibited a greater increase in magnitude with the substitution of Ti for Ta. Ta exhibite d a decrease in segregation when Ti was substituted for Ta. Ti was the least segregated element of the formers. The overall segregation increases according to kB graphs, but this trend not immediately observed in the graph. The overall segregation based on was

PAGE 145

125 determined mathematically, and agreed with the kB analysis in that when 1 at% Ti was substituted for 1 at% Ta segregation increase d. However, the increase shown by k could be attributed to error in the analysis ( i1 = 150, and i14 = 153). A difference in this kB and analyses was noted with the se gregation behavior of Ti: the kB indicated that Ti it was the most se verely segregated of the formers, and indicated Ti was the least segregated. This difference is being at tributed to the high scatter when determining k, and the argument brought forth in the example in this chapter. 5.2.12.2. Effect of decreased aluminum with titanium The effect of substituting 1 at% Ti for 1 at% Al on solidification and segregation was examined using LMSX-1 (8.6 wt% Ta, 0 wt % Ti) and -15 (5.1 wt% Al, 0.8 wt% Ti). Both of these alloys were examined in the as-cast condition to inve stigate each elements segregation pattern as a func tion of the alloy chemistry. Figures 4-33 and 4-34 contain the kB graphs when 1 at% Ti was substituted for 1 at% Al, and Figure 4-52 contains the graph for the same change in alloy chemistry. Both sets of data and graphs show differe nt trends when Ti was substituted for Al. kRe, kW, kCo, and kCr were all greater than one, indicating segregation to the dendrite cores. The degree of segregation beha vior of Re increased severely when Ti was substituted for Al in this alloy chemistry. W exhibited an increase in segregation when 1 at% Ti was substituted for 1 at% Ta. The degree of segregation of Cr and Co both increased. Co was observed to segregate mo re than Cr, but the segregation of Cr increased more than the segregation for Co when substituting Ti for Al. kTi, kTa, kAl, and kNi were all less than one, indicating segreg ation to the interdendritic region. The segregation behavior of Ta a nd Al increased by similar amounts as Ti was substituted for

PAGE 146

126 Ta in this change in alloy chemistry. Howeve r, the segregation of Ni decreased slightly when this substitution was done. Ti itself was se gregated more than Ta, Al, or Ni when it was added as a substitute for Al. The curvature, values for these elements follow the same trends as kB (i.e. kB < 1.00, and < 0). The segregation behavior of Re was observed to decrease slightly due to the substitution of 1 at% Ti for 1 at% Al. The segregation behavi ors for W, Co, and Cr all increased by similar amounts (W was the mo st segregated of these three, followed by Co and then Cr) when Ti was substituted for Al Al and Ni exhibite d slight increases in their respective degrees of segregation when 1 at% Ti was substituted for 1 at% Al. Ta exhibited a decrease in segregation wh en substituting 1 at% Ti for 1 at% Al. The overall segregati on trends differ for kB and kB indicated an increase in segregation when 1 at% Ti for 1 at% Al, while indicated that the overall segregation decreases slightly. A difference in the analyses for kB and was observed in the segregation behavior of Ti: the kB indicated Ti was the most severely segregated of the formers, and indicated that Ti was the least segr egated. This difference is from the method and data that is used to calc ulate k. The value used for the xdendrite core was 1.42 and the xinterdentic region was 0.42, therefore kTi was 0.372. A final comparison was done between LMSX-14 and -15 to examine the full effect of substituting Ti for Ta and Al. Figures 4-35 and 4-36 contain the kB graphs, and Figure 4-53 contains the graph. The overall segregation follows very closely to that shown in Figure 4-52. The degree of segrega tion of Re was observed to increase more severely when 1 at% Al was substituted with 1 at% Ta with 1 at% Ti. W and Co both exhibited increases in segregation when Al was substituted for Ta with Ti, and the

PAGE 147

127 segregation of Cr was observed to decrease. The segregatio n behaviors of the elements segregating to the interdendritic (Ni, Al, Ta and Ti), all exhibited increased degrees of segregation with the modificati on to alloy chemistry. Ti was the most segregated of these elements. There were few similarities between kB and trends when 1 at% Al was substituted with 1 at% Ta and a constant level of 1 at% Ti was maintained in the alloy. Re, Co, and Cr exhibited increased segregation as 1 at% Al was substituted with 1 at% Ta with 1 at% Ti. W exhibited a decreasing se gregation due to this change in alloy composition. The segregation of Ti increased slightly and Al segregated slightly less when Al was substituted for Ta. Finally the segregation of Ta was observed to increase the same amount that the segregation of Ni was observed to decrease. Overall, when 1 at% Al was substituted with 1 at% Ta with 1 at% Ti maintained in the alloy, kB indicates an increase in segregati on. The overall effect as indicated by had to be determined mathematically ( i14 = 153, and i15 = 158), which only indicated a slight in crease in segregation. However th e difference calculated may be within experimental error. 5.3. Scheil Analysis To check the validity of this technique of data analysis, data was collected for LMSX-3 in the method described by M.N. Gungor36, using 225 data points.11,38 Data was also collected for CMSX-4 using the techniqu es described in this study and compared to similar graphs found in literature to exam ine the general accuracy of the technique.

PAGE 148

128 5.3.1. Analysis of LMSX-3 The Full analysis was done on LMSX-3 and graphs were then plotted showing the liquid to solid segregation curve that is common to the Gungor method. The data collected from the Short analysis (the technique used in this investigation) was added to these curves and then compared. The curves were only examined for general shape, and no Scheil regression work was done. The curves generated by the Full and Shor t analyses were similar to each another (Figures 5-4, 5-5, and Appendix D). The goa l of this was to see if the shape of the curves were similar for both analyses (Full and Short). Both curves did have similar shapes from both analyses. The similar shapes of the two curves were used to verify that the data collected by the Short analysis was indeed generally accurate when compared to that of the Full analysis. 5.3.2. Analysis of CMSX-4 The LMSX models have little published on their properties and characteristics. Therefore, to evaluate the an alysis technique used in this study, a specimen of as-cast CMSX-4, and then Scheil curves were deve loped and compared to similar curves in literature (Figures 5-6 through 513). In the graphs found in th e literature, th e error bars were ignored and only the average poin ts examined for comparison purposes. The curves for Re (Figures 5-6 and 5-7), Ta (Figures 5-8 and 5-9), and W (Figures 5-11 and 5-16) all look similar in shape and slope and were well within acceptable agreement. The curves for Ti (Figures 5-10 and 5-11) have some s light differences, but still show the same general shape. The Ti curve in Figure 5-10 s hows Ti increasing at a uniform rate, whereas in Figure 5-11, Ti is shown to begin from a constant amount and then begin to increase at a non-uniform rate.

PAGE 149

129 With the Scheil curves generated for CMSX -4 by the technique described in this report and the Scheil curves f ound in open literature, there is some degree of correlation between the two methods. Even though the co mmon analysis is statistically unbiased, the technique used in this report, which is statistically biase d, provides the same information in approximately half of the time.

PAGE 150

130 LMSX-3 Cr Scheil Comparison0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.10.20.30.40.50.60.70.80.91 vol%wt% Cr Full Short Figure 5-4: LMSX-3 Scheil curves for Full and Short techniques for Cr. LMSX-3 Al Scheil Analysis0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.10.20.30.40.50.60.70.80.91 vol%wt% Al Full Short Figure 5-5: LMSX-3 Scheil curves for Full and Short techniques for Al.

PAGE 151

131 Figures 5-6 and 5-7: Scheil curves for Re from CMSX-4. Figure 5-6 was done using the techniques described in this study, and Figure 5-7 was from literature.43 Figures 5-8 and 5-9: Scheil curves for Ta from CMSX-4. Figure 5-8 was done using the techniques described in this study, and Figure 5-9 was from literature.43 Scheil Analysis for Re in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Re Re Scheil Analysis for Ta in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ta Ta

PAGE 152

132 Figures 5-10 and 5-11: Scheil curves for Ti from CMSX-4. Figure 5-10 was done using the techniques described in this study, and Figure 5-11 was from literature.43 Figure 5-12 and 5-13: Scheil curves for W from CMSX-4. Figure 5-12was done using the techniques described in this study, and Figure 5-13 was from literature.43 Scheil Analysis for Ti in CMSX-40.00 0.50 1.00 1.50 2.00 2.50 3.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ti Ti Scheil Analysis for W in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% W W

PAGE 153

133 CHAPTER 6 CONCLUSIONS The purpose of this study was to improve upon the understanding of how differential elemental additions affect the segregation of elements in superalloys. A new technique was developed to determine the individual elem ental segregations; instead of random points from the dendrite core and inte rdendritic region, a line scan fro m dendrite core to dendrite core through the interdendritic region was used. The partitioning coefficient, k, was determined using this new technique (kB in this study), and compar ed to a k value done using a more tradit ional technique (kA in this study, done by F. Fela). A k < 1.00 indicated segregation to the in terdendritic region, and a k > 1.00 indicated segregation to the dendrite core. The k values determine by this new technique compared very closely to that of the prior work. The only exceptions ca me from elements that showed very little segregation preference between the dendrite core and the interdendritic region. Scheil curves were also developed to compar e the shape and slope of the curves from the new (Short analysis) technique and compared to a standard (Full analysis) technique. The shapes and slopes of both curves were very similar and agreed wi th one another. An advantage of the new (Short analysis) is its ti me requirement. The scans for LMSX-3 were done in 4.5 hrs using the new (Short analysis ), and 12.5 hrs using the standard (Full analysis). The Short analysis, although st atistically skewed, directly indicates the composition gradient between dendrite cores. Wh ereas the Full analysis looses this direct indication of the composition gradient at th e cost of being stat istically unskewed. In

PAGE 154

134 addition, the Scheil curves for CMSX-4 were developed using the new (Short analysis) technique and compared favorably with the literature. Having shown that kB is equivalent to kA, and the Scheil curves for the data were similar, the study could progress further. k does not give a clear idea of the degree of segregation due to the way it is calculated. The degree of segregat ion was determined by calculating the curvature, from a trendline from the line scan data. A > 0.00 indicated segregation to the de ndrite core, and a < 0.00 indicated segregati on to the interdendritic region. Since kB agreed with kA and the Scheil curves, the data collected is valid. With the data collection valid, and the part itioning based on this data al so verified, further analyses done with the data that provide similar results are also valid. This further analysis was done using The effects of elemental segregation for th irteen trends were evaluated based on the The complete results of the effects of elemental segregation are listed in Table 6-1. The overall effects of the changes in alloy chem istry/composition are listed as follows: Increasing the Co content caused segregation to decrease slightly with the increased Co from 4 wt% (4 at%) content of 8 wt% (8 at%), and a slightly greater decrease as the Co content was increased to 12.2 wt% (13 at%) Increasing the Cr content caused the overall segregation within th e alloy to decrease slightly as Cr content was increased from 2.1 wt% (4 at%) to 6.15 wt% (6 at%). Increasing the Re content caused segregation to increase, with a large initial increase when 1 at% Re was added, and a slight furt her increase with the addition of a second 1 at% Re. When 3 at% Re was added th ere was a very large increase in the segregation within the alloy. Increasing the W content caused segregati on to increase as wt% W was increased from 5.85 wt% (2 at%) to 8.6 wt% (3 at%).

PAGE 155

135 Increasing the W content with an additi on of Mo caused segr egation to increase slightly due to the addition of 1.6 wt% (1 at%) Mo and W content increased form 3.1 wt% (1 at%) to 5.85 wt% (2 at%). Increasing the Mo content caused segregation within the alloy to decrease due to the addition of 1.6 wt% (1 at%) Mo. Increasing the Ru content caused no initia l change in segrega tion when 1.6 wt% (1 at%) Ru was added. However, the additi on of a second 1.6 wt% (1 at%) Ru, for a total of 3.2 wt% (2 at%), cause d a large increase in the overall segreg ation within the alloy. Increasing the Pd content was increased fr om 0 wt% to 1.7 wt% (1 at%), there was an overall increase in the elemental segrega tion within the alloy. Substituting equal amounts of Mo (1 at% Mo) for W (1 at% W) caused the overall segregation decrease. Substituting equal amounts of Ta (1 at% Ta) fo r Al (1 at%) caused very little change in the overall elemental segregation within the alloy as Ta was substituted for Al. However, the segregation di d decrease very slightly. Substituting equal amounts of Al (1 at%) for Ta (1 at%) caused an increase in the elemental segregation as Al was substituted for Ta. Substituting equal amounts of Ta (1 at%) fo r an addition of Ti (1 at%) caused segregation not to change. Substituting equal amounts of Al (1 at%) fo r an addition of Ti (1 at%) caused the overall segregation to decrease slightly. The i also provides a ready indication to the segregation between different alloys. LMSX-9 indicated the lowest degree of segregation and LMSX-11 the greatest degree of segregation (Table 5-1). This ma y help narrow down the search for new alloy compositions, and decrease cost and time in their development, as well as give insight as to how some alloys were developed.

PAGE 156

136 Table 6-1: Elemental segregation effects for each combination of alloy compared. indicates an increase in segregation, indicates a decrease in segregation, and indicates no change in segr egation. Number of arrows is indicative of degree of segregation. AlloysNi CrCoMoWRe Ta AlTiRu wt% Co 4 wt%-8 wt% 1,2 8 wt%-12.2 wt% 2,3 wt% Cr 2.1 wt%-4.1 wt% 5,1 4.1 wt%-6.15 wt% 1,4 wt% Re 0 wt%-2.95 wt% 9,10 2.95 wt%-5.9 wt% 10,1 5.9 wt%-8.7 wt% 1,11 wt% W 5.85 wt%-8.6 wt% 1,6 wt% W +Mo 3.1 wt%-5.85 wt% 7,8 wt% Mo 0 wt%-1.6 wt% 1,8 wt% Ru 0 wt%-1.6 wt% 1,16 1.6 wt%3.2 wt% 16,17 wt% Pd 0 wt%1.7 wt% 1,18 Mo substitution for W + 1 at% Mo, 1 at% W 3.1 wt% W, 1.6 wt% Mo 1,7 5.85 wt% W, 1.6 wt% Mo 6,8

PAGE 157

137 Table 6-1 (cont.): Elemental segregation eff ects for each combination of alloy compared. indicates an increase in segregation, indicates a decrease in segregation, and indicates no change in segr egation. Number of arrows is indicative of degree of segregation. AlloysNiCrCoMoWRe Ta Al Ti Ru Ta substitution for Al + 1 at% Ta, -1 at% Al 11.2 wt% Ta, 5 wt% Al 1,12 Al substitution for Ta + 1 at% Al, -1 at% Ta 6 wt% Ta, 6.15 wt% Al 1,13 1 at% Ta v at% Al 12,13 Ti substitution for Ta + 1 at% Ti, -1 at% Ta 0.8 wt% Ti, 6 wt% Ta 1,14 Ti substitution for Al + 1 at% Ti, -1 at% Al 0.8 wt% Ti, 5.1 wt% Al 1,15 +1 at% Ti, 1 at% (Ta, Al) 14,15

PAGE 158

138 CHAPTER 7 FUTURE WORK This paper has required a tremendous amount of data to be generated. This chapter serves to provide for possible future analyses and experiments to develop an even better understanding of segregation and partitio ning phenomena due to various alloying additions. 7.1. Solidification Front Curves from EMPA All the work in this study was done using normalized weight percents and normalized PDAS, but all the data could be recalculated in three different ways: Normalize Weight Percent and PDAS Atomic Percent and Normalized PDAS Atomic Percent and PDAS The last combination (atomic percent and PDAS) is composition per distance in the cast alloy. The derivative of this is x C and the second derivative is 2 2 x C The use of x C could provide insight into the diffusion gr adients and constants to develop a better understanding of diffusion. 2 2 x C is part of Ficks Second Law, 2 2 x C D t CB B This would become B B BD t C

PAGE 159

139 7.2. Other Elemental Interaction It has been widely speculat ed about many of the elemen tal interactions that are occurring in superalloys. Most analyses onl y vary one elemental composition at a time, and then base more universal results on this narrow change. Expanding the test matrix to cover secondary and tertiary interactions would enhance understanding. The difficultly in expanding the test matrix is cost to manuf acture the alloys. Based on the work in this paper, the following systems are recommende d for examination into understanding the segregation using only solid solution st rengtheners. Table 7-1 gives the recommendations in approximate wt%, and Ta ble 7-1 gives the recommended alloying in at%. Table 7-1 Recommended alloying vari ations to investigate in wt%. Weight Percent (target) Ni Cr Co Mo W Ta Re Al Ti Hf Ru Pd EXSX-1 60.7 4.3 12.6 0.0 6.0 8.9 0.0 5.8 0.0 0.1 1.7 0.0 EXSX-2 59.3 4.2 12.5 0.0 6.0 8.8 0.0 5.7 0.0 0.1 3.3 0.0 EXSX-3 58.5 4.2 12.3 0.0 5.9 8.7 3.0 5.6 0.0 0.1 1.6 0.0 EXSX-4 57.1 4.2 12.2 0.0 5.9 8.7 3.0 5.6 0.0 0.1 3.2 0.0 EXSX-5 64.8 4.1 3.7 1.5 5.8 8.6 5.9 5.5 0.0 0.1 0.0 0.0 EXSX-6 61.1 4.1 7.4 1.5 5.8 8.6 5.9 5.5 0.0 0.1 0.0 0.0 EXSX-7 57.4 4.1 11.2 1.5 5.8 8.6 5.9 5.5 0.0 0.1 0.0 0.0 EXSX-8 56.1 4.1 11.1 1.5 5.8 8.5 5.8 5.5 0.0 0.1 1.6 0.0 EXSX-9 59.7 4.1 7.4 1.5 5.8 8.5 5.8 5.5 0.0 0.1 1.6 0.0 EXSX-10 63.4 4.1 3.7 1.5 5.8 8.5 5.8 5.5 0.0 0.1 1.6 0.0 EXSX-11 61.0 4.1 7.4 0.0 5.8 8.6 5.9 5.5 0.0 0.1 1.6 0.0 EXSX-12 64.7 4.1 3.7 0.0 5.8 8.6 5.9 5.5 0.0 0.1 1.6 0.0

PAGE 160

140 Table 7-2: Recommended alloyi ng variations based on at%. Atomic Percent (target) Ni Cr Co Mo W Ta Re Al Ti Hf Ru Pd EXSX-1 63.0 5.0 13.00.0 2.03.0 0.013.00.00.0 1.0 0.0 EXSX-2 62.0 5.0 13.00.0 2.03.0 0.013.00.00.0 2.0 0.0 EXSX-3 62.0 5.0 13.00.0 2.03.0 1.013.00.00.0 1.0 0.0 EXSX-4 61.0 5.0 13.00.0 2.03.0 1.013.00.00.0 2.0 0.0 EXSX-5 70.0 5.0 4.0 1.0 2.03.02.013.00.00.0 0.0 0.0 EXSX-6 66.0 5.0 8.0 1.0 2.03.02.013.00.00.0 0.0 0.0 EXSX-7 62.0 5.0 12.0 1.0 2.03.02.013.00.00.0 0.0 0.0 EXSX-8 61.0 5.0 12.0 1.0 2.03.02.013.00.00.0 1.0 0.0 EXSX-9 65.0 5.0 8.0 1.0 2.03.02.013.00.00.0 1.0 0.0 EXSX-10 69.0 5.0 4.0 1.0 2.03.02.013.00.00.0 1.0 0.0 EXSX-11 66.0 5.0 8.0 0.0 2.03.02.013.00.00.0 1.0 0.0 EXSX-12 70.0 5.0 4.0 0.0 2.03.02.013.00.00.0 1.0 0.0

PAGE 161

141 APPENDIX A SAMPLE BACKSCATTERED ELECTRON IMAGES This appendix contains a selection of the back scattered electron images that were used to calculate the primary dendrite arm spacing. Two images for each alloy are shown to present a representative sample of the micr ostructure. All images were taken at 100x, and resized for placement in this appendix.

PAGE 162

142 Figure A-1: BSE image of LMSX-1 at 100x. Figure A-2: BSE image of LMSX-1 at 100x.

PAGE 163

143 Figure A-3: BSE image of LMSX-2 at 100x. Figure A-4: BSE image of LMSX-2 at 100x.

PAGE 164

144 Figure A-5: BSE image of LMSX-3 at 100x. Figure A-6: BSE image of LMSX-3 at 100x.

PAGE 165

145 Figure A-7: BSE image of LMSX-4 at 100x. Figure A-8: BSE image of LMSX-4 at 100x.

PAGE 166

146 Figure A-9: BSE image of LMSX-5 at 100x. Figure A-10: BSE image of LMSX-5 at 100x.

PAGE 167

147 Figure A-11: BSE image of LMSX-6 at 100x. Figure A-12: BSE image of LMSX-6 at 100x.

PAGE 168

148 Figure A-13: BSE image of LMSX-7 at 100x. Figure A-14: BSE image of LMSX-7 at 100x.

PAGE 169

149 Figure A-15: BSE image of LMSX-8 at 100x. Figure A-16: BSE image of LMSX-8 at 100x.

PAGE 170

150 Figure A-17: BSE image of LMSX-9 at 100x. Figure A-18: BSE image of LMSX-9 at 100x.

PAGE 171

151 Figure A-19: BSE image of LMSX-10 at 100x. Figure A-20: BSE image of LMSX-10 at 100x.

PAGE 172

152 Figure A-21: BSE image of LMSX-11 at 100x. Figure A-22: BSE image of LMSX-11 at 100x.

PAGE 173

153 Figure A-23: BSE image of LMSX-12 at 100x Figure A-24: BSE image of LMSX-12 at 100x.

PAGE 174

154 Figure A-25: BSE image of LMSX-13 at 100x. Figure A-26: BSE image of LMSX-13 at 100x.

PAGE 175

155 Figure A-27: BSE image of LMSX-14 at 100x. Figure A-28: BSE image of LMSX-14 at 100x.

PAGE 176

156 Figure A-29: BSE image of LMSX-15 at 100x. Figure A-30: BSE image of LMSX-15 at 100x.

PAGE 177

157 Figure A-31: BSE image of LMSX-16 at 100x. Figure A-32: BSE image of LMSX-16 at 100x.

PAGE 178

158 Figure A-33: BSE image of LMSX-17 at 100x. Figure A-34: BSE image of LMSX-17 at 100x.

PAGE 179

159 Figure A-35: BSE image of LMSX-18 at 100x. Figure A-36: BSE image of LMSX-18 at 100x.

PAGE 180

160 APPENDIX B ELECTRON MICROPROBE ANALYSIS SCHEDULES AND SUMMARY OF PROCEDURE USED This appendix contains the schedules used to measure the EMPA data, and a summary of the procedure used in this study fo r ready examination and instruction

PAGE 181

161 Basic Schedule: This was used for all scans other than those specified below. The elements scanned for were based on those f ound in the alloy. See Table 1 for complete elemental composition of all alloys. SETUP SCH [schedule name] PKCNT NI CR CO W RE TA AL HF [the elements particular to this scan] RUN PRZ END Modified Schedule A: Due to the age of the equipment, some of the trace elements were difficult to detect. To detect these trace elem ents, another step was added to the schedule. For alloys LMSX-7 and -8, a step was adde d to measure Mo. For alloys LMSX-14 and15 a similar step was added to measure Ti. For LMSX-16, a step was added to measure the Ru in the alloy. SETUP SCH [schedule name] PKCNT NI CR CO W RE TA AL HF [the elements particular to this scan] MEAS [element specified from above. (i.e. Mo or Ti)] RUN PRZ END Modified Schedule B: Done for the same r eason as the modified schedule A, but only used to measure the compositions in CMSX4. Hf was omitted to shorten scan time. SETUP SCH [schedule name] PKCNT NI CR CO MO W RE TA AL TI MEAS MO MEAS TI RUN PRZ END

PAGE 182

162 Procedure for calculation of segregation behavior 1.) Perform a line scan from dendrite co re to dendrite core through the interdendritic region while trying to a void crossing through any secondary or tertiary dendrite arms 2.) Repeat scans as necessary to generate satisfactory average values. Three were line scans were used in this study 3.) Tabulated data and calculate the averag e value for each element per point of the line scan. 4.) Plot the average values of the elements and fit a second orde r trendline to the data set. 5.) Determine the equation for the trendline 6.) Calculate the second derivative of the trendline equa tion. This is 7.) Repeat for all elements being examined and for all alloys being examined.

PAGE 183

163 APPENDIX C AVERAGE ELECTRON MICROPROBE ANALYSES RESULTS This appendix contains the average results for the EMPA scans done on the eighteen model alloys in both atomic pe rcent and normalized weight percent.

PAGE 184

164Table C-1: Average EMPA data for LMSX-1 Atomic percent (at%) Normalize Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 62.03 4.86 14.79 2.42 3.81 1.74 10.37 0.00 55.89 3.88 13.38 6.84 10.87 4.84 4.30 0.00 61.91 5.19 14.51 2.46 3.74 1.76 10.41 0.00 55.84 4.15 13.14 6.97 10.70 4.89 4.32 0.00 63.24 4.65 13.63 2.17 2.80 2.21 11.29 0.00 58.18 3.79 12.59 6.24 8.15 6.28 4.78 0.00 62.85 5.46 14.33 1.86 2.27 2.34 10.88 0.00 58.57 4.50 13.40 5.43 6.70 6.74 4.57 0.00 64.11 4.70 12.68 1.58 1.43 3.23 12.28 0.00 60.43 3.92 11.98 4.66 4.29 9.40 5.32 0.00 64.41 4.29 11.93 1.46 1.15 3.68 13.09 0.00 60.91 3.59 11.33 4.31 3.44 10.72 5.69 0.00 64.84 4.01 11.87 1.48 1.01 3.73 13.07 0.00 61.37 3.36 11.28 4.38 3.04 10.89 5.68 0.00 64.27 4.40 12.17 1.45 1.26 3.49 12.96 0.00 60.83 3.69 11.56 4.29 3.79 10.20 5.64 0.00 63.88 4.66 12.54 1.54 1.31 3.35 12.73 0.00 60.42 3.90 11.90 4.56 3.93 9.75 5.53 0.00 63.93 4.62 12.07 1.52 1.26 3.54 13.06 0.00 60.41 3.87 11.45 4.51 3.79 10.30 5.67 0.00 64.27 4.41 12.22 1.40 1.04 3.73 12.92 0.00 60.88 3.70 11.61 4.16 3.12 10.90 5.62 0.00 64.22 4.27 11.72 1.34 0.98 3.96 13.50 0.00 60.89 3.59 11.12 3.97 2.94 11.57 5.88 0.00 64.70 4.00 11.56 1.40 0.98 3.91 13.44 0.00 61.29 3.36 10.99 4.15 2.93 11.44 5.85 0.00 64.12 4.01 11.69 1.41 0.92 3.89 13.96 0.00 60.97 3.38 11.15 4.21 2.78 11.40 6.10 0.00 64.33 4.19 11.95 1.39 1.06 3.84 13.26 0.00 60.89 3.51 11.35 4.11 3.17 11.20 5.77 0.00 64.17 4.31 12.00 1.46 1.07 3.68 13.31 0.00 60.85 3.62 11.42 4.33 3.21 10.77 5.80 0.00 63.43 4.94 12.74 1.66 1.66 3.15 12.41 0.00 59.57 4.10 12.00 4.89 4.94 9.13 5.36 0.00 63.73 4.65 12.40 1.58 1.44 3.43 12.77 0.00 60.00 3.87 11.70 4.64 4.28 9.98 5.53 0.00 63.47 4.58 12.66 1.74 1.72 3.37 12.46 0.00 59.19 3.77 11.83 5.08 5.07 9.71 5.35 0.00 62.69 5.19 13.67 1.79 2.14 2.81 11.72 0.00 58.37 4.28 12.78 5.22 6.29 8.05 5.02 0.00 63.69 4.51 12.53 1.59 1.53 3.35 12.80 0.00 59.91 3.76 11.82 4.68 4.57 9.73 5.54 0.00 63.20 5.29 13.11 1.49 1.59 3.24 12.08 0.00 59.48 4.41 12.38 4.38 4.73 9.39 5.23 0.00 63.79 4.48 12.55 1.57 1.41 3.50 12.70 0.00 59.97 3.73 11.83 4.62 4.19 10.16 5.49 0.00 64.66 4.06 11.96 1.45 1.15 3.64 13.07 0.00 61.19 3.40 11.35 4.29 3.44 10.64 5.69 0.00 64.56 4.13 12.33 1.52 1.24 3.42 12.69 0.00 61.13 3.46 11.70 4.51 3.71 9.98 5.52 0.00 63.99 4.52 12.96 1.73 1.79 2.82 12.19 0.00 60.15 3.76 12.23 5.09 5.32 8.18 5.27 0.00 63.67 4.79 13.27 1.86 2.12 2.52 11.78 0.00 59.55 3.96 12.44 5.44 6.28 7.26 5.06 0.00 62.78 4.96 14.06 2.17 3.10 2.08 10.86 0.00 57.46 4.02 12.91 6.21 8.97 5.87 4.57 0.00 62.40 4.98 14.23 2.38 3.71 1.83 10.47 0.00 56.34 3.98 12.89 6.72 10.63 5.09 4.34 0.00 Average 62.02 5.04 14.58 2.39 3.86 1.79 10.33 0.00 55.83 4.01 13.17 6.74 11.01 4.96 4.28 0.00

PAGE 185

165Table C-2: Average EMPA data for LMSX-2 Atomic percent (at%) Normalize Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 65.82 5.35 9.98 2.44 3.91 1.69 10.81 0.00 59.41 4.27 9.04 6.90 11.19 4.70 4.49 0.00 65.97 5.55 10.09 2.41 4.05 1.62 10.32 0.00 59.37 4.43 9.11 6.80 11.54 4.49 4.27 0.00 66.20 5.48 9.79 2.21 3.18 1.93 11.22 0.00 60.76 4.45 9.02 6.34 9.23 5.46 4.73 0.00 67.25 4.92 8.61 1.79 2.04 2.68 12.70 0.00 63.20 4.10 8.12 5.25 6.06 7.78 5.49 0.00 67.65 4.41 8.14 1.47 1.40 3.45 13.49 0.00 64.07 3.70 7.74 4.35 4.21 10.06 5.87 0.00 66.48 5.62 8.90 1.53 1.91 2.98 12.58 0.00 62.62 4.68 8.41 4.50 5.69 8.65 5.45 0.00 67.63 4.18 7.61 1.41 1.03 3.77 14.37 0.00 64.51 3.51 7.27 4.20 3.09 11.11 6.30 0.00 67.49 4.49 7.93 1.49 1.35 3.45 13.80 0.00 64.06 3.78 7.55 4.45 4.06 10.09 6.02 0.00 66.61 5.37 8.45 1.56 1.74 3.07 13.19 0.00 62.97 4.49 8.02 4.61 5.22 8.96 5.73 0.00 67.29 4.82 7.78 1.51 1.42 3.35 13.82 0.00 63.91 4.05 7.42 4.48 4.28 9.83 6.03 0.00 66.37 5.47 8.43 1.48 1.69 3.26 13.30 0.00 62.72 4.57 7.99 4.37 5.07 9.51 5.78 0.00 68.41 3.42 7.10 1.20 0.66 4.29 14.91 0.00 65.47 2.90 6.82 3.59 1.99 12.67 6.54 0.00 67.78 3.74 7.28 1.33 0.89 3.93 15.05 0.00 64.91 3.17 7.00 3.99 2.71 11.60 6.63 0.00 67.43 4.31 7.40 1.42 1.09 3.69 14.66 0.00 64.41 3.65 7.10 4.24 3.28 10.88 6.44 0.00 67.59 4.09 7.54 1.50 1.18 3.52 14.56 0.00 64.51 3.45 7.22 4.48 3.57 10.38 6.39 0.00 64.05 7.75 10.05 1.85 2.86 2.31 11.12 0.00 59.30 6.33 9.31 5.34 8.33 6.65 4.74 0.00 67.53 4.26 8.06 1.45 1.35 3.48 13.70 0.18 63.85 3.56 7.64 4.29 4.04 10.16 5.96 0.51 67.88 4.06 7.47 1.57 1.26 3.47 14.31 0.00 64.58 3.40 7.12 4.67 3.77 10.19 6.26 0.00 66.72 5.09 8.58 1.63 1.71 3.16 13.11 0.00 62.89 4.25 8.11 4.79 5.11 9.17 5.68 0.00 66.69 5.13 8.27 1.44 1.42 3.55 13.49 0.00 63.13 4.28 7.84 4.26 4.25 10.36 5.87 0.00 67.18 4.75 7.79 1.27 1.17 3.83 14.01 0.00 63.91 4.00 7.43 3.78 3.52 11.23 6.13 0.00 66.28 5.84 8.37 1.34 1.37 3.50 13.31 0.00 62.97 4.90 7.98 3.97 4.12 10.24 5.81 0.00 67.64 4.20 7.43 1.35 1.12 3.79 14.47 0.00 64.47 3.54 7.11 4.02 3.38 11.15 6.34 0.00 67.88 3.87 7.48 1.35 0.98 3.93 14.52 0.00 64.70 3.26 7.16 4.02 2.96 11.56 6.36 0.00 67.24 4.51 8.21 1.27 1.35 3.63 13.79 0.00 63.89 3.78 7.82 3.79 4.05 10.64 6.03 0.00 66.33 5.93 9.17 1.37 1.96 3.01 12.22 0.00 62.46 4.93 8.65 4.05 5.84 8.77 5.30 0.00 66.83 4.85 8.70 1.71 1.94 2.99 12.98 0.00 62.74 4.02 8.19 5.01 5.77 8.66 5.60 0.00 65.90 5.37 9.30 2.18 3.23 2.10 11.92 0.00 60.46 4.37 8.57 6.27 9.39 5.93 5.02 0.00 66.25 4.91 9.58 2.39 3.78 1.86 11.25 0.00 59.91 3.93 8.69 6.76 10.85 5.19 4.67 0.00 Average 66.19 5.13 9.53 2.37 3.78 1.80 11.22 0.00 59.96 4.11 8.66 6.73 10.85 5.02 4.67 0.00

PAGE 186

166Table C-3: Average EMPA data for LMSX-3. Atomic percent (at%) Normalize Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 71.86 4.88 4.69 2.35 3.66 1.78 10.78 0.00 65.14 3.91 4.27 6.68 10.53 4.98 4.49 0.00 71.52 5.32 5.01 2.42 3.98 1.61 10.14 0.00 64.38 4.24 4.53 6.81 11.37 4.46 4.19 0.00 71.45 5.01 4.72 2.37 3.48 1.87 11.10 0.00 64.99 4.04 4.31 6.73 10.04 5.25 4.64 0.00 71.72 5.60 4.80 2.07 2.91 2.01 10.87 0.00 66.14 4.57 4.44 5.98 8.51 5.74 4.61 0.00 72.20 5.06 4.19 1.63 1.73 2.83 12.37 0.00 68.21 4.23 3.97 4.81 5.18 8.23 5.37 0.00 72.62 3.72 3.60 1.32 1.04 3.73 13.98 0.00 69.28 3.12 3.43 3.91 3.08 11.03 6.14 0.00 72.52 4.05 3.70 1.48 1.20 3.49 13.55 0.00 68.94 3.39 3.52 4.37 3.57 10.28 5.93 0.00 71.60 4.96 4.20 1.62 1.92 2.90 12.80 0.00 67.44 4.14 3.97 4.76 5.71 8.43 5.55 0.00 71.91 4.57 4.14 1.71 1.86 2.94 12.89 0.00 67.66 3.80 3.90 5.01 5.51 8.54 5.58 0.00 72.17 4.32 3.78 1.68 1.56 3.10 13.40 0.00 68.28 3.62 3.59 4.97 4.68 9.05 5.83 0.00 71.15 5.54 4.50 1.71 2.15 2.70 12.25 0.00 66.72 4.60 4.23 5.00 6.36 7.80 5.28 0.00 71.05 6.33 4.43 1.63 1.94 2.63 12.00 0.00 67.05 5.30 4.19 4.82 5.80 7.64 5.21 0.00 71.25 5.03 4.15 1.45 1.45 3.26 13.41 0.00 67.72 4.23 3.96 4.30 4.36 9.56 5.86 0.00 71.93 4.22 3.67 1.33 1.04 3.71 14.10 0.00 68.70 3.57 3.51 3.96 3.13 10.94 6.19 0.00 72.34 3.83 3.56 1.23 0.73 3.96 14.35 0.00 69.37 3.25 3.42 3.69 2.22 11.71 6.33 0.00 71.99 4.42 3.66 1.19 0.86 3.83 14.04 0.00 69.01 3.74 3.52 3.58 2.62 11.35 6.19 0.00 71.89 4.31 3.80 1.23 0.96 3.66 14.16 0.00 69.00 3.66 3.66 3.70 2.90 10.82 6.25 0.00 71.35 4.97 3.90 1.41 1.32 3.43 13.62 0.00 67.89 4.18 3.72 4.21 3.97 10.05 5.96 0.00 72.60 3.14 3.48 1.19 0.60 4.12 14.87 0.00 69.80 2.67 3.36 3.59 1.82 12.20 6.57 0.00 71.21 5.85 4.51 1.46 1.86 2.86 12.24 0.00 67.27 4.90 4.28 4.33 5.57 8.33 5.32 0.00 72.04 4.27 3.82 1.49 1.27 3.28 13.83 0.00 68.73 3.60 3.65 4.45 3.84 9.67 6.06 0.00 71.76 5.15 4.08 1.54 1.76 2.87 12.84 0.00 68.00 4.31 3.88 4.57 5.25 8.39 5.59 0.00 71.51 5.68 4.46 1.46 1.93 2.72 12.23 0.00 67.65 4.75 4.23 4.33 5.78 7.94 5.33 0.00 71.24 6.24 4.58 1.40 1.80 2.76 11.98 0.00 67.58 5.24 4.35 4.14 5.39 8.07 5.23 0.00 72.54 4.16 3.80 1.26 1.07 3.51 13.66 0.00 69.45 3.52 3.65 3.76 3.23 10.38 6.01 0.00 72.43 4.40 3.75 1.57 1.28 3.12 13.46 0.00 69.09 3.72 3.59 4.68 3.86 9.17 5.90 0.00 72.15 4.82 4.30 1.77 2.19 2.46 12.31 0.00 67.79 4.00 4.05 5.19 6.52 7.13 5.32 0.00 71.64 5.01 4.60 2.20 3.08 1.99 11.49 0.00 65.89 4.08 4.24 6.31 8.97 5.64 4.86 0.00 71.66 5.12 4.83 2.41 3.80 1.64 10.53 0.00 64.83 4.11 4.39 6.83 10.89 4.57 4.38 0.00 Average 71.73 4.88 4.77 2.37 3.76 1.75 10.74 0.00 64.90 3.92 4.33 6.71 10.79 4.89 4.46 0.00

PAGE 187

167Table C-4: Average EMPA data for LMSX-4. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 59.58 7.82 14.65 2.34 3.78 1.52 10.31 0.00 54.19 6.30 13.37 6.67 10.89 4.26 4.31 0.00 59.78 7.82 14.22 2.23 3.35 1.76 10.83 0.00 54.87 6.35 13.10 6.40 9.72 5.00 4.57 0.00 60.22 7.63 13.84 2.08 2.91 1.95 11.36 0.00 55.86 6.27 12.89 6.03 8.53 5.58 4.85 0.00 61.00 6.91 13.17 1.94 2.45 2.45 12.07 0.00 56.90 5.69 12.31 5.65 7.19 7.09 5.18 0.00 61.30 6.84 12.67 1.61 1.80 3.04 12.74 0.00 57.82 5.70 11.98 4.76 5.34 8.87 5.53 0.00 59.87 7.85 13.87 1.84 2.71 2.19 11.67 0.00 55.89 6.48 12.97 5.35 7.96 6.33 5.01 0.00 60.74 7.69 13.02 1.73 2.02 2.48 12.33 0.00 57.44 6.44 12.36 5.11 6.05 7.24 5.36 0.00 61.38 7.09 12.52 1.42 1.31 3.44 12.79 0.05 58.20 5.95 11.91 4.21 3.94 10.06 5.57 0.15 61.62 6.89 12.15 1.48 1.39 3.21 13.26 0.00 58.72 5.82 11.62 4.41 4.19 9.42 5.81 0.00 60.79 7.18 12.90 1.80 2.32 2.62 12.41 0.00 56.95 5.95 12.10 5.25 6.81 7.59 5.35 0.00 60.51 7.32 13.12 1.82 2.04 2.59 12.61 0.00 57.05 6.11 12.40 5.35 6.07 7.55 5.47 0.00 59.96 7.77 13.05 1.84 2.28 2.68 12.43 0.00 56.13 6.42 12.24 5.38 6.70 7.77 5.35 0.00 60.88 7.46 12.37 1.45 1.43 3.29 13.11 0.00 57.91 6.28 11.80 4.31 4.31 9.66 5.73 0.00 62.42 5.77 11.90 1.48 1.21 3.65 13.56 0.00 59.20 4.84 11.32 4.38 3.64 10.70 5.92 0.00 60.47 7.32 12.77 1.66 1.88 3.20 12.69 0.00 56.73 6.07 12.01 4.86 5.56 9.29 5.48 0.00 62.09 6.18 11.71 1.35 1.05 3.80 13.82 0.00 59.16 5.21 11.19 4.03 3.16 11.18 6.05 0.00 60.33 7.74 13.48 1.64 2.01 2.67 12.13 0.00 56.89 6.46 12.75 4.84 5.99 7.80 5.26 0.00 60.12 7.72 13.17 1.68 2.12 2.64 12.56 0.00 56.71 6.45 12.46 4.93 6.31 7.69 5.45 0.00 59.78 8.30 12.89 1.49 1.77 2.95 12.83 0.00 56.77 6.98 12.28 4.43 5.33 8.62 5.60 0.00 61.47 6.87 11.71 1.54 1.20 3.69 13.52 0.00 58.26 5.77 11.14 4.56 3.60 10.78 5.89 0.00 61.44 6.29 12.34 1.76 1.93 3.16 13.08 0.00 57.61 5.20 11.58 5.14 5.63 9.19 5.65 0.00 60.74 6.82 12.82 1.69 1.95 3.13 12.85 0.00 56.97 5.65 12.04 4.94 5.76 9.09 5.54 0.00 61.97 6.20 11.80 1.47 1.19 3.65 13.72 0.00 58.90 5.21 11.25 4.35 3.59 10.69 6.00 0.00 62.88 5.45 11.54 1.37 1.13 3.74 13.89 0.00 59.86 4.58 11.01 4.08 3.38 11.01 6.08 0.00 62.01 6.13 12.13 1.59 1.51 3.36 13.27 0.00 58.60 5.12 11.49 4.69 4.53 9.80 5.77 0.00 60.74 7.48 12.82 1.61 1.86 2.93 12.58 0.00 57.34 6.25 12.13 4.74 5.54 8.54 5.46 0.00 61.87 6.43 12.52 1.71 2.04 2.98 12.45 0.00 57.93 5.30 11.74 5.00 6.00 8.66 5.36 0.00 60.38 7.38 13.63 2.00 2.91 2.17 11.54 0.00 55.91 6.05 12.65 5.77 8.49 6.21 4.92 0.00 60.20 7.66 13.85 2.11 3.06 1.93 11.18 0.00 55.60 6.27 12.84 6.09 8.95 5.51 4.75 0.00 Average 59.53 7.72 14.44 2.29 3.76 1.60 10.66 0.00 54.23 6.23 13.21 6.54 10.86 4.48 4.46 0.00

PAGE 188

168Table C-5: Average EMPA data for LMSX-5. Atomic percent (at%) Normalize Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 65.14 3.15 14.75 1.97 3.12 1.24 10.62 0.00 60.58 2.59 13.77 5.74 9.21 3.56 4.54 0.00 65.33 2.60 14.94 1.99 3.14 1.29 10.71 0.00 60.64 2.14 13.92 5.79 9.25 3.69 4.57 0.00 65.81 3.09 14.14 1.75 2.54 1.52 11.15 0.00 62.06 2.58 13.38 5.15 7.57 4.42 4.84 0.00 66.50 2.48 13.57 1.46 1.89 1.90 12.20 0.00 63.75 2.11 13.04 4.38 5.70 5.64 5.38 0.00 66.29 2.95 13.31 1.52 1.63 1.95 12.35 0.00 63.83 2.51 12.86 4.57 4.96 5.79 5.47 0.00 66.32 2.66 13.51 1.51 1.79 1.92 12.28 0.00 63.64 2.26 13.02 4.53 5.45 5.68 5.42 0.00 65.93 3.04 13.63 1.53 1.73 1.87 12.28 0.00 63.40 2.59 13.15 4.60 5.28 5.55 5.43 0.00 66.56 2.46 13.34 1.42 1.57 2.02 12.62 0.00 64.26 2.10 12.92 4.30 4.81 6.00 5.60 0.00 66.29 3.06 13.48 1.31 1.49 2.00 12.37 0.00 64.24 2.63 13.11 3.98 4.57 5.97 5.51 0.00 67.08 2.50 12.86 1.23 1.16 2.26 12.90 0.00 65.36 2.16 12.58 3.75 3.59 6.78 5.78 0.00 66.66 2.90 12.87 1.10 1.07 2.36 13.04 0.00 65.18 2.52 12.59 3.38 3.33 7.11 5.86 0.00 67.23 2.35 12.52 1.17 0.96 2.51 13.26 0.00 65.66 2.03 12.27 3.56 2.97 7.55 5.95 0.00 66.51 3.00 13.06 1.14 1.12 2.31 12.86 0.00 64.94 2.59 12.80 3.48 3.46 6.96 5.77 0.00 66.78 2.58 12.95 1.25 1.08 2.29 13.07 0.00 65.15 2.23 12.68 3.81 3.36 6.90 5.86 0.00 66.45 3.07 13.14 1.15 1.16 2.23 12.80 0.00 64.88 2.65 12.87 3.54 3.59 6.72 5.75 0.00 66.84 2.43 13.07 1.22 1.20 2.28 12.95 0.00 65.06 2.10 12.77 3.71 3.71 6.86 5.79 0.00 66.20 2.99 13.42 1.18 1.24 2.24 12.73 0.00 64.47 2.58 13.11 3.60 3.81 6.73 5.70 0.00 66.77 2.48 13.05 1.14 1.08 2.31 13.18 0.00 65.31 2.15 12.81 3.47 3.35 6.98 5.93 0.00 66.54 3.08 12.77 1.28 1.17 2.20 12.95 0.00 64.88 2.66 12.51 3.92 3.61 6.61 5.80 0.00 66.59 2.49 13.04 1.37 1.34 2.06 13.13 0.00 64.80 2.14 12.74 4.16 4.12 6.17 5.87 0.00 66.25 2.90 13.29 1.42 1.47 1.98 12.70 0.00 64.20 2.49 12.92 4.30 4.50 5.93 5.66 0.00 66.47 2.57 13.35 1.41 1.53 1.99 12.68 0.00 64.31 2.20 12.96 4.27 4.70 5.93 5.64 0.00 66.65 2.94 13.18 1.37 1.49 1.96 12.41 0.00 64.56 2.52 12.81 4.16 4.57 5.85 5.52 0.00 66.84 2.43 13.24 1.33 1.44 2.09 12.63 0.00 64.73 2.08 12.86 4.05 4.41 6.24 5.62 0.00 66.50 2.91 13.18 1.33 1.35 2.12 12.60 0.00 64.51 2.50 12.82 4.05 4.15 6.35 5.62 0.00 66.78 2.45 13.15 1.43 1.51 1.98 12.69 0.00 64.60 2.10 12.77 4.35 4.62 5.92 5.64 0.00 65.95 2.95 14.06 1.65 2.13 1.60 11.66 0.00 62.88 2.50 13.45 4.93 6.44 4.69 5.11 0.00 65.82 2.59 14.46 1.94 2.89 1.35 10.96 0.00 61.49 2.14 13.56 5.67 8.56 3.87 4.71 0.00 65.32 3.07 14.38 2.02 3.20 1.31 10.70 0.00 60.55 2.52 13.39 5.86 9.40 3.73 4.56 0.00 Average 65.41 2.62 15.05 1.95 3.15 1.25 10.56 0.00 60.75 2.16 14.03 5.68 9.29 3.58 4.51 0.00

PAGE 189

169Table C-6: Average EMPA data for LMSX-6. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 61.92 5.11 14.83 2.74 3.01 1.20 11.19 0.00 57.17 4.17 13.75 7.93 8.82 3.41 4.75 0.00 60.73 5.75 15.19 2.94 3.16 1.21 10.92 0.00 55.72 4.67 13.97 8.44 9.17 3.43 4.60 0.00 61.95 4.80 14.72 2.64 2.73 1.37 11.77 0.00 57.60 3.95 13.74 7.68 8.06 3.94 5.03 0.00 62.20 4.97 14.22 2.57 2.49 1.52 12.03 0.00 58.12 4.10 13.33 7.52 7.36 4.39 5.17 0.00 61.60 5.52 14.43 2.47 2.28 1.59 12.12 0.00 57.95 4.59 13.60 7.25 6.74 4.62 5.25 0.00 62.02 5.46 13.94 2.26 1.82 1.91 12.59 0.00 58.92 4.58 13.26 6.69 5.42 5.62 5.50 0.00 62.01 5.62 13.99 1.94 1.65 2.04 12.76 0.00 59.35 4.77 13.44 5.81 5.00 6.02 5.61 0.00 63.93 4.17 12.40 1.75 1.06 2.45 14.25 0.00 62.10 3.58 12.07 5.30 3.25 7.34 6.37 0.00 63.49 4.47 12.68 1.84 1.25 2.39 13.89 0.00 61.30 3.81 12.27 5.53 3.78 7.13 6.17 0.00 63.91 4.22 12.27 1.75 1.00 2.60 14.23 0.00 61.95 3.61 11.92 5.30 3.06 7.81 6.34 0.00 61.25 6.46 13.85 2.04 1.71 2.01 12.69 0.00 58.53 5.45 13.27 6.09 5.18 5.91 5.57 0.00 61.95 5.66 13.48 2.02 1.59 2.09 13.25 0.00 59.34 4.80 12.96 6.05 4.83 6.17 5.83 0.00 62.01 5.40 13.44 1.83 1.44 2.17 13.70 0.00 59.89 4.61 13.02 5.52 4.40 6.48 6.08 0.00 62.53 5.08 12.99 1.80 1.26 2.52 13.82 0.00 60.28 4.32 12.54 5.40 3.81 7.52 6.13 0.00 63.37 4.35 12.28 1.46 0.92 2.85 14.76 0.00 61.76 3.75 12.01 4.47 2.84 8.46 6.61 0.00 62.49 5.30 12.63 1.58 1.11 2.71 14.17 0.00 60.55 4.54 12.28 4.80 3.41 8.10 6.32 0.00 63.53 4.44 12.06 1.41 0.89 2.97 14.71 0.00 61.85 3.83 11.79 4.29 2.75 8.90 6.58 0.00 62.65 5.25 12.76 1.51 1.16 2.60 14.07 0.00 60.83 4.50 12.42 4.61 3.56 7.79 6.28 0.00 64.40 3.98 11.88 1.42 0.82 2.74 14.76 0.00 63.07 3.45 11.67 4.34 2.54 8.29 6.65 0.00 63.26 4.60 12.40 1.66 1.03 2.48 14.57 0.00 61.68 3.97 12.14 5.07 3.18 7.43 6.53 0.00 62.88 4.89 12.96 1.94 1.51 2.17 13.64 0.00 60.46 4.16 12.49 5.82 4.57 6.46 6.04 0.00 62.30 5.26 13.38 2.02 1.63 1.97 13.45 0.00 59.83 4.47 12.90 6.08 4.97 5.82 5.94 0.00 62.00 5.02 13.71 2.17 1.79 1.90 13.41 0.00 59.26 4.24 13.14 6.47 5.40 5.61 5.90 0.00 62.04 5.39 13.51 2.15 1.74 1.93 13.25 0.00 59.69 4.26 12.92 6.38 5.18 5.73 5.83 0.00 62.07 5.31 13.78 2.23 1.96 1.83 12.81 0.00 58.93 4.46 13.13 6.61 5.89 5.38 5.60 0.00 62.10 5.35 13.94 2.28 2.13 1.70 12.51 0.00 58.75 4.48 13.24 6.77 6.38 4.95 5.44 0.00 62.26 5.09 14.27 2.32 2.32 1.57 12.17 0.00 58.66 4.24 13.49 6.85 6.92 4.56 5.27 0.00 61.42 5.70 14.69 2.66 2.88 1.29 11.36 0.00 56.97 4.67 13.66 7.71 8.44 3.70 4.84 0.00 61.40 5.25 15.10 3.05 3.16 1.18 10.85 0.00 56.12 4.25 13.86 8.71 9.16 3.33 4.56 0.00 Average 60.83 5.75 15.23 2.89 3.12 1.25 10.94 0.00 55.80 4.67 14.02 8.30 9.07 3.53 4.62 0.00

PAGE 190

170Table C-7: Average EMPA data for LMSX-7. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co Mo W Re Ta Al Hf Ni Cr Co Mo W Re Ta Al Hf 63.87 5.01 14.07 1.04 0.97 2.92 1.34 10.69 0.00 60.53 4.20 13.39 1.61 2.88 8.76 3.92 4.70 0.00 63.25 5.44 14.14 0.99 0.97 2.93 1.38 10.89 0.00 59.97 4.57 13.46 1.53 2.88 8.80 4.05 4.75 0.00 63.67 5.13 14.03 1.00 0.92 2.38 1.64 11.23 0.00 60.89 4.35 13.47 1.56 2.75 7.20 4.84 4.93 0.00 64.58 5.07 12.50 1.00 0.77 1.37 2.22 12.49 0.00 62.97 4.37 12.22 1.60 2.33 4.22 6.68 5.60 0.00 65.05 4.58 12.39 0.96 0.77 1.17 2.41 12.67 0.00 63.49 3.95 12.12 1.53 2.36 3.61 7.22 5.69 0.00 64.22 5.48 12.49 1.16 0.73 1.24 2.27 12.41 0.00 62.69 4.73 12.23 1.84 2.24 3.85 6.84 5.57 0.00 64.79 4.79 12.75 1.06 0.73 1.28 2.26 12.34 0.00 63.18 4.12 12.48 1.69 2.22 3.96 6.80 5.53 0.00 64.36 5.20 12.60 1.11 0.71 1.18 2.39 12.47 0.00 62.80 4.50 12.34 1.76 2.17 3.65 7.19 5.58 0.00 64.10 4.84 12.97 1.12 0.73 1.34 2.39 12.51 0.00 62.31 4.17 12.65 1.78 2.21 4.13 7.16 5.59 0.00 63.73 5.40 12.73 1.22 0.76 1.33 2.43 12.39 0.00 61.82 4.63 12.39 1.93 2.30 4.10 7.30 5.52 0.00 64.69 4.39 12.42 0.83 0.71 1.19 2.62 13.15 0.00 63.10 3.79 12.16 1.32 2.17 3.70 7.87 5.90 0.00 64.05 5.32 12.48 1.08 0.69 1.14 2.54 12.70 0.00 62.49 4.59 12.23 1.72 2.11 3.53 7.63 5.70 0.00 64.18 4.92 12.46 1.15 0.69 1.13 2.47 13.00 0.00 62.75 4.26 12.23 1.84 2.12 3.51 7.45 5.84 0.00 64.00 5.32 12.11 1.35 0.72 1.19 2.41 12.90 0.00 62.48 4.60 11.86 2.16 2.21 3.67 7.24 5.79 0.00 64.22 4.83 12.42 1.39 0.83 1.19 2.46 12.67 0.00 62.34 4.15 12.10 2.20 2.51 3.67 7.37 5.65 0.00 63.37 5.88 13.20 1.15 0.67 1.35 2.30 12.08 0.00 61.68 5.07 12.89 1.82 2.04 4.17 6.92 5.40 0.00 64.07 4.99 12.92 1.25 0.69 1.26 2.37 12.45 0.00 62.41 4.29 12.62 1.99 2.09 3.90 7.12 5.57 0.00 63.59 5.57 13.14 1.13 0.65 1.23 2.47 12.23 0.00 61.91 4.80 12.84 1.80 1.97 3.79 7.41 5.47 0.00 63.57 5.45 13.40 1.14 0.77 1.40 2.25 12.02 0.00 61.71 4.69 13.07 1.81 2.32 4.32 6.72 5.36 0.00 64.80 4.69 12.00 0.94 0.83 1.24 2.65 12.86 0.00 62.84 4.02 11.68 1.48 2.51 3.80 7.93 5.73 0.00 64.51 4.57 12.56 1.00 0.78 1.16 2.55 12.87 0.00 62.82 3.93 12.27 1.60 2.37 3.59 7.67 5.76 0.00 63.63 5.51 13.15 1.14 0.70 1.46 2.28 12.13 0.00 61.80 4.74 12.81 1.82 2.13 4.48 6.81 5.41 0.00 64.60 4.57 12.40 1.35 0.80 1.40 2.31 12.59 0.00 62.66 3.92 12.07 2.12 2.42 4.29 6.91 5.61 0.00 63.41 5.88 13.42 1.02 0.77 1.49 1.99 12.03 0.00 61.83 5.07 13.13 1.62 2.37 4.59 5.99 5.39 0.00 64.20 4.98 13.21 0.97 0.84 1.57 2.02 12.21 0.00 62.40 4.28 12.88 1.54 2.57 4.83 6.04 5.45 0.00 63.73 5.51 13.28 1.10 0.83 1.66 1.88 12.02 0.00 61.94 4.74 12.96 1.74 2.50 5.12 5.61 5.37 0.00 64.27 5.03 13.65 1.10 0.79 2.01 1.74 11.42 0.00 62.01 4.30 13.22 1.73 2.38 6.13 5.18 5.06 0.00 63.56 5.63 13.74 1.03 0.90 2.57 1.49 11.08 0.00 60.72 4.76 13.17 1.61 2.70 7.78 4.39 4.86 0.00 63.67 5.01 14.24 1.04 0.99 2.92 1.35 10.77 0.00 60.30 4.20 13.54 1.61 2.94 8.77 3.95 4.69 0.00 Average 63.20 5.63 14.30 0.95 0.91 2.86 1.36 10.77 0.00 60.11 4.74 13.65 1.48 2.70 8.64 3.97 4.72 0.00

PAGE 191

171Table C-8: Average EMPA data for LMSX-8. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co Mo W Re Ta Al Hf Ni Cr Co Mo W Re Ta Al Hf 61.76 5.05 14.68 1.00 1.91 3.09 1.27 11.23 0.00 57.47 4.16 13.71 1.53 5.55 9.14 3.64 4.80 0.00 62.04 5.32 14.35 0.99 1.89 2.96 1.37 11.07 0.00 57.75 4.39 13.41 1.51 5.52 8.75 3.94 4.73 0.00 62.22 5.02 14.15 1.15 1.79 2.64 1.52 11.50 0.00 58.31 4.17 13.31 1.76 5.24 7.86 4.40 4.95 0.00 61.85 5.76 14.08 1.21 1.65 2.15 1.76 11.54 0.00 58.47 4.82 13.35 1.87 4.88 6.43 5.15 5.01 0.00 62.18 5.53 13.78 1.30 1.49 1.81 2.10 11.81 0.00 59.04 4.65 13.13 2.02 4.44 5.44 6.13 5.16 0.00 63.71 4.66 12.31 0.86 1.44 1.32 2.57 13.13 0.00 61.14 3.95 11.83 1.34 4.32 3.99 7.63 5.80 0.00 62.48 5.23 13.54 1.24 1.50 1.73 2.15 12.12 0.00 59.43 4.40 12.92 1.93 4.47 5.23 6.30 5.30 0.00 62.07 5.68 13.45 1.25 1.45 1.68 2.04 12.39 0.00 59.41 4.82 12.92 1.95 4.33 5.11 6.02 5.45 0.00 62.32 5.21 13.47 1.34 1.46 1.52 2.20 12.48 0.00 59.62 4.40 12.93 2.09 4.38 4.62 6.47 5.49 0.00 62.48 5.56 13.35 1.18 1.40 1.48 2.25 12.30 0.00 59.85 4.72 12.84 1.85 4.20 4.48 6.66 5.42 0.00 63.53 4.73 12.95 1.04 1.33 1.22 2.39 12.81 0.00 61.26 4.04 12.54 1.64 4.01 3.74 7.09 5.68 0.00 62.15 5.39 13.33 1.09 1.44 1.54 2.10 12.96 0.00 59.82 4.59 12.87 1.70 4.34 4.69 6.25 5.73 0.00 62.31 5.51 13.48 1.25 1.40 1.72 2.08 12.25 0.00 59.55 4.67 12.93 1.95 4.19 5.21 6.14 5.38 0.00 64.53 4.15 11.64 0.79 1.20 0.85 2.89 13.97 0.00 62.71 3.58 11.33 1.25 3.63 2.60 8.68 6.24 0.00 63.88 3.94 12.18 0.95 1.25 1.13 2.59 14.07 0.00 61.97 3.38 11.84 1.50 3.81 3.47 7.75 6.28 0.00 61.78 5.69 13.41 1.20 1.50 1.62 2.16 12.64 0.00 59.10 4.82 12.97 1.88 4.50 4.90 6.37 5.56 0.00 62.92 5.07 13.02 1.18 1.41 1.36 2.39 12.64 0.00 60.31 4.30 12.53 1.85 4.24 4.14 7.06 5.57 0.00 63.73 4.67 11.87 1.14 1.29 0.95 2.84 13.52 0.00 61.50 3.98 11.49 1.80 3.89 2.90 8.44 6.00 0.00 62.96 4.99 12.98 1.18 1.26 1.28 2.46 12.89 0.00 60.63 4.25 12.52 1.86 3.80 3.92 7.29 5.71 0.00 63.14 5.11 12.45 1.16 1.32 1.27 2.50 13.04 0.00 60.75 4.35 12.02 1.83 3.96 3.88 7.44 5.77 0.00 63.53 4.68 12.72 1.02 1.36 1.32 2.37 12.99 0.00 61.19 3.98 12.29 1.60 4.11 4.01 7.06 5.75 0.00 63.38 4.90 12.41 1.00 1.39 1.30 2.39 13.24 0.00 61.11 4.18 12.01 1.58 4.17 3.98 7.11 5.87 0.00 63.83 4.43 12.51 0.96 1.37 1.32 2.33 13.25 0.00 61.60 3.78 12.12 1.51 4.15 4.03 6.92 5.88 0.00 63.05 5.17 12.62 1.09 1.36 1.34 2.36 13.02 0.00 60.74 4.41 12.19 1.71 4.09 4.09 7.00 5.77 0.00 62.52 5.44 13.35 1.12 1.40 1.52 2.20 12.46 0.00 60.00 4.61 12.84 1.75 4.21 4.60 6.50 5.50 0.00 63.06 5.23 13.11 1.03 1.35 1.48 2.22 12.52 0.00 60.61 4.45 12.64 1.62 4.06 4.51 6.58 5.53 0.00 62.86 4.76 13.92 1.09 1.51 1.77 1.92 12.18 0.00 60.06 4.03 13.34 1.70 4.52 5.35 5.65 5.35 0.00 62.36 5.27 13.89 1.03 1.81 2.48 1.61 11.55 0.00 58.58 4.38 13.09 1.57 5.33 7.38 4.68 4.99 0.00 62.42 4.95 14.49 0.96 1.90 2.97 1.36 10.93 0.00 58.05 4.08 13.53 1.46 5.54 8.76 3.91 4.67 0.00 Average 62.09 5.39 14.26 1.01 1.97 2.91 1.36 11.01 0.00 57.77 4.44 13.32 1.54 5.73 8.59 3.91 4.71 0.00

PAGE 192

172Table C-9: Average EMPA data for LMSX-9. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 66.82 4.55 13.26 2.45 0.43 1.86 10.62 0.00 64.35 3.88 12.82 7.39 1.33 5.53 4.70 0.00 66.51 4.59 13.52 2.48 0.48 1.85 10.56 0.00 63.95 3.91 13.06 7.47 1.45 5.49 4.67 0.00 66.91 4.47 12.70 2.16 0.33 2.26 11.17 0.00 64.63 3.82 12.31 6.54 1.00 6.73 4.96 0.00 67.12 4.28 12.19 1.67 0.15 2.82 11.76 0.00 65.18 3.68 11.89 5.10 0.47 8.43 5.25 0.00 66.86 4.60 12.15 1.46 0.10 3.11 11.71 0.00 64.93 3.95 11.84 4.44 0.30 9.31 5.23 0.00 66.69 4.39 11.89 1.53 0.14 3.26 12.10 0.00 64.52 3.76 11.55 4.65 0.42 9.71 5.38 0.00 66.52 4.46 11.96 1.56 0.08 3.30 12.15 0.00 64.38 3.83 11.60 4.72 0.23 9.83 5.40 0.00 66.41 4.69 12.28 1.60 0.08 3.11 11.82 0.00 64.35 4.03 11.94 4.86 0.26 9.28 5.26 0.00 66.49 4.54 12.11 1.55 0.11 3.19 12.01 0.00 64.41 3.90 11.77 4.72 0.33 9.54 5.35 0.00 66.45 4.81 12.25 1.54 0.13 3.07 11.76 0.00 64.45 4.12 11.93 4.67 0.40 9.18 5.24 0.00 66.36 4.75 12.42 1.64 0.11 3.02 11.70 0.00 64.29 4.07 12.08 4.98 0.34 9.03 5.21 0.00 66.40 4.71 12.28 1.63 0.15 3.02 11.80 0.00 64.31 4.04 11.95 4.95 0.47 9.03 5.25 0.00 66.47 4.59 12.34 1.69 0.10 2.97 11.83 0.00 64.44 3.94 12.01 5.14 0.32 8.88 5.27 0.00 66.05 5.07 13.14 1.81 0.21 2.47 11.24 0.00 64.21 4.37 12.83 5.52 0.65 7.40 5.02 0.00 66.07 4.99 12.96 1.87 0.20 2.53 11.38 0.00 64.13 4.29 12.62 5.68 0.61 7.58 5.08 0.00 65.76 5.06 13.16 1.94 0.23 2.47 11.38 0.00 63.79 4.35 12.81 5.88 0.72 7.38 5.07 0.00 66.53 4.42 11.92 1.69 0.11 3.10 12.24 0.00 64.45 3.79 11.59 5.14 0.33 9.25 5.45 0.00 66.37 4.62 12.37 1.57 0.10 3.15 11.82 0.00 64.28 3.96 12.03 4.76 0.30 9.41 5.26 0.00 66.57 4.45 11.98 1.51 0.08 3.31 12.11 0.00 64.45 3.82 11.64 4.57 0.26 9.87 5.39 0.00 66.07 5.22 12.47 1.45 0.05 3.19 11.55 0.00 64.12 4.49 12.15 4.42 0.14 9.54 5.15 0.00 66.35 4.72 12.12 1.51 0.10 3.32 11.88 0.00 64.14 4.04 11.76 4.58 0.31 9.89 5.28 0.00 66.57 4.62 12.06 1.43 0.11 3.21 12.00 0.00 64.64 3.97 11.75 4.31 0.34 9.59 5.36 0.00 66.39 4.68 12.46 1.58 0.15 2.97 11.78 0.00 64.45 4.02 12.14 4.80 0.47 8.88 5.25 0.00 66.78 4.28 11.85 1.57 0.10 3.23 12.18 0.00 64.67 3.68 11.53 4.78 0.30 9.63 5.42 0.00 66.58 4.70 12.43 1.64 0.14 2.95 11.57 0.00 64.53 4.03 12.09 4.97 0.42 8.80 5.15 0.00 66.70 4.75 12.33 1.66 0.14 2.90 11.51 0.00 64.66 4.08 12.00 5.02 0.44 8.66 5.13 0.00 66.92 4.56 12.38 1.88 0.26 2.55 11.44 0.00 64.83 3.92 12.04 5.71 0.80 7.62 5.10 0.00 66.56 4.58 13.42 2.28 0.40 2.07 10.69 0.00 64.13 3.90 12.98 6.89 1.22 6.14 4.73 0.00 66.59 4.66 13.55 2.44 0.44 1.88 10.44 0.00 64.06 3.97 13.08 7.36 1.35 5.57 4.61 0.00 Average 66.76 4.45 13.21 2.43 0.45 1.89 10.80 0.00 64.31 3.79 12.77 7.33 1.40 5.62 4.78 0.00

PAGE 193

173Table C-10: Average EMPA data for LMSX-10. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 64.30 4.78 14.37 2.35 1.91 1.75 10.52 0.00 60.31 3.97 13.53 6.91 5.69 5.05 4.54 0.00 64.74 4.74 13.96 2.40 1.84 1.76 10.57 0.00 60.75 3.94 13.14 7.06 5.46 5.09 4.55 0.00 63.24 4.46 13.84 4.01 3.07 2.97 8.58 0.00 60.50 3.93 13.28 7.01 5.44 5.29 4.57 0.00 65.00 4.53 13.38 2.27 1.53 2.08 11.21 0.00 61.35 3.79 12.68 6.70 4.58 6.05 4.86 0.00 65.39 4.55 12.98 1.87 1.17 2.38 11.66 0.00 62.44 3.85 12.44 5.60 3.53 7.02 5.12 0.00 65.33 4.53 12.74 1.65 0.88 2.85 12.01 0.00 62.58 3.84 12.24 4.95 2.67 8.43 5.29 0.00 65.79 4.20 12.16 1.56 0.74 3.26 12.27 0.00 62.85 3.58 11.66 4.68 2.24 9.63 5.39 0.00 66.62 3.38 11.06 1.48 0.51 3.90 13.05 0.00 63.47 2.85 10.57 4.40 1.52 11.46 5.72 0.00 65.62 4.12 11.99 1.61 0.68 3.43 12.55 0.00 62.60 3.47 11.47 4.80 2.03 10.11 5.50 0.00 64.45 5.16 13.39 1.59 0.92 2.89 11.58 0.00 61.61 4.37 12.85 4.75 2.77 8.55 5.09 0.00 65.91 3.97 11.82 1.61 0.70 3.45 12.54 0.00 62.82 3.35 11.30 4.81 2.08 10.14 5.50 0.00 65.45 4.54 12.26 1.62 0.76 3.27 12.08 0.00 62.38 3.83 11.73 4.85 2.31 9.62 5.29 0.00 65.07 4.64 12.59 1.62 0.83 3.19 12.05 0.00 62.03 3.92 12.05 4.84 2.49 9.39 5.28 0.00 65.22 4.64 12.48 1.63 0.75 3.16 12.12 0.00 62.32 3.93 11.96 4.89 2.26 9.32 5.33 0.00 65.07 4.77 12.69 1.50 0.70 3.27 12.01 0.00 62.25 4.04 12.19 4.48 2.12 9.64 5.28 0.00 65.63 4.24 11.87 1.50 0.55 3.62 12.59 0.00 62.69 3.59 11.38 4.50 1.67 10.65 5.53 0.00 65.65 4.28 11.71 1.44 0.54 3.64 12.74 0.00 62.83 3.62 11.25 4.32 1.63 10.75 5.60 0.00 65.43 4.41 12.20 1.47 0.53 3.50 12.45 0.00 62.67 3.74 11.73 4.41 1.63 10.34 5.48 0.00 65.51 4.42 11.96 1.44 0.48 3.52 12.67 0.00 62.93 3.76 11.54 4.31 1.46 10.41 5.59 0.00 66.24 3.71 11.31 1.45 0.39 3.83 13.07 0.00 63.42 3.15 10.87 4.33 1.17 11.31 5.75 0.00 66.06 3.84 11.35 1.46 0.41 3.75 13.12 0.00 63.31 3.26 10.92 4.40 1.24 10.99 5.78 0.00 65.27 4.59 12.52 1.47 0.63 3.17 12.35 0.00 62.80 3.91 12.09 4.42 1.93 9.39 5.47 0.00 65.31 4.52 12.37 1.63 0.78 3.12 12.27 0.00 62.46 3.82 11.87 4.87 2.36 9.22 5.40 0.00 65.37 4.28 12.25 1.59 0.76 3.24 12.50 0.00 62.50 3.62 11.76 4.77 2.30 9.55 5.50 0.00 65.57 4.52 12.49 1.59 0.75 3.08 12.01 0.00 62.77 3.82 11.99 4.77 2.26 9.09 5.28 0.00 65.38 4.56 12.58 1.65 0.85 2.90 12.08 0.00 62.62 3.90 12.10 4.94 2.58 8.57 5.32 0.00 65.07 4.76 13.31 1.84 1.05 2.46 11.50 0.00 62.21 4.03 12.78 5.51 3.18 7.26 5.05 0.00 64.81 4.64 13.30 2.22 1.45 2.17 11.42 0.00 61.30 3.89 12.63 6.56 4.33 6.33 4.96 0.00 64.69 4.87 13.74 2.39 1.77 1.88 10.66 0.00 60.68 4.05 12.94 7.04 5.26 5.44 4.60 0.00 Average 64.87 4.62 13.72 2.41 1.85 1.84 10.68 0.00 60.78 3.83 12.91 7.07 5.49 5.32 4.60 0.00

PAGE 194

174Table C-11: Average EMPA data for LMSX-11. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 60.38 5.90 15.05 1.80 5.09 1.15 10.62 0.00 54.42 4.71 13.62 5.08 14.55 3.20 4.40 0.00 60.68 5.21 15.02 1.82 4.81 1.31 11.16 0.00 54.93 4.17 13.65 5.15 13.81 3.65 4.64 0.00 60.09 6.23 15.47 1.73 4.71 1.29 10.48 0.00 54.51 5.00 14.07 4.91 13.50 3.63 4.37 0.00 61.88 5.34 14.65 1.35 2.88 1.72 12.19 0.00 58.70 4.47 13.90 3.98 8.57 5.04 5.33 0.00 62.31 5.65 14.40 1.11 2.26 1.94 12.34 0.00 59.96 4.79 13.85 3.34 6.81 5.79 5.47 0.00 66.16 3.49 11.12 0.97 0.85 2.86 14.55 0.00 65.10 3.04 10.98 2.98 2.65 8.66 6.58 0.01 64.84 3.78 11.44 0.90 0.78 3.21 15.05 0.00 63.73 3.27 11.27 2.77 2.43 9.73 6.80 0.00 65.04 3.74 11.36 0.94 0.91 3.00 15.02 0.00 63.95 3.26 11.21 2.88 2.82 9.09 6.79 0.00 62.52 5.54 13.20 0.99 1.57 2.50 13.67 0.00 60.84 4.77 12.89 3.02 4.85 7.51 6.12 0.00 65.22 3.83 11.60 1.04 1.13 2.72 14.46 0.00 63.87 3.32 11.40 3.17 3.51 8.21 6.51 0.00 63.74 4.97 12.33 1.09 1.43 2.50 13.93 0.00 62.14 4.29 12.07 3.33 4.42 7.52 6.24 0.00 64.36 4.10 12.06 1.03 1.12 2.74 14.59 0.00 63.09 3.46 11.86 3.15 3.49 8.27 6.57 0.00 63.46 5.02 12.25 1.02 1.27 2.69 14.28 0.00 62.04 4.34 12.02 3.13 3.93 8.12 6.42 0.00 64.06 4.37 12.16 1.04 1.12 2.83 14.43 0.00 62.63 3.78 11.93 3.18 3.46 8.52 6.48 0.00 65.23 3.90 11.05 0.91 0.66 3.23 15.02 0.00 64.23 3.40 10.92 2.79 2.06 9.79 6.80 0.00 64.05 4.18 12.19 0.98 0.96 3.09 14.54 0.00 62.62 3.61 11.95 3.01 2.97 9.31 6.53 0.00 63.73 4.86 12.11 0.99 1.16 2.82 14.33 0.00 62.37 4.19 11.87 3.02 3.58 8.52 6.45 0.00 63.85 4.79 12.36 1.08 1.36 2.56 13.98 0.00 62.27 4.14 12.11 3.31 4.20 7.70 6.27 0.00 62.71 5.52 13.07 1.03 1.66 2.47 13.53 0.00 60.86 4.74 12.72 3.14 5.11 7.39 6.04 0.00 64.58 3.93 11.92 1.17 1.32 2.58 14.50 0.00 63.03 3.39 11.66 3.57 4.07 7.78 6.51 0.00 62.36 5.73 13.79 1.22 2.17 2.15 12.57 0.00 59.82 4.83 13.21 3.66 6.52 6.39 5.56 0.00 62.90 5.11 13.27 1.22 2.06 2.19 13.25 0.00 60.58 4.34 12.81 3.66 6.24 6.50 5.87 0.00 63.95 4.63 12.27 1.17 1.70 2.41 13.87 0.00 61.98 3.98 11.93 3.53 5.20 7.20 6.18 0.00 64.12 4.25 12.60 1.14 1.59 2.47 13.83 0.00 62.22 3.64 12.25 3.46 4.86 7.40 6.17 0.00 65.20 3.83 11.23 1.09 1.02 2.83 14.81 0.00 63.92 3.32 11.04 3.34 3.16 8.55 6.67 0.00 65.41 3.45 11.63 1.07 1.15 2.74 14.55 0.00 63.97 2.99 11.34 3.27 3.55 8.27 6.54 0.00 62.28 5.57 14.25 1.30 2.57 1.78 12.25 0.00 59.41 4.70 13.64 3.87 7.77 5.24 5.37 0.00 61.43 5.57 14.79 1.57 3.78 1.47 11.39 0.00 56.95 4.58 13.76 4.54 11.10 4.21 4.86 0.00 60.43 5.83 15.04 1.82 4.89 1.26 10.73 0.00 54.58 4.66 13.63 5.15 14.01 3.51 4.45 0.00 Average 60.24 5.80 15.26 1.71 5.16 1.18 10.65 0.00 54.30 4.63 13.80 4.82 14.75 3.29 4.41 0.00

PAGE 195

175Table C-12: Average EMPA data for LMSX-12. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 62.70 5.07 15.03 2.05 3.03 1.81 10.31 0.00 57.72 4.13 13.89 5.90 8.85 5.15 4.36 0.00 62.49 5.31 14.98 1.98 3.11 1.84 10.30 0.00 57.49 4.33 13.83 5.71 9.08 5.21 4.35 0.00 62.60 5.20 14.92 1.90 2.62 2.08 10.69 0.00 58.09 4.27 13.90 5.52 7.70 5.97 4.56 0.00 63.01 5.77 14.45 1.65 1.54 2.50 11.08 0.00 59.78 4.86 13.76 4.90 4.55 7.33 4.83 0.00 63.81 4.31 13.69 1.53 1.63 2.95 12.09 0.00 60.27 3.59 12.94 4.50 4.81 8.64 5.26 0.00 64.09 4.58 13.16 1.40 1.37 3.02 12.33 0.00 60.90 3.84 12.54 4.17 4.31 8.85 5.39 0.00 63.16 5.11 13.93 1.44 1.40 3.04 11.91 0.00 59.89 4.29 13.25 4.29 4.21 8.87 5.19 0.00 63.68 5.30 13.06 1.39 1.18 3.31 12.09 0.00 60.47 4.46 12.44 4.13 3.54 9.69 5.28 0.00 63.18 5.10 13.58 1.32 1.14 3.38 12.31 0.00 60.10 4.30 12.97 3.92 3.43 9.90 5.38 0.00 64.54 4.36 12.30 1.23 0.75 3.82 12.99 0.00 61.63 3.68 11.79 3.67 2.27 11.26 5.71 0.00 63.46 4.86 13.11 1.32 1.07 3.49 12.70 0.00 60.43 4.09 12.53 3.93 3.24 10.22 5.56 0.00 63.78 5.15 13.09 1.31 1.17 3.28 12.22 0.00 60.75 4.34 12.51 3.89 3.54 9.63 5.35 0.00 65.03 3.80 12.07 1.28 0.80 3.52 13.51 0.00 62.48 3.23 11.64 3.84 2.43 10.42 5.96 0.00 63.51 5.21 13.30 1.37 1.32 3.10 12.20 0.00 60.44 4.39 12.70 4.09 3.97 9.08 5.33 0.00 64.02 4.40 12.96 1.27 1.09 3.31 12.95 0.00 61.26 3.73 12.44 3.80 3.31 9.76 5.70 0.00 64.07 4.62 12.56 1.28 1.09 3.41 12.94 0.00 61.16 3.90 12.03 3.81 3.37 10.04 5.68 0.00 64.31 4.11 12.71 1.29 0.99 3.50 13.08 0.00 61.42 3.47 12.19 3.85 3.01 10.32 5.74 0.00 63.13 5.44 13.45 1.35 1.35 3.17 12.13 0.00 59.98 4.57 12.82 4.01 4.04 9.29 5.30 0.00 64.18 4.19 12.80 1.26 0.94 3.54 13.09 0.00 61.38 3.55 12.29 3.77 2.84 10.43 5.75 0.00 63.53 5.27 13.31 1.39 1.27 3.23 12.00 0.00 60.31 4.41 12.66 4.12 3.81 9.44 5.24 0.00 63.08 5.26 13.76 1.48 1.41 3.07 11.94 0.00 59.74 4.40 13.06 4.38 4.24 8.97 5.20 0.00 63.57 5.38 13.26 1.43 1.30 3.13 11.94 0.00 60.35 4.52 12.63 4.23 3.90 9.14 5.21 0.00 63.80 4.73 13.24 1.36 1.11 3.25 12.52 0.00 60.88 3.99 12.68 4.05 3.35 9.56 5.49 0.00 63.32 5.47 13.68 1.43 1.40 3.09 11.62 0.00 59.93 4.59 12.99 4.23 4.19 9.01 5.05 0.00 63.79 4.46 13.35 1.51 1.47 3.23 12.17 0.00 60.13 3.72 12.63 4.46 4.38 9.41 5.27 0.00 63.56 4.80 13.32 1.56 1.72 3.06 11.98 0.00 59.74 3.98 12.53 4.57 5.07 8.93 5.18 0.00 63.10 4.91 14.30 1.72 2.16 2.58 11.24 0.00 58.92 4.06 13.40 5.02 6.36 7.42 4.83 0.00 62.51 5.62 14.56 1.86 2.70 2.08 10.68 0.00 58.00 4.61 13.55 5.39 7.92 5.97 4.56 0.00 62.56 5.17 15.12 2.02 2.97 1.85 10.30 0.00 57.66 4.22 13.98 5.84 8.68 5.25 4.36 0.00 Average 62.46 5.41 14.69 2.07 3.02 1.85 10.51 0.00 57.53 4.41 13.58 5.97 8.80 5.26 4.45 0.00

PAGE 196

176Table C-13: Average EMPA data for LMSX-13. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Hf Ni Cr Co W Re Ta Al Hf 62.93 4.95 14.46 1.93 3.34 0.70 11.70 0.00 59.38 4.14 13.69 5.69 10.01 2.03 5.07 0.00 62.95 5.18 14.35 1.95 3.32 0.78 11.48 0.00 59.27 4.32 13.56 5.74 9.89 2.25 4.97 0.00 63.46 4.94 13.86 1.79 2.83 0.87 12.26 0.00 60.66 4.18 13.29 5.37 8.55 2.56 5.39 0.00 64.27 4.89 13.17 1.39 1.83 1.18 13.28 0.00 63.27 4.25 12.98 4.24 5.64 3.59 6.02 0.00 65.21 4.52 12.08 1.12 1.12 1.49 14.46 0.00 65.46 4.02 12.16 3.51 3.55 4.63 6.67 0.00 65.45 4.43 11.48 1.01 0.77 1.71 15.16 0.00 66.30 3.98 11.67 3.20 2.48 5.33 7.06 0.00 65.10 4.61 11.94 1.01 0.91 1.64 14.80 0.00 65.71 4.12 12.09 3.18 2.92 5.11 6.87 0.00 64.59 5.21 12.33 1.04 1.03 1.52 14.29 0.00 65.02 4.64 12.44 3.28 3.29 4.70 6.61 0.00 64.96 4.57 12.08 1.09 0.98 1.56 14.76 0.00 65.44 4.07 12.21 3.46 3.14 4.84 6.83 0.00 65.29 4.58 11.39 1.00 0.83 1.81 15.07 0.00 65.90 4.09 11.53 3.17 2.66 5.65 7.00 0.00 64.60 4.94 12.20 1.05 0.99 1.69 14.52 0.00 64.89 4.40 12.30 3.31 3.15 5.24 6.71 0.00 62.18 7.29 14.49 0.93 1.36 1.16 12.58 0.00 62.31 6.47 14.58 2.92 4.33 3.60 5.79 0.00 64.98 4.58 11.99 1.02 0.88 1.66 14.88 0.00 65.61 4.10 12.15 3.25 2.81 5.18 6.90 0.00 64.80 5.12 11.71 0.96 0.78 1.74 14.90 0.00 65.62 4.60 11.90 3.03 2.50 5.42 6.94 0.00 66.00 3.86 10.91 0.86 0.53 2.05 15.78 0.00 67.13 3.48 11.14 2.75 1.70 6.42 7.37 0.00 64.32 5.18 12.16 0.97 0.86 1.68 14.82 0.00 65.05 4.63 12.35 3.09 2.75 5.24 6.89 0.00 64.46 4.94 12.60 1.07 1.09 1.47 14.38 0.00 64.83 4.40 12.71 3.37 3.48 4.57 6.65 0.00 64.73 4.82 12.05 1.11 1.02 1.55 14.73 0.00 65.17 4.30 12.17 3.49 3.25 4.79 6.81 0.00 65.63 4.14 11.61 1.01 0.91 1.63 15.06 0.00 66.32 3.71 11.77 3.20 2.92 5.08 7.00 0.00 64.95 4.70 11.75 1.02 0.83 1.68 15.08 0.00 65.73 4.21 11.93 3.23 2.64 5.23 7.01 0.00 65.14 4.72 11.93 1.01 0.94 1.57 14.69 0.00 65.76 4.22 12.09 3.20 3.03 4.88 6.82 0.00 64.79 4.76 11.89 1.05 0.86 1.64 15.02 0.00 65.50 4.26 12.07 3.32 2.74 5.13 6.98 0.00 64.88 4.49 12.09 1.02 0.96 1.67 14.90 0.00 65.41 4.01 12.23 3.22 3.06 5.18 6.90 0.00 65.54 4.46 11.34 0.98 0.71 1.84 15.13 0.00 66.33 3.99 11.51 3.10 2.29 5.73 7.04 0.00 65.32 4.39 12.08 0.99 0.93 1.58 14.70 0.00 65.98 3.92 12.25 3.12 2.97 4.94 6.83 0.00 65.16 4.50 11.90 1.20 1.12 1.51 14.60 0.00 65.30 4.05 11.96 3.76 3.57 4.69 6.73 0.00 64.00 5.04 13.56 1.56 2.08 1.04 12.72 0.00 62.40 4.34 13.26 4.75 6.42 3.13 5.70 0.00 63.14 5.08 13.91 1.82 2.79 0.92 12.32 0.00 60.32 4.29 13.33 5.43 8.51 2.72 5.41 0.00 63.22 4.70 14.21 1.93 3.39 0.76 11.68 0.00 59.49 3.92 13.52 5.70 10.10 2.22 5.05 0.00 Average 62.89 5.20 14.15 2.01 3.34 0.75 11.65 0.00 59.18 4.34 13.36 5.94 9.97 2.18 5.04 0.00

PAGE 197

177Table C-14: Average EMPA data for LMSX-14. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Ti Hf Ni Cr Co W Re Ta Al Ti Hf 65.14 5.03 14.64 1.78 2.50 0.79 9.45 0.72 0.00 61.98 4.24 13.97 5.28 7.51 2.34 4.10 0.56 0.00 64.76 5.59 14.50 1.76 2.43 0.82 9.42 0.72 0.00 61.75 4.72 13.86 5.25 7.30 2.41 4.13 0.57 0.00 65.48 5.23 14.06 1.75 2.23 0.86 9.68 0.73 0.00 62.71 4.43 13.51 5.24 6.75 2.53 4.26 0.57 0.00 65.69 5.34 13.55 1.45 1.70 0.96 10.39 0.90 0.00 64.12 4.62 13.27 4.45 5.26 2.91 4.66 0.72 0.00 65.76 4.94 14.07 1.39 1.60 1.06 10.24 0.94 0.00 64.19 4.27 13.79 4.25 4.97 3.19 4.60 0.75 0.00 65.46 5.58 13.67 1.26 1.54 1.10 10.49 0.91 0.00 64.27 4.84 13.44 3.89 4.76 3.33 4.74 0.73 0.00 66.20 4.67 13.13 1.27 1.39 1.24 11.03 1.07 0.00 65.18 4.06 12.94 3.88 4.27 3.79 5.01 0.87 0.00 65.73 5.37 13.14 1.18 1.42 1.25 10.73 1.15 0.00 64.74 4.67 12.95 3.62 4.46 3.83 4.88 0.93 0.00 67.06 4.18 12.47 0.99 0.92 1.45 11.66 1.27 0.00 66.98 3.69 12.48 3.08 2.88 4.48 5.37 1.04 0.00 65.84 5.38 13.18 1.03 1.16 1.25 11.01 1.15 0.00 65.47 4.74 13.15 3.19 3.64 3.84 5.04 0.94 0.00 66.05 4.82 13.34 1.12 1.23 1.25 11.01 1.19 0.00 65.42 4.22 13.25 3.47 3.82 3.84 5.03 0.96 0.00 66.19 4.97 12.86 1.01 1.06 1.33 11.34 1.22 0.00 65.96 4.38 12.86 3.16 3.33 4.11 5.21 1.00 0.00 66.27 4.83 13.00 0.93 0.97 1.39 11.40 1.23 0.00 66.26 4.27 13.04 2.89 3.05 4.25 5.25 1.01 0.00 65.54 5.64 13.05 1.06 1.02 1.32 11.10 1.28 0.00 65.30 4.97 13.05 3.29 3.20 4.06 5.10 1.04 0.00 66.62 4.55 12.64 1.06 0.91 1.37 11.46 1.40 0.00 66.52 4.02 12.66 3.30 2.85 4.23 5.28 1.14 0.00 65.41 5.15 12.71 0.91 0.73 1.41 12.29 1.39 0.00 66.07 4.61 12.88 2.87 2.34 4.38 5.70 1.15 0.00 66.05 4.41 12.13 0.91 0.66 1.45 12.64 1.76 0.00 66.87 3.96 12.33 2.87 2.11 4.52 5.88 1.45 0.01 66.22 4.61 12.06 0.82 0.62 1.57 12.55 1.55 0.00 67.03 4.13 12.25 2.59 2.00 4.89 5.84 1.28 0.00 65.65 4.73 13.02 0.95 0.80 1.35 12.01 1.50 0.00 66.13 4.21 13.16 2.99 2.53 4.19 5.57 1.23 0.00 65.70 5.12 12.60 0.94 0.78 1.40 12.08 1.39 0.00 66.20 4.57 12.74 2.95 2.48 4.34 5.60 1.14 0.00 65.67 4.71 12.91 0.89 0.87 1.37 12.14 1.45 0.00 66.15 4.18 13.03 2.80 2.75 4.27 5.63 1.19 0.00 65.25 5.26 13.16 0.98 0.96 1.24 11.90 1.25 0.00 65.55 4.67 13.27 3.07 3.07 3.84 5.50 1.03 0.00 65.63 4.77 13.10 1.18 1.10 1.19 11.81 1.22 0.00 65.45 4.21 13.11 3.68 3.46 3.68 5.43 0.99 0.00 66.30 4.59 12.21 1.04 0.80 1.40 12.36 1.29 0.01 66.65 4.08 12.31 3.27 2.56 4.33 5.71 1.06 0.02 65.86 4.51 12.98 1.03 0.92 1.30 12.13 1.27 0.00 66.10 4.01 13.07 3.23 2.93 4.01 5.60 1.04 0.00 66.52 4.46 12.26 1.04 0.81 1.38 12.33 1.20 0.00 66.86 3.96 12.35 3.26 2.58 4.29 5.70 0.98 0.00 65.92 4.41 13.45 1.45 1.38 1.05 11.42 0.91 0.00 64.96 3.85 13.30 4.48 4.32 3.19 5.17 0.73 0.00 64.33 5.40 14.55 1.79 2.32 0.74 10.14 0.73 0.00 61.73 4.59 14.01 5.38 7.07 2.18 4.47 0.58 0.00 64.08 5.04 15.16 1.97 2.82 0.61 9.69 0.64 0.00 60.62 4.23 14.40 5.82 8.45 1.77 4.21 0.49 0.00 Average 63.77 5.44 15.15 1.97 2.88 0.66 9.50 0.63 0.00 60.15 4.55 14.34 5.82 8.60 1.93 4.12 0.48 0.00

PAGE 198

178Table C-15: Average EMPA data for LMSX-15. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Ti Hf Ni Cr Co W Re Ta Al Ti Hf 62.84 5.26 14.86 1.97 3.29 1.26 9.95 0.59 0.00 58.23 4.32 13.82 5.72 9.66 3.58 4.20 0.42 0.00 62.35 5.61 14.85 2.08 3.22 1.29 9.96 0.63 0.00 57.71 4.60 13.80 6.03 9.46 3.69 4.24 0.48 0.00 63.69 5.16 14.16 1.67 2.33 1.55 10.69 0.75 0.00 60.43 4.33 13.48 4.97 7.02 4.53 4.66 0.58 0.00 64.15 5.12 13.36 1.40 1.56 2.02 11.43 0.97 0.00 61.89 4.37 12.92 4.20 4.75 6.02 5.07 0.77 0.00 64.99 4.46 12.36 1.11 1.01 2.37 12.48 1.21 0.00 63.68 3.87 12.15 3.41 3.13 7.17 5.62 0.97 0.00 64.64 4.70 12.17 1.28 1.08 2.42 12.40 1.32 0.00 62.96 4.06 11.89 3.90 3.34 7.26 5.55 1.05 0.00 65.06 4.02 12.20 1.06 0.92 2.59 12.77 1.38 0.00 63.73 3.48 11.98 3.25 2.87 7.83 5.75 1.11 0.00 64.19 4.98 12.54 1.07 1.04 2.46 12.32 1.39 0.00 62.80 4.31 12.31 3.28 3.21 7.42 5.54 1.12 0.00 65.14 4.23 12.30 1.09 0.98 2.56 12.37 1.33 0.00 63.63 3.65 12.05 3.33 3.00 7.73 5.56 1.06 0.00 63.21 5.80 13.28 1.24 1.37 2.24 11.62 1.24 0.00 61.27 4.97 12.91 3.77 4.22 6.70 5.18 0.98 0.00 64.57 4.72 12.61 1.14 1.14 2.43 12.00 1.39 0.00 62.86 4.07 12.33 3.47 3.52 7.29 5.37 1.10 0.00 61.90 5.84 12.91 0.87 1.10 2.33 11.06 1.61 2.37 58.14 4.85 12.19 2.63 3.32 6.66 4.78 1.20 6.22 63.96 5.03 12.85 1.14 1.15 2.38 12.17 1.32 0.00 62.40 4.34 12.58 3.47 3.54 7.16 5.46 1.05 0.00 64.36 5.03 12.33 1.10 1.03 2.51 12.26 1.36 0.00 62.86 4.35 12.08 3.37 3.18 7.58 5.50 1.08 0.00 63.75 5.34 13.17 1.13 1.23 2.33 11.70 1.34 0.00 62.00 4.61 12.86 3.45 3.80 6.99 5.23 1.06 0.00 65.09 4.34 11.47 1.10 0.77 2.65 13.15 1.41 0.00 63.99 3.78 11.32 3.39 2.40 8.04 5.94 1.13 0.00 64.30 4.97 12.86 0.98 1.16 2.41 12.00 1.33 0.00 62.83 4.29 12.59 2.99 3.59 7.27 5.39 1.06 0.00 63.52 5.08 12.34 1.16 1.04 2.37 12.14 2.36 0.00 62.19 4.40 12.12 3.57 3.21 7.15 5.46 1.89 0.00 63.13 5.05 12.46 1.05 1.05 2.38 11.80 3.08 0.00 61.91 4.36 12.24 3.21 3.25 7.21 5.33 2.49 0.00 65.88 3.56 10.80 1.04 0.50 2.98 13.65 1.59 0.00 64.92 3.10 10.67 3.20 1.57 9.07 6.18 1.27 0.00 64.85 4.34 12.16 1.09 1.02 2.57 12.56 1.42 0.00 63.34 3.75 11.91 3.33 3.14 7.74 5.64 1.14 0.00 65.31 4.11 11.30 1.04 0.65 2.78 13.33 1.48 0.00 64.34 3.59 11.18 3.19 2.03 8.44 6.03 1.19 0.00 65.81 3.53 11.29 0.90 0.55 2.94 13.31 1.67 0.00 64.91 3.07 11.18 2.77 1.69 8.94 6.03 1.34 0.00 65.27 4.00 11.10 0.90 0.47 3.06 13.49 1.70 0.00 64.45 3.49 10.99 2.79 1.45 9.34 6.12 1.37 0.00 64.78 4.17 12.21 0.94 0.74 2.80 12.83 1.52 0.00 63.64 3.63 12.04 2.90 2.31 8.47 5.79 1.22 0.00 63.16 5.96 13.58 1.12 1.28 2.26 11.33 1.31 0.00 61.38 5.12 13.24 3.41 3.96 6.78 5.06 1.04 0.00 65.18 3.99 12.35 1.11 1.07 2.54 12.46 1.30 0.00 63.57 3.43 12.06 3.37 3.26 7.66 5.59 1.04 0.00 63.51 5.57 13.81 1.70 2.08 1.71 10.82 0.81 0.00 60.45 4.69 13.19 5.04 6.26 5.02 4.74 0.63 0.00 63.59 5.00 14.09 1.87 2.94 1.41 10.38 0.69 0.00 59.42 4.14 13.22 5.46 8.72 4.05 4.47 0.53 0.00 Average 62.53 5.70 14.75 2.07 3.29 1.21 9.85 0.60 0.00 57.87 4.67 13.71 6.01 9.66 3.45 4.19 0.45 0.00

PAGE 199

179Table C-16: Average EMPA data for LMSX-16. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Ru Hf Ni Cr Co W Re Ta Al Ru Hf 61.79 5.50 14.62 1.76 3.18 1.31 10.77 1.02 0.00 57.37 4.52 13.68 5.11 9.35 3.75 4.59 1.63 0.00 61.88 4.96 14.97 2.01 3.26 1.28 10.59 1.04 0.00 57.01 4.05 13.85 5.79 9.53 3.64 4.48 1.65 0.00 62.39 5.37 14.31 1.66 2.80 1.46 11.11 0.91 0.00 58.46 4.45 13.46 4.87 8.31 4.21 4.78 1.47 0.00 62.65 5.08 14.19 1.56 2.06 1.69 11.93 0.84 0.00 59.70 4.28 13.57 4.66 6.23 4.98 5.22 1.37 0.00 63.17 5.13 13.55 1.31 1.49 1.94 12.38 1.02 0.00 60.99 4.39 13.14 3.96 4.57 5.77 5.50 1.69 0.00 63.66 4.40 13.11 1.30 1.12 2.40 13.12 0.89 0.00 61.63 3.77 12.74 3.94 3.43 7.18 5.84 1.48 0.00 63.40 5.10 12.79 1.18 1.14 2.45 13.17 0.76 0.00 61.55 4.38 12.46 3.60 3.51 7.34 5.88 1.27 0.00 63.07 4.84 13.32 1.19 1.16 2.50 12.92 0.99 0.00 60.94 4.14 12.92 3.61 3.56 7.45 5.73 1.65 0.00 62.79 5.61 13.10 1.00 1.29 2.35 12.88 0.97 0.00 60.97 4.83 12.77 3.05 3.97 7.03 5.75 1.62 0.00 62.96 4.84 13.29 1.24 1.23 2.45 12.99 1.00 0.00 60.77 4.14 12.87 3.73 3.77 7.28 5.77 1.66 0.00 63.28 5.24 12.68 1.02 1.17 2.49 13.16 0.97 0.00 61.48 4.50 12.36 3.09 3.61 7.45 5.88 1.63 0.00 64.10 4.05 12.59 1.26 0.90 2.68 13.64 0.78 0.00 62.23 3.48 12.27 3.83 2.77 8.02 6.09 1.31 0.00 63.27 5.20 12.78 1.19 1.29 2.37 12.96 0.95 0.00 61.19 4.45 12.40 3.60 3.93 7.09 5.76 1.58 0.00 63.04 4.62 13.11 1.35 1.20 2.54 13.21 0.94 0.00 60.73 3.94 12.67 4.05 3.66 7.53 5.85 1.56 0.00 62.98 5.48 13.05 1.11 1.27 2.31 12.97 0.83 0.00 61.20 4.71 12.71 3.36 3.91 6.93 5.80 1.38 0.00 63.24 4.70 13.22 1.22 1.29 2.25 13.29 0.79 0.00 61.41 4.04 12.88 3.69 3.98 6.73 5.93 1.32 0.00 63.70 4.80 12.52 1.10 1.23 2.51 13.27 0.87 0.00 61.73 4.12 12.17 3.32 3.78 7.52 5.91 1.45 0.00 63.75 3.89 12.35 1.19 1.03 2.65 14.12 0.92 0.00 61.96 3.43 12.05 3.59 3.16 7.95 6.31 1.55 0.00 63.31 5.11 12.66 1.07 1.24 2.41 13.29 0.90 0.00 61.50 4.39 12.34 3.26 3.82 7.24 5.94 1.51 0.00 63.69 4.34 12.78 1.23 1.07 2.50 13.48 0.91 0.00 61.80 3.73 12.44 3.74 3.29 7.47 6.01 1.51 0.00 63.71 4.88 12.45 1.02 1.07 2.63 13.49 0.75 0.00 62.04 4.20 12.16 3.09 3.31 7.90 6.04 1.26 0.00 63.20 4.54 13.11 1.11 1.18 2.53 13.36 0.96 0.00 61.23 3.90 12.75 3.37 3.63 7.56 5.95 1.60 0.00 63.38 5.18 12.81 1.07 1.24 2.43 13.03 0.86 0.00 61.51 4.45 12.47 3.25 3.81 7.27 5.81 1.44 0.00 62.65 4.83 13.64 1.20 1.33 2.36 12.86 1.12 0.00 60.40 4.12 13.20 3.62 4.07 7.03 5.70 1.86 0.00 63.58 4.80 12.53 1.16 1.08 2.67 13.35 0.84 0.00 61.57 4.12 12.18 3.50 3.32 7.97 5.94 1.39 0.00 63.50 4.21 12.97 1.21 1.11 2.59 13.49 0.90 0.00 61.47 3.60 12.59 3.68 3.40 7.74 6.01 1.50 0.00 63.24 5.25 13.20 1.28 1.56 2.16 12.48 0.82 0.00 60.87 4.48 12.75 3.85 4.77 6.40 5.52 1.37 0.00 62.19 4.95 14.44 1.77 2.46 1.68 11.52 0.99 0.00 58.36 4.11 13.60 5.18 7.31 4.86 5.08 1.60 0.00 62.22 5.40 14.43 1.81 3.15 1.34 10.76 0.90 0.00 57.74 4.45 13.44 5.26 9.26 3.84 4.59 1.44 0.00 Average 61.50 5.12 15.24 1.90 3.21 1.25 10.68 1.10 0.00 56.88 4.19 14.15 5.52 9.41 3.55 4.54 1.76 0.00

PAGE 200

180Table C-17: Average EMPA data for LMSX-17. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Ru Hf Ni Cr Co W Re Ta Al Ru Hf 60.65 5.06 14.73 2.02 3.34 1.31 10.76 2.14 0.00 55.41 4.10 13.50 5.77 9.66 3.68 4.52 3.36 0.00 60.70 5.20 14.85 1.98 3.40 1.22 10.44 2.22 0.00 55.39 4.20 13.60 5.66 9.85 3.43 4.38 3.49 0.00 60.54 5.19 14.95 1.91 3.16 1.33 10.74 2.17 0.00 55.57 4.22 13.77 5.50 9.20 3.77 4.53 3.42 0.00 61.38 5.07 14.18 1.69 2.33 1.68 11.58 2.10 0.00 57.49 4.19 13.29 4.93 6.86 4.87 5.00 3.37 0.00 62.48 4.49 13.15 1.44 1.74 2.20 12.61 1.88 0.00 59.27 3.76 12.48 4.26 5.16 6.48 5.51 3.07 0.00 61.70 5.07 13.68 1.44 1.78 2.12 12.06 2.14 0.00 58.33 4.25 12.97 4.25 5.27 6.21 5.25 3.48 0.00 60.80 5.80 14.48 1.45 1.91 1.92 11.47 2.17 0.00 57.39 4.85 13.70 4.27 5.69 5.59 4.98 3.53 0.00 62.40 4.93 12.88 1.46 1.53 2.23 12.56 2.03 0.00 59.32 4.15 12.28 4.32 4.57 6.39 5.49 3.31 0.00 62.81 4.46 12.83 1.35 1.30 2.37 12.97 1.91 0.00 60.10 3.78 12.31 4.02 3.94 7.00 5.70 3.14 0.00 62.32 4.79 12.89 1.31 1.21 2.40 13.18 1.90 0.00 59.82 4.06 12.41 3.94 3.68 7.12 5.82 3.15 0.00 62.51 4.70 12.84 1.20 1.08 2.54 13.23 1.91 0.00 60.16 4.00 12.40 3.60 3.28 7.54 5.85 3.17 0.00 63.15 4.30 12.13 1.15 0.87 2.86 13.52 2.01 0.00 60.72 3.66 11.70 3.47 2.65 8.50 5.97 3.33 0.00 63.59 4.04 11.86 1.07 0.69 3.06 13.80 1.89 0.00 61.35 3.45 11.48 3.24 2.12 9.09 6.12 3.14 0.00 62.51 4.51 12.45 1.08 0.80 2.96 13.60 2.09 0.00 60.17 3.84 12.02 3.25 2.45 8.78 6.01 3.46 0.00 63.65 3.75 11.31 1.03 0.51 3.40 14.47 1.89 0.00 61.49 3.21 10.97 3.10 1.55 10.11 6.42 3.14 0.00 63.51 3.76 11.51 1.02 0.55 3.41 14.30 1.94 0.00 61.22 3.21 11.14 3.07 1.68 10.13 6.34 3.21 0.00 63.10 4.31 12.03 1.06 0.78 3.00 13.84 1.87 0.00 60.90 3.68 11.65 3.21 2.38 8.93 6.14 3.11 0.00 63.15 4.25 11.95 1.15 0.78 2.86 13.84 2.01 0.00 60.94 3.63 11.57 3.49 2.39 8.50 6.14 3.33 0.00 61.66 5.23 13.44 1.19 1.21 2.46 12.84 2.06 0.00 59.13 4.45 12.85 3.57 3.68 7.26 5.66 3.40 0.00 63.81 3.96 11.57 1.21 0.71 2.81 14.23 1.70 0.00 61.90 3.40 11.27 3.66 2.19 8.40 6.35 2.83 0.00 63.20 4.30 12.36 1.15 0.84 2.70 13.55 1.89 0.00 61.06 3.68 11.98 3.49 2.57 8.05 6.02 3.15 0.00 63.11 4.33 12.28 1.24 0.93 2.56 13.65 1.90 0.00 60.96 3.70 11.90 3.76 2.84 7.63 6.06 3.16 0.00 62.65 4.64 12.71 1.27 1.14 2.40 13.12 2.01 0.00 60.22 3.95 12.33 3.82 3.47 7.10 5.79 3.32 0.00 62.00 5.25 13.37 1.30 1.38 2.20 12.39 2.12 0.00 59.28 4.44 12.83 3.89 4.17 6.47 5.45 3.48 0.00 62.01 5.00 13.29 1.33 1.43 2.16 12.78 1.99 0.00 59.39 4.23 12.76 3.98 4.32 6.39 5.63 3.28 0.00 62.01 5.00 13.51 1.43 1.66 2.09 12.26 2.04 0.00 58.87 4.21 12.87 4.24 4.99 6.14 5.35 3.33 0.00 61.14 5.48 14.46 1.64 2.33 1.62 11.14 2.20 0.00 57.20 4.55 13.58 4.79 6.88 4.67 4.79 3.55 0.00 61.34 5.05 13.92 1.92 2.75 1.53 11.26 2.24 0.00 56.67 4.13 12.91 5.54 8.04 4.37 4.78 3.57 0.00 60.40 5.24 14.90 1.91 3.33 1.31 10.63 2.27 0.00 55.22 4.24 13.67 5.47 9.65 3.69 4.47 3.58 0.00 Average 60.27 5.25 14.99 2.02 3.47 1.25 10.45 2.29 0.00 54.83 4.24 13.69 5.77 10.00 3.52 4.37 3.59 0.00

PAGE 201

181Table C-18: Average EMPA data for LMSX-18. Atomic percent (at%) Normalized Weight percent (wt%) Ni Cr Co W Re Ta Al Pd Hf Ni Cr Co W Re Ta Al Pd Hf 62.40 5.09 15.05 2.11 3.48 1.32 10.25 0.31 0.00 57.26 4.13 13.86 6.06 10.12 3.74 4.33 0.51 0.00 61.84 5.32 15.13 2.06 3.37 1.34 10.45 0.48 0.00 56.89 4.33 13.97 5.94 9.84 3.82 4.42 0.81 0.00 62.62 5.04 14.50 1.80 2.74 1.64 11.04 0.61 0.00 58.43 4.17 13.58 5.25 8.08 4.71 4.74 1.04 0.00 63.35 4.71 13.50 1.41 1.64 2.17 12.25 0.98 0.00 60.50 3.97 12.91 4.19 4.93 6.40 5.38 1.71 0.00 64.38 3.84 11.75 1.06 0.71 2.70 14.10 1.47 0.00 62.75 3.31 11.49 3.23 2.18 8.12 6.32 2.59 0.00 64.01 3.85 11.55 0.96 0.64 2.83 14.41 1.75 0.00 62.41 3.32 11.30 2.92 1.98 8.53 6.46 3.09 0.00 62.32 5.27 13.41 1.12 1.18 2.36 12.86 1.47 0.00 60.18 4.50 13.00 3.48 3.62 7.02 5.71 2.58 0.00 63.90 4.08 11.71 1.09 0.74 2.81 14.07 1.61 0.00 62.00 3.51 11.40 3.31 2.27 8.41 6.27 2.83 0.00 64.65 3.26 10.91 1.00 0.52 3.04 14.87 1.74 0.00 62.99 2.81 10.67 3.04 1.62 9.14 6.66 3.07 0.00 62.60 4.78 12.57 1.12 1.07 2.52 13.59 1.75 0.00 60.48 4.09 12.19 3.37 3.29 7.50 6.03 3.05 0.00 62.00 5.32 13.38 1.22 1.28 2.26 13.03 1.50 0.00 59.80 4.54 12.94 3.67 3.92 6.74 5.78 2.62 0.00 63.75 4.08 11.69 1.11 0.80 2.80 14.08 1.69 0.00 61.75 3.49 11.35 3.36 2.43 8.38 6.27 2.97 0.00 62.77 4.96 12.63 1.06 1.06 2.43 13.46 1.64 0.00 60.85 4.25 12.28 3.22 3.25 7.27 5.99 2.88 0.00 63.62 4.01 11.56 0.96 0.73 2.92 14.29 1.92 0.00 61.69 3.44 11.25 2.91 2.23 8.74 6.37 3.37 0.00 62.19 5.37 13.06 1.08 1.16 2.42 13.01 1.71 0.00 60.00 4.59 12.65 3.27 3.55 7.18 5.77 3.00 0.00 62.42 5.22 12.55 1.08 1.01 2.50 13.54 1.68 0.00 60.48 4.47 12.20 3.28 3.11 7.47 6.03 2.95 0.00 63.50 4.30 11.48 1.00 0.72 2.80 14.46 1.74 0.00 61.84 3.71 11.22 3.05 2.23 8.41 6.47 3.08 0.00 64.11 3.40 10.94 0.98 0.45 3.06 15.13 1.93 0.00 62.55 2.94 10.71 3.00 1.41 9.21 6.78 3.41 0.00 63.16 4.59 12.26 1.05 0.93 2.65 13.79 1.57 0.00 61.27 3.95 11.94 3.19 2.85 7.92 6.15 2.76 0.00 63.92 3.61 11.49 1.06 0.70 2.97 14.81 1.44 0.00 62.20 3.11 11.23 3.21 2.17 8.91 6.62 2.55 0.00 64.57 3.53 11.15 0.95 0.52 3.04 14.65 1.58 0.00 63.00 3.05 10.93 2.90 1.62 9.14 6.57 2.79 0.00 64.30 3.67 11.15 0.98 0.54 3.04 14.76 1.55 0.00 62.72 3.17 10.91 2.99 1.74 9.13 6.62 2.73 0.00 64.09 4.02 11.62 1.03 0.71 2.80 14.15 1.57 0.00 62.36 3.46 11.34 3.15 2.19 8.39 6.33 2.77 0.00 62.94 4.72 12.34 1.03 0.86 2.70 14.03 1.39 0.00 61.28 4.07 12.05 3.13 2.64 8.10 6.28 2.45 0.00 64.52 3.90 11.50 0.98 0.63 2.89 14.10 1.47 0.00 62.86 3.37 11.25 2.99 1.94 8.68 6.31 2.60 0.00 66.88 3.58 12.13 1.03 0.87 2.25 11.95 1.23 0.08 64.86 3.08 11.81 3.11 2.66 6.75 5.34 2.17 0.23 63.81 4.16 12.45 1.28 1.15 2.30 13.44 1.41 0.00 61.67 3.56 12.07 3.88 3.52 6.85 5.97 2.48 0.00 62.87 5.12 14.28 1.76 2.46 1.59 11.18 0.74 0.00 59.07 4.26 13.47 5.18 7.34 4.60 4.83 1.26 0.00 61.94 5.45 15.04 2.06 3.49 1.39 10.18 0.45 0.00 56.74 4.42 13.84 5.90 10.13 3.93 4.28 0.75 0.00 Average 62.31 5.06 14.86 2.04 3.44 1.36 10.45 0.48 0.00 57.23 4.12 13.71 5.86 10.03 3.84 4.41 0.80 0.00

PAGE 202

182 APPENDIX D SCHEIL ANALYSIS GRAPHS FOR LMSX-3 This appendix contains all the graphs de veloped from the scheil analysis of LMSX3 for both the Full and Short methods as well as the EMPA data used for the Full method.

PAGE 203

183 LMSX-3 Ni Scheil Comparison60.00 65.00 70.00 75.00 80.00 85.00 90.00 00.20.40.60.811.2 vol%wt% Ni Full Short Figure D-1: Scheil curves comparing full and short techniques for Ni in LMSX-3 LMSX-3 Cr Scheil Comparison0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.20.40.60.811.2 vol%wt% Cr Full Short Figure D-2: Scheil curves comparing full and short techniques for Cr in LMSX-3.

PAGE 204

184 LMSX-3 Co Scheil Analysis0.00 1.00 2.00 3.00 4.00 5.00 6.00 00.20.40.60.811.2 vol%wt% Co Full Short Figure D-3: Scheil curves for both full a nd short techniques for Co in LMSX-3. LMSX-3 W Scheil Analysis0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.20.40.60.811.2 vol%wt% W Full Short Figure D-4: Scheil curves for both full and short techniques for W in LMSX-3.

PAGE 205

185 LMSX-3 Re Scheil Analysis0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 00.20.40.60.811.2 vol%wt% Re Full Short Figure D-5: Scheil curves for both long and short techniques for Re in LMSX-3. LMSX-3 Ta Scheil Analysis0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 00.20.40.60.811.2 vol%wt% Ta Full Short Figure D-6: Scheil curves for both long and short techniques for Ta in LMSX-3.

PAGE 206

186 LMSX-3 Al Scheil Analysis0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.20.40.60.811.2 vol%wt% Al Full Short Figure D-7: Scheil curves for both full a nd short techniques for Al in LMSX-3

PAGE 207

187Table D-1: EMPA data fo r LMSX-3 scheil analysis Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 73.63 4.12 3.92 0.97 0.78 2.71 13.86 72.55 3.60 3.88 3.01 2.45 8.23 6.28 73.05 5.10 4.80 1.67 2.48 1.54 11.35 69.27 4.29 4.57 4.97 7.47 4.50 4.94 72.84 6.01 4.91 1.65 3.00 1.51 10.07 68.03 4.97 4.61 4.83 8.89 4.35 4.32 73.26 4.27 3.85 1.02 0.84 2.99 13.77 71.61 3.70 3.78 3.12 2.59 9.01 6.19 73.52 4.75 4.06 1.40 1.68 2.16 12.44 70.78 4.05 3.92 4.22 5.12 6.41 5.50 72.93 5.49 4.22 1.20 1.47 2.46 12.22 70.36 4.69 4.09 3.62 4.51 7.32 5.42 73.01 5.15 4.11 1.46 1.91 2.22 12.13 69.69 4.35 3.94 4.38 5.78 6.54 5.32 72.57 5.71 4.74 1.57 2.87 1.84 10.70 67.82 4.73 4.45 4.61 8.52 5.29 4.59 73.41 4.91 3.61 1.13 1.02 3.24 12.68 70.60 4.18 3.48 3.42 3.10 9.62 5.60 72.65 5.85 3.96 1.18 1.39 3.00 11.97 69.42 4.95 3.80 3.52 4.22 8.84 5.25 72.70 6.73 4.63 1.40 2.51 2.12 9.92 68.11 5.59 4.35 4.10 7.46 6.12 4.27 73.06 5.87 4.48 1.45 2.24 2.30 10.60 68.68 4.88 4.22 4.27 6.68 6.67 4.58 73.39 5.68 4.16 1.38 1.82 2.65 10.91 69.31 4.75 3.95 4.09 5.45 7.72 4.74 72.80 5.92 4.47 1.60 2.91 2.29 10.02 67.15 4.83 4.14 4.63 8.50 6.50 4.25 1 73.55 6.00 4.08 1.43 1.94 2.64 10.36 69.06 4.99 3.85 4.20 5.78 7.65 4.47 72.60 5.68 4.55 1.34 1.69 1.97 12.16 70.19 4.86 4.41 4.07 5.18 5.87 5.40 73.31 4.76 3.92 1.01 0.95 2.62 13.42 71.95 4.13 3.86 3.11 2.97 7.92 6.05 74.19 4.27 3.82 1.21 1.20 2.28 13.02 72.44 3.70 3.75 3.69 3.71 6.87 5.84 72.42 6.20 4.71 1.72 3.11 1.63 10.20 67.28 5.10 4.39 5.01 9.18 4.68 4.36 72.64 5.40 4.62 1.48 2.35 2.05 11.47 68.72 4.52 4.38 4.39 7.04 5.97 4.98 72.46 5.80 4.26 1.51 2.27 2.11 11.58 68.60 4.86 4.05 4.47 6.82 6.16 5.04 73.59 3.19 3.24 0.92 0.24 4.17 14.66 71.53 2.74 3.16 2.79 0.73 12.50 6.55 73.20 5.27 3.71 1.11 1.35 2.89 12.47 70.38 4.49 3.58 3.34 4.13 8.57 5.51 72.15 5.70 4.37 1.73 3.29 2.10 10.66 66.31 4.64 4.03 4.97 9.59 5.96 4.50 73.03 5.21 4.18 1.60 2.58 2.33 11.07 68.07 4.30 3.92 4.66 7.62 6.69 4.74 72.26 7.21 4.89 1.28 2.45 2.14 9.77 67.90 6.00 4.62 3.76 7.30 6.21 4.22 73.41 5.21 4.09 1.37 1.84 2.78 11.30 69.23 4.35 3.87 4.05 5.51 8.09 4.90 72.79 5.62 4.71 1.65 3.51 2.05 9.68 66.45 4.54 4.32 4.70 10.16 5.77 4.06 73.01 6.29 4.41 1.58 3.05 2.23 9.43 67.09 5.12 4.07 4.53 8.89 6.32 3.98 2 72.98 6.35 4.74 1.69 3.82 2.04 8.38 65.80 5.07 4.29 4.77 10.94 5.66 3.47

PAGE 208

188Table D-1 (cont.): EMPA data for LMSX-3 scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 72.88 4.14 4.14 0.93 0.87 2.73 14.32 71.91 3.60 4.10 2.90 2.71 8.29 6.50 74.41 2.72 4.82 1.74 2.18 1.81 12.31 70.69 2.29 4.60 5.17 6.57 5.31 5.38 72.46 6.26 3.77 1.57 2.08 2.06 11.81 68.98 5.28 3.60 4.67 6.27 6.04 5.17 72.68 5.32 4.83 1.64 2.57 1.76 11.20 68.49 4.44 4.57 4.85 7.69 5.12 4.85 72.46 5.35 5.18 1.79 3.21 1.61 10.41 67.14 4.39 4.81 5.20 9.42 4.59 4.43 73.28 5.12 4.89 1.47 2.45 1.86 10.93 69.23 4.29 4.63 4.36 7.33 5.41 4.74 72.60 5.80 4.61 1.31 2.27 2.09 11.31 68.93 4.88 4.40 3.90 6.84 6.13 4.94 75.18 3.37 3.36 1.37 1.48 2.60 12.63 72.05 2.86 3.2 4.12 4.49 7.68 5.56 72.30 5.96 3.82 1.46 2.19 2.44 11.83 68.27 4.99 3.62 4.32 6.56 7.11 5.13 73.85 4.85 4.17 1.11 1.50 2.80 11.71 70.60 4.11 4.00 3.33 4.54 8.26 5.15 73.17 4.69 3.97 1.43 1.50 3.05 12.20 69.33 3.94 3.77 4.24 4.52 8.89 5.31 72.53 5.74 4.54 1.79 3.44 2.09 9.87 66.13 4.63 4.15 5.12 9.94 5.88 4.13 71.08 7.38 5.11 1.38 2.16 2.30 10.58 67.12 6.17 4.84 4.08 6.48 6.71 4.59 72.66 6.49 4.37 1.51 3.24 2.08 9.63 66.88 5.29 4.05 4.34 9.45 5.91 4.08 3 74.08 4.58 4.37 1.64 3.48 2.32 9.54 67.22 3.68 3.98 4.65 10.01 6.48 3.98 78.86 4.29 4.41 0.91 0.70 1.78 9.05 77.47 3.74 4.35 2.79 2.19 5.38 4.10 73.35 5.17 4.79 1.76 2.67 1.41 10.89 69.16 4.32 4.53 5.20 7.98 4.10 4.70 73.96 5.00 4.45 1.38 1.90 1.70 11.60 71.26 4.27 4.30 4.18 5.82 5.04 5.14 73.27 4.78 4.31 1.16 1.27 2.23 12.97 71.59 4.14 4.23 3.56 3.93 6.73 5.82 72.81 5.24 4.36 1.23 1.23 2.25 12.89 71.09 4.53 4.27 3.76 3.80 6.76 5.78 73.18 4.39 3.99 0.97 0.79 2.64 14.04 72.30 3.84 3.96 3.01 2.47 8.04 6.37 74.15 3.30 3.61 0.91 0.68 2.81 14.54 73.39 2.90 3.59 2.83 2.12 8.57 6.61 73.75 4.57 4.39 1.60 2.49 1.60 11.60 69.99 3.84 4.18 4.76 7.50 4.67 5.06 72.97 4.69 4.84 1.89 2.90 1.50 11.21 68.27 3.89 4.54 5.55 8.60 4.33 4.82 73.19 5.44 4.56 1.51 2.05 1.75 11.51 70.04 4.61 4.38 4.52 6.21 5.17 5.06 73.04 5.26 4.68 1.62 2.43 1.57 11.41 69.40 4.42 4.46 4.81 7.34 4.59 4.98 73.68 4.78 4.28 1.36 1.49 1.92 12.49 71.62 4.11 4.17 4.15 4.60 5.77 5.58 72.93 5.37 4.35 1.20 1.30 2.19 12.66 71.16 4.64 4.26 3.66 4.01 6.58 5.68 73.22 5.40 4.85 1.76 2.88 1.51 10.38 68.47 4.47 4.55 5.15 8.54 4.35 4.46 4 73.64 3.92 4.00 0.93 0.84 2.71 13.96 72.57 3.42 3.96 2.88 2.63 8.22 6.32

PAGE 209

189Table D-1 (cont.): EMPA data for LMSX-3 scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 79.00 4.21 4.09 0.64 0.42 2.20 9.44 77.99 3.70 4.10 2.00 1.33 6.69 4.30 73.05 5.32 4.32 1.19 1.30 2.29 12.54 71.11 4.54 4.22 3.62 4.00 6.86 5.61 72.92 5.25 4.74 1.29 1.98 1.89 11.94 70.15 4.47 4.57 3.87 6.04 5.61 5.28 73.62 4.81 5.05 1.53 2.26 1.60 11.13 70.14 4.06 4.83 4.57 6.84 4.70 4.87 73.38 4.98 4.66 1.79 2.64 1.45 11.09 69.22 4.16 4.42 5.29 7.90 4.20 4.81 73.83 4.65 3.97 1.08 1.11 2.33 13.03 72.39 4.04 3.90 3.30 3.46 7.03 5.87 72.45 6.02 4.42 1.26 1.42 2.13 12.30 70.43 5.18 4.31 3.84 4.37 6.38 5.49 73.69 5.20 4.70 1.69 2.56 1.45 10.71 69.64 4.36 4.50 5.01 7.67 4.22 4.65 73.13 5.16 4.57 1.52 2.10 1.67 11.83 70.10 4.38 4.41 4.56 6.39 4.95 5.21 75.06 4.72 4.65 1.65 0.00 1.71 12.20 75.09 4.18 4.67 5.17 0.00 5.27 5.61 73.22 5.88 4.42 1.07 1.54 2.02 11.86 71.25 5.06 4.32 3.27 4.74 6.06 5.30 73.80 4.88 3.96 1.01 0.92 2.54 12.89 72.40 4.24 3.90 3.11 2.87 7.67 5.81 72.76 7.08 4.60 1.37 1.93 1.70 10.56 69.85 6.02 4.43 4.12 5.89 5.03 4.66 73.56 5.41 4.73 1.33 1.71 1.73 11.52 71.19 4.64 4.59 4.04 5.25 5.17 5.12 5 73.07 5.35 4.93 1.71 2.78 1.45 10.72 68.74 4.46 4.65 5.03 8.29 4.20 4.63 78.48 4.74 4.60 1.15 0.88 1.50 8.66 76.73 4.10 4.51 3.52 2.73 4.51 3.90 72.57 4.75 4.36 1.50 1.86 1.86 13.09 70.11 4.07 4.23 4.55 5.70 5.53 5.81 72.63 6.35 5.22 1.08 1.72 1.82 11.18 70.47 5.46 5.08 3.28 5.28 5.45 4.98 73.98 4.30 3.99 1.21 1.10 2.22 13.21 72.54 3.73 3.93 3.71 3.42 6.71 5.95 72.98 4.82 4.59 1.69 2.29 1.54 12.09 69.69 4.07 4.40 5.06 6.95 4.52 5.30 73.01 4.82 3.95 1.06 0.73 2.60 13.83 72.12 4.22 3.91 3.27 2.28 7.91 6.28 73.11 4.99 4.67 1.46 1.74 1.72 12.30 70.79 4.28 4.54 4.43 5.35 5.13 5.48 73.13 5.02 4.60 1.43 1.69 1.82 12.32 70.82 4.30 4.47 4.32 5.18 5.42 5.48 70.70 7.87 5.10 1.17 1.65 2.06 11.45 68.44 6.75 4.95 3.56 5.06 6.15 5.09 73.56 3.98 3.89 1.27 1.14 2.25 13.91 72.18 3.46 3.83 3.89 3.56 6.81 6.27 73.56 4.69 4.50 1.60 2.13 1.73 11.78 70.22 3.97 4.31 4.78 6.45 5.10 5.17 72.90 4.80 4.57 1.92 2.51 1.52 11.78 68.89 4.01 4.34 5.69 7.53 4.42 5.12 73.04 6.30 5.61 1.80 2.99 1.09 9.17 68.29 5.21 5.26 5.28 8.86 3.15 3.94 72.19 6.19 5.61 1.89 3.50 1.09 9.55 66.81 5.07 5.21 5.46 10.26 3.12 4.06 6 73.29 5.09 4.53 1.67 2.60 1.59 11.23 69.21 4.26 4.29 4.95 7.80 4.62 4.87

PAGE 210

190Table D-1 (cont.): EMPA data for LMSX-3 scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.21 4.22 4.61 1.21 1.00 1.49 9.25 76.38 3.70 4.50 3.70 3.11 4.48 4.20 73.56 4.80 4.00 1.16 1.37 2.21 12.90 71.73 4.14 3.91 3.55 4.23 6.65 5.78 74.53 3.94 3.83 1.27 1.10 2.24 13.10 72.90 3.41 3.76 3.88 3.40 6.75 5.89 73.66 3.09 3.35 1.04 0.39 2.94 15.53 73.34 2.73 3.35 3.23 1.22 9.02 7.11 73.35 4.29 4.17 1.61 2.17 1.87 12.54 70.00 3.62 3.99 4.81 6.57 5.50 5.50 73.56 4.13 3.97 1.54 1.49 2.06 13.24 71.27 3.55 3.86 4.68 4.59 6.16 5.90 72.61 4.91 4.65 1.86 2.94 1.42 11.63 68.20 4.08 4.38 5.46 8.75 4.11 5.02 72.18 5.94 4.40 1.17 1.41 2.27 12.63 70.20 5.12 4.3 3.56 4.36 6.82 5.65 72.72 5.26 4.03 1.08 0.98 2.50 13.43 71.44 4.58 3.98 3.31 3.05 7.57 6.07 73.52 4.58 3.87 1.23 1.04 2.41 13.35 71.96 3.97 3.81 3.77 3.22 7.28 6.00 74.04 3.79 3.86 1.53 1.53 1.94 13.31 71.87 3.26 3.76 4.66 4.70 5.81 5.94 73.66 2.78 3.27 0.77 0.07 3.58 15.87 73.40 2.45 3.27 2.42 0.21 10.99 7.27 73.37 4.51 4.25 1.66 2.00 1.78 12.44 70.32 3.83 4.08 4.97 6.06 5.26 5.48 72.01 5.85 4.88 1.53 2.45 1.78 11.50 68.29 4.91 4.65 4.55 7.38 5.21 5.01 7 73.87 4.29 4.21 1.44 1.51 1.88 12.80 71.83 3.69 4.11 4.37 4.64 5.63 5.72 78.60 4.47 5.18 1.20 1.38 1.27 7.89 75.98 3.83 5.03 3.65 4.23 3.78 3.5 77.14 4.99 5.01 1.65 2.05 1.09 8.07 73.23 4.20 4.77 4.90 6.18 3.19 3.52 77.55 3.95 4.30 0.86 0.48 2.12 10.73 76.73 3.46 4.27 2.68 1.52 6.47 4.88 76.94 4.54 4.37 1.47 1.13 1.42 10.13 75.02 3.92 4.27 4.49 3.48 4.28 4.54 76.50 4.33 4.71 1.45 1.12 1.38 10.51 74.84 3.75 4.62 4.43 3.47 4.16 4.73 75.04 5.44 4.97 1.87 2.01 1.09 9.59 71.57 4.59 4.75 5.60 6.07 3.21 4.20 74.02 6.25 5.07 1.32 1.18 1.50 10.63 72.56 5.43 4.98 4.05 3.67 4.52 4.79 73.94 5.88 5.46 1.68 1.98 1.22 9.85 70.81 4.99 5.25 5.03 6.00 3.59 4.33 74.32 4.37 4.23 1.41 0.95 1.91 12.81 73.12 3.80 4.18 4.35 2.97 5.79 5.79 73.26 5.55 4.60 1.17 1.11 1.82 12.49 72.30 4.85 4.56 3.61 3.46 5.55 5.66 72.71 6.85 5.73 1.34 2.07 1.26 10.04 70.04 5.84 5.54 4.06 6.33 3.75 4.44 71.79 6.83 6.05 2.09 3.63 0.89 8.72 66.01 5.56 5.58 6.03 10.59 2.53 3.68 73.35 4.99 4.98 1.83 2.75 1.33 10.78 69.02 4.16 4.70 5.40 8.21 3.84 4.66 72.90 4.87 4.87 1.91 2.80 1.41 11.24 68.48 4.05 4.60 5.61 8.34 4.07 4.85 8 72.45 6.11 4.77 1.45 1.89 1.76 11.57 69.71 5.21 4.60 4.36 5.78 5.22 5.12

PAGE 211

191Table D-1 (cont.): EMPA data for LMSX-3 scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co Pass Ni Cr Co Pass Ni Cr Co Pass Ni Cr Co 78.49 4.40 4.50 9 78.49 4.40 4.50 9 78.49 4.40 4.50 9 78.49 4.40 4.50 73.90 4.06 4.22 73.90 4.06 4.22 73.90 4.06 4.22 73.90 4.06 4.22 73.96 3.97 4.05 73.96 3.97 4.05 73.96 3.97 4.05 73.96 3.97 4.05 73.20 5.42 4.55 73.20 5.42 4.55 73.20 5.42 4.55 73.20 5.42 4.55 73.62 4.10 3.99 73.62 4.10 3.99 73.62 4.10 3.99 73.62 4.10 3.99 73.65 4.06 4.01 73.65 4.06 4.01 73.65 4.06 4.01 73.65 4.06 4.01 73.67 4.23 3.79 73.67 4.23 3.79 73.67 4.23 3.79 73.67 4.23 3.79 73.42 5.22 4.51 73.42 5.22 4.51 73.42 5.22 4.51 73.42 5.22 4.51 72.07 6.10 4.36 72.07 6.10 4.36 72.07 6.10 4.36 72.07 6.10 4.36 73.65 4.98 4.21 73.65 4.98 4.21 73.65 4.98 4.21 73.65 4.98 4.21 73.70 4.05 3.69 73.70 4.05 3.69 73.70 4.05 3.69 73.70 4.05 3.69 73.20 4.40 4.21 73.20 4.40 4.21 73.20 4.40 4.21 73.20 4.40 4.21 74.17 2.36 3.09 74.17 2.36 3.09 74.17 2.36 3.09 74.17 2.36 3.09 73.54 3.93 3.78 73.54 3.93 3.78 73.54 3.93 3.78 73.54 3.93 3.78 9 72.95 5.86 4.68 72.95 5.86 4.68 72.95 5.86 4.68 72.95 5.86 4.68 78.99 4.98 5.20 10 78.99 4.98 5.20 10 78.99 4.98 5.20 10 78.99 4.98 5.20 73.03 5.17 4.15 73.03 5.17 4.15 73.03 5.17 4.15 73.03 5.17 4.15 73.00 4.24 4.11 73.00 4.24 4.11 73.00 4.24 4.11 73.00 4.24 4.11 72.44 5.69 4.71 72.44 5.69 4.71 72.44 5.69 4.71 72.44 5.69 4.71 73.27 4.13 3.75 73.27 4.13 3.75 73.27 4.13 3.75 73.27 4.13 3.75 72.87 4.52 3.89 72.87 4.52 3.89 72.87 4.52 3.89 72.87 4.52 3.89 73.28 4.68 4.15 73.28 4.68 4.15 73.28 4.68 4.15 73.28 4.68 4.15 72.74 5.36 4.61 72.74 5.36 4.61 72.74 5.36 4.61 72.74 5.36 4.61 72.80 4.99 4.48 72.80 4.99 4.48 72.80 4.99 4.48 72.80 4.99 4.48 71.89 6.16 4.65 71.89 6.16 4.65 71.89 6.16 4.65 71.89 6.16 4.65 73.33 4.21 4.34 73.33 4.21 4.34 73.33 4.21 4.34 73.33 4.21 4.34 72.84 5.08 4.66 72.84 5.08 4.66 72.84 5.08 4.66 72.84 5.08 4.66 72.31 4.72 3.91 72.31 4.72 3.91 72.31 4.72 3.91 72.31 4.72 3.91 72.81 5.82 4.62 72.81 5.82 4.62 72.81 5.82 4.62 72.81 5.82 4.62 10 73.64 4.29 3.84 73.64 4.29 3.84 73.64 4.29 3.84 73.64 4.29 3.84

PAGE 212

192Table D-1 (cont.): EMPA data for LMSX-3 scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.56 4.15 4.14 0.90 0.46 2.08 9.70 77.37 3.6 4.1 2.8 1.44 6.32 4.4 72.64 6.00 5.40 1.79 3.67 1.17 9.33 66.94 4.90 5.00 5.18 10.72 3.32 3.95 72.67 5.00 4.31 1.30 1.57 2.05 13.10 70.69 4.31 4.21 3.96 4.83 6.14 5.86 72.22 6.02 4.59 1.10 1.38 2.17 12.53 70.52 5.21 4.50 3.36 4.27 6.53 5.62 73.34 5.45 4.83 1.62 2.79 1.34 10.63 69.21 4.55 4.58 4.78 8.36 3.91 4.61 73.94 3.33 3.83 1.13 0.70 2.62 14.46 73.06 2.91 3.80 3.51 2.18 7.98 6.57 72.68 4.83 4.29 1.71 2.25 1.78 12.46 69.25 4.08 4.10 5.10 6.79 5.21 5.46 71.45 6.69 4.80 1.16 1.51 2.12 12.28 69.52 5.76 4.7 3.55 4.65 6.36 5.49 73.34 4.29 3.71 1.17 0.76 2.53 14.20 72.44 3.75 3.68 3.62 2.37 7.69 6.45 73.37 4.62 4.42 1.30 1.56 2.03 12.69 71.23 3.97 4.31 3.95 4.81 6.06 5.66 72.77 5.07 4.21 1.46 1.65 1.95 12.88 70.48 4.35 4.09 4.43 5.08 5.83 5.73 73.05 5.23 4.88 1.67 2.55 1.43 11.18 69.27 4.40 4.65 4.97 7.66 4.18 4.87 70.00 8.60 5.48 1.03 2.11 1.89 10.89 67.39 7.33 5.29 3.10 6.45 5.61 4.82 72.69 4.93 4.76 1.66 2.23 1.63 12.11 69.45 4.17 4.56 4.98 6.74 4.79 5.32 11 74.13 3.62 3.77 1.38 1.15 2.16 13.78 72.60 3.14 3.71 4.25 3.57 6.53 6.20 77.96 4.44 4.97 1.43 1.25 1.36 8.59 75.36 3.80 4.82 4.33 3.82 4.05 3.8 73.23 4.80 4.39 1.49 1.89 1.70 12.49 70.72 4.10 4.26 4.50 5.80 5.07 5.54 73.03 4.75 4.45 1.78 2.62 1.60 11.76 68.93 3.97 4.22 5.26 7.86 4.66 5.10 72.38 6.00 5.26 1.87 3.46 1.25 9.77 66.92 4.91 4.88 5.41 10.14 3.57 4.15 73.48 5.21 4.72 1.55 2.11 1.60 11.33 70.30 4.41 4.53 4.65 6.40 4.72 4.98 73.23 4.95 4.12 0.97 0.80 2.54 13.40 72.29 4.33 4.08 2.99 2.51 7.71 6.08 72.66 5.40 4.89 1.71 2.66 1.59 11.08 68.44 4.51 4.62 5.05 7.95 4.63 4.80 72.36 5.75 4.82 1.58 2.10 1.55 11.84 69.50 4.89 4.64 4.76 6.39 4.59 5.23 72.55 6.54 4.95 1.23 1.93 1.78 11.01 69.86 5.58 4.79 3.71 5.90 5.30 4.87 73.38 5.90 4.98 1.28 2.12 1.53 10.81 70.55 5.02 4.81 3.85 6.47 4.52 4.78 72.96 4.56 4.25 1.24 1.20 2.11 13.68 71.70 3.97 4.19 3.82 3.75 6.39 6.18 73.00 4.63 4.61 1.86 2.77 1.54 11.60 68.61 3.85 4.35 5.46 8.26 4.45 5.01 72.29 6.65 5.04 1.29 2.02 1.83 10.87 69.30 5.65 4.85 3.87 6.14 5.41 4.79 72.31 5.89 4.39 1.26 1.50 2.11 12.54 70.26 5.07 4.28 3.84 4.63 6.32 5.60 12 72.66 5.23 4.86 1.85 2.86 1.43 11.11 68.20 4.35 4.58 5.43 8.52 4.13 4.79

PAGE 213

193Table D-1 (cont.): EMPA data for LMSX-3 scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.72 5.08 4.50 0.95 0.94 1.42 8.38 77.22 4.4 4.4 2.9 2.92 4.3 3.8 73.91 4.65 4.08 1.38 1.68 1.99 12.31 71.36 3.97 3.95 4.18 5.15 5.92 5.46 72.98 5.48 4.81 1.43 2.43 1.74 11.12 69.28 4.61 4.58 4.26 7.32 5.09 4.85 73.08 5.03 4.71 1.67 3.09 1.47 10.95 68.39 4.17 4.42 4.91 9.17 4.24 4.71 73.64 4.26 4.06 1.34 1.45 2.00 13.24 71.82 3.68 3.97 4.10 4.50 6.00 5.93 73.81 4.16 3.75 1.02 0.73 2.70 13.84 72.76 3.63 3.71 3.15 2.28 8.20 6.27 73.70 4.64 3.96 1.23 1.21 2.34 12.91 71.82 4.01 3.88 3.74 3.74 7.04 5.78 73.92 4.15 3.74 1.33 1.14 2.29 13.43 72.22 3.59 3.7 4.06 3.53 6.90 6.03 73.21 4.88 4.10 0.86 0.94 2.69 13.32 71.97 4.25 4.05 2.64 2.93 8.15 6.02 73.71 4.09 3.84 0.88 0.67 2.76 14.05 72.96 3.59 3.81 2.72 2.11 8.42 6.39 73.27 4.88 4.07 1.30 1.32 2.07 13.08 71.59 4.22 3.99 3.97 4.10 6.24 5.87 73.24 5.00 4.49 1.73 2.58 1.56 11.40 69.22 4.19 4.26 5.13 7.72 4.53 4.95 72.38 6.02 4.48 1.23 1.30 2.18 12.42 70.55 5.19 4.39 3.77 4.01 6.54 5.56 73.38 4.94 4.12 1.28 1.30 2.14 12.85 71.59 4.27 4.03 3.90 4.01 6.44 5.76 13 71.58 7.11 5.17 1.19 1.92 1.80 11.24 69.11 6.08 5.01 3.60 5.87 5.35 4.99 78.57 4.64 4.37 0.80 0.53 1.95 9.14 77.44 4.05 4.33 2.47 1.64 5.93 4.1 72.86 5.53 4.42 1.26 1.35 2.10 12.46 70.99 4.78 4.33 3.84 4.17 6.32 5.58 73.30 5.51 4.32 1.27 1.71 1.92 11.97 70.94 4.72 4.20 3.84 5.26 5.72 5.33 73.16 5.43 4.23 1.33 1.66 1.97 12.22 70.80 4.65 4.11 4.03 5.09 5.88 5.44 73.38 4.93 4.77 1.61 2.24 1.57 11.50 70.01 4.17 4.57 4.80 6.79 4.63 5.04 71.77 6.25 4.76 1.27 1.57 2.10 12.28 69.57 5.37 4.63 3.85 4.83 6.28 5.47 74.31 2.89 3.20 0.86 0.29 3.32 15.11 73.65 2.54 3.19 2.68 0.92 10.14 6.88 74.45 3.80 3.43 1.31 1.09 2.15 13.77 73.16 3.30 3.38 4.02 3.40 6.52 6.22 73.32 4.73 3.90 0.96 0.96 2.54 13.58 72.20 4.12 3.86 2.96 3.01 7.70 6.15 73.14 4.55 4.50 1.86 2.68 1.49 11.79 69.00 3.80 4.26 5.49 8.01 4.32 5.11 73.21 4.90 4.31 1.36 1.67 1.88 12.66 71.04 4.21 4.20 4.14 5.14 5.62 5.65 72.59 5.64 5.04 1.72 2.54 1.49 10.97 68.66 4.73 4.79 5.08 7.63 4.35 4.77 73.46 4.71 4.34 1.53 1.90 1.86 12.21 70.54 4.01 4.18 4.59 5.80 5.49 5.39 72.49 5.89 4.02 0.78 0.76 2.69 13.36 71.75 5.16 4.00 2.42 2.40 8.20 6.08 14 70.47 9.66 5.58 0.97 1.87 1.73 9.71 68.15 8.27 5.42 2.95 5.73 5.17 4.31

PAGE 214

194Table D-1 (cont): EMPA data for LMSX-3 scheil analysis Atomic Percent Weight Percent Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.11 4.50 4.28 1.04 0.50 1.80 9.76 77.12 3.93 4.24 3.23 1.57 5.48 4.43 73.26 4.88 4.03 0.91 1.05 2.74 13.13 71.62 4.23 3.95 2.80 3.25 8.25 5.90 71.20 7.88 5.40 1.30 2.37 1.63 10.23 67.88 6.65 5.16 3.87 7.16 4.79 4.48 72.96 5.46 4.50 1.15 1.39 2.13 12.41 71.11 4.71 4.40 3.51 4.30 6.41 5.56 72.49 6.34 5.31 1.81 3.25 1.19 9.60 67.44 5.23 4.96 5.26 9.59 3.42 4.10 72.83 5.37 4.83 1.61 2.41 1.49 11.46 69.37 4.53 4.62 4.80 7.29 4.37 5.02 74.16 3.03 3.29 0.91 0.46 2.98 15.16 73.70 2.67 3.28 2.84 1.44 9.14 6.92 74.03 3.77 3.81 1.27 1.04 2.25 13.84 72.76 3.28 3.76 3.91 3.23 6.81 6.25 73.33 5.21 4.67 1.75 2.70 1.39 10.95 69.19 4.35 4.42 5.18 8.08 4.03 4.75 72.66 4.68 4.52 1.84 2.69 1.57 12.05 68.54 3.91 4.28 5.42 8.05 4.58 5.22 73.81 3.93 3.93 1.50 1.68 1.84 13.30 71.62 3.38 3.83 4.55 5.17 5.51 5.93 72.97 5.01 4.67 1.68 2.21 1.57 11.88 69.70 4.24 4.48 5.04 6.69 4.63 5.22 73.02 5.03 4.27 1.72 2.40 1.70 11.85 69.24 4.23 4.07 5.10 7.22 4.97 5.17 74.06 2.57 3.24 0.73 0.10 3.49 15.81 73.91 2.27 3.25 2.28 0.32 10.72 7.25 15 74.10 2.69 3.26 0.96 0.23 3.36 15.40 73.42 2.36 3.25 2.99 0.72 10.26 7.01

PAGE 215

195 APPENDIX E SCHEIL ANALYSIS DATA AND GRAPHS FOR CMSX-4 This appendix contains the data and graphs that were used to evaluate the accuracy of the analysis used in this study on a co mmon commercial alloy whose properties have been widely examined.

PAGE 216

196 Scheil Analysis for Ni in CMSX-40.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ni Ni Figure E-1: Scheil curv e for Ni from CMSX-4. Scheil Analysis for Cr in CMSX-40.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Cr Cr Figure E-2: Scheil curv e for Cr from CMSX-4.

PAGE 217

197 Scheil Analysis for Co in CMSX-40.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Co Co Figure E-3: Scheil curv e for Co from CMSX-4. Scheil Analysis for Mo in CMSX-40.00 0.50 1.00 1.50 2.00 2.50 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Mo Mo Figure E-4: Scheil curve for Mo from CMSX-4.

PAGE 218

198 Scheil Analysis for W in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% W W Figure E-5: Scheil curve for W in CMSX-4. Scheil Analysis for Re in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Re Re Figure E-6: Scheil curv e for Re in CMSX-4.

PAGE 219

199 Scheil Analysis for Ta in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ta Ta Figure E-7: Scheil curv e for Ta from CMSX-4. Scheil Analysis for Al in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Al Al Figure E-8: Scheil curv e for Al from CMSX-4.

PAGE 220

200 Scheil Analysis for Ti in CMSX-40.00 0.50 1.00 1.50 2.00 2.50 3.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ti Ti Figure E-9: Scheil curve for Ti from CMSX-4

PAGE 221

201 Table E-1: Scheil curve data for CMSX-4 Ni Cr Co Mo W Re Ta Al Ti 69.09 15.16 7.57 2.24 1.84 0.00 8.89 7.26 2.42 69.02 13.04 7.68 1.55 2.26 0.17 8.89 7.19 2.27 68.81 12.25 7.70 1.22 2.42 0.19 8.66 7.13 2.17 68.77 11.98 7.74 1.21 2.52 0.31 8.26 7.09 1.94 68.67 11.18 7.75 1.16 2.56 0.36 8.08 7.08 1.90 68.33 10.24 7.88 0.93 2.62 0.46 7.85 7.08 1.88 68.09 9.66 7.91 0.92 2.66 0.64 7.63 6.97 1.85 68.03 9.53 7.95 0.90 2.68 0.72 7.52 6.95 1.83 67.99 9.18 8.02 0.89 2.72 0.75 7.51 6.94 1.80 67.93 9.09 8.05 0.87 3.00 0.76 7.29 6.90 1.77 67.65 8.96 8.08 0.86 3.03 0.78 7.01 6.88 1.72 67.61 8.93 8.16 0.85 3.04 0.80 6.96 6.87 1.72 67.59 8.83 8.20 0.84 3.06 0.92 6.94 6.86 1.69 67.53 8.67 8.21 0.84 3.07 0.92 6.91 6.86 1.63 67.41 8.00 8.23 0.83 3.14 0.95 6.88 6.82 1.61 67.39 7.90 8.27 0.81 3.16 0.95 6.77 6.81 1.61 67.37 7.78 8.27 0.81 3.17 0.96 6.76 6.79 1.60 67.35 7.72 8.32 0.80 3.18 1.02 6.70 6.77 1.60 67.26 7.66 8.42 0.79 3.22 1.05 6.60 6.73 1.59 67.22 7.59 8.42 0.77 3.23 1.13 6.42 6.63 1.55 66.84 7.56 8.50 0.77 3.31 1.30 6.37 6.61 1.53 66.56 7.53 8.54 0.77 3.37 1.46 6.32 6.55 1.53 66.48 7.46 8.87 0.75 3.37 1.49 6.28 6.54 1.50 66.45 7.35 8.88 0.75 3.38 1.52 6.12 6.54 1.49 66.38 7.31 8.90 0.75 3.42 1.55 6.03 6.52 1.48 66.11 7.28 8.92 0.74 3.51 1.56 6.03 6.47 1.47 65.90 7.26 8.93 0.73 3.59 1.66 6.00 6.46 1.42 65.87 7.16 8.98 0.72 3.69 1.70 5.86 6.46 1.41 65.72 7.16 9.00 0.72 3.72 1.74 5.85 6.42 1.40 65.70 6.98 9.00 0.69 3.73 1.75 5.80 6.42 1.36 65.61 6.97 9.04 0.69 3.76 1.77 5.70 6.39 1.35 65.53 6.88 9.05 0.68 3.76 1.77 5.62 6.39 1.32 65.47 6.81 9.13 0.67 3.77 1.81 5.57 6.38 1.31 65.47 6.60 9.14 0.67 3.78 1.86 5.57 6.37 1.30 65.41 6.54 9.14 0.66 3.79 1.92 5.53 6.37 1.30 65.40 6.50 9.15 0.64 3.82 1.93 5.41 6.36 1.28 65.32 6.45 9.25 0.63 3.83 1.94 5.37 6.36 1.27 65.30 6.41 9.26 0.62 3.86 1.97 5.34 6.32 1.25 65.28 6.29 9.32 0.62 3.87 1.97 5.29 6.24 1.25 65.25 6.26 9.32 0.61 3.91 2.029 5.29 6.21 1.24 65.10 6.23 9.34 0.61 3.93 2.05 5.26 6.15 1.24 65.09 6.20 9.35 0.61 3.94 2.10 5.20 6.15 1.22 65.07 6.19 9.39 0.60 3.95 2.13 5.19 6.12 1.22

PAGE 222

202 Table E-1 (cont.): Scheil curve data for CMSX-4 Ni Cr Co Mo W Re Ta Al Ti 65.06 6.18 9.40 0.60 4.04 2.13 5.09 6.10 1.20 64.84 6.16 9.41 0.59 4.04 2.19 5.03 6.04 1.20 64.82 6.08 9.43 0.59 4.06 2.20 4.92 6.02 1.20 64.75 6.05 9.49 0.59 4.07 2.36 4.90 6.02 1.19 64.75 6.03 9.62 0.58 4.14 2.39 4.87 6.01 1.19 64.56 6.03 9.67 0.58 4.14 2.41 4.87 6.01 1.19 64.47 5.90 9.79 0.58 4.17 2.48 4.86 5.99 1.18 64.22 5.89 9.82 0.58 4.18 2.50 4.84 5.95 1.17 64.08 5.87 9.85 0.57 4.19 2.55 4.83 5.90 1.14 64.04 5.79 9.90 0.57 4.21 2.57 4.81 5.85 1.13 63.66 5.71 9.91 0.56 4.21 2.63 4.79 5.81 1.13 63.61 5.70 9.96 0.55 4.22 2.64 4.69 5.78 1.12 63.55 5.66 10.03 0.55 4.23 2.72 4.59 5.76 1.11 63.55 5.64 10.08 0.54 4.24 2.73 4.57 5.74 1.09 63.54 5.53 10.08 0.54 4.26 2.74 4.56 5.73 1.09 63.39 5.44 10.09 0.54 4.27 2.83 4.51 5.72 1.08 63.35 5.42 10.13 0.54 4.32 2.83 4.49 5.72 1.08 63.33 5.41 10.13 0.54 4.33 2.93 4.48 5.72 1.06 63.26 5.41 10.15 0.54 4.36 2.94 4.36 5.70 1.06 63.04 5.38 10.18 0.54 4.39 2.98 4.24 5.63 1.02 62.84 5.30 10.19 0.53 4.48 3.05 4.20 5.59 1.00 62.63 5.29 10.20 0.53 4.49 3.16 4.19 5.46 0.96 62.58 5.27 10.31 0.52 4.57 3.32 4.05 5.45 0.96 62.50 5.22 10.56 0.51 4.57 3.33 3.87 5.43 0.95 62.18 5.15 10.59 0.50 4.64 3.44 3.85 5.40 0.95 62.06 5.11 10.59 0.50 4.70 3.54 3.85 5.37 0.94 61.83 5.08 10.62 0.48 4.75 3.60 3.77 5.30 0.93 61.77 4.62 10.73 0.48 4.83 3.71 3.73 5.09 0.88 61.69 4.60 10.76 0.48 4.89 3.71 3.66 5.06 0.87 61.68 4.58 10.90 0.48 4.90 3.72 3.65 5.01 0.86 61.64 4.44 10.95 0.47 4.90 3.80 3.52 4.98 0.85 61.62 4.40 11.10 0.46 5.20 3.95 3.51 4.96 0.82 61.62 4.38 11.10 0.46 5.21 4.00 3.45 4.96 0.80 61.45 4.30 11.19 0.45 5.32 4.02 3.43 4.92 0.79 61.42 4.26 11.22 0.44 5.69 4.20 3.38 4.90 0.71 61.20 4.17 11.27 0.44 5.89 4.41 3.17 4.87 0.70 61.07 4.04 11.31 0.43 5.96 4.43 3.01 4.87 0.69 60.48 4.01 11.54 0.41 6.19 4.69 2.98 4.83 0.66 60.43 3.86 11.56 0.41 6.19 4.89 2.93 4.83 0.64 60.40 3.80 11.56 0.39 6.26 4.91 2.93 4.82 0.63 59.89 3.49 11.64 0.37 6.35 5.05 2.89 4.81 0.62 58.91 3.39 11.67 0.30 6.48 5.10 2.88 4.73 0.62

PAGE 223

203 Table E-1 (cont.): Scheil curve data for CMSX-4 Ni Cr Co Mo W Re Ta Al Ti 58.18 3.16 11.78 0.30 6.50 5.15 2.84 4.63 0.61 57.94 3.11 12.32 0.27 6.53 5.22 2.80 4.60 0.61 56.63 3.09 12.36 0.25 6.55 5.36 2.66 4.04 0.58 56.42 3.03 12.47 0.25 6.56 5.41 2.34 3.97 0.54 54.26 2.88 13.19 0.21 6.57 5.77 1.97 3.91 0.51

PAGE 224

204 APPENDIX F SCHEIL ANALYSIS GRAPHS FOR LMSX-3 This appendix contains all the graphs de veloped from the scheil analysis of LMSX3 for both the Full and Short methods as well as the EMPA data used for the Full method.

PAGE 225

205 LMSX-3 Ni Scheil Comparison60.00 65.00 70.00 75.00 80.00 85.00 90.00 00.20.40.60.811.2 vol%wt% Ni Full Short Figure F-1: Scheil curves comparing full and short techniques for Ni in LMSX-3 LMSX-3 Cr Scheil Comparison0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.20.40.60.811.2 vol%wt% Cr Full Short Figure F-2: Scheil curves comparing full and short techniques for Cr in LMSX-3.

PAGE 226

206 LMSX-3 Co Scheil Analysis0.00 1.00 2.00 3.00 4.00 5.00 6.00 00.20.40.60.811.2 vol%wt% Co Full Short Figure F-3: Scheil curves for both full and short techniques for Co in LMSX-3. LMSX-3 W Scheil Analysis0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.20.40.60.811.2 vol%wt% W Full Short Figure F-4: Scheil curves for both full and short techniques for W in LMSX-3.

PAGE 227

207 LMSX-3 Re Scheil Analysis0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 00.20.40.60.811.2 vol%wt% Re Full Short Figure F-5: Scheil curves for both long a nd short techniques for Re in LMSX-3. LMSX-3 Ta Scheil Analysis0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 00.20.40.60.811.2 vol%wt% Ta Full Short Figure F-6: Scheil curves for both long a nd short techniques for Ta in LMSX-3.

PAGE 228

208 LMSX-3 Al Scheil Analysis0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 00.20.40.60.811.2 vol%wt% Al Full Short Figure F-7: Scheil curves for both full and short techniques for Al in LMSX-3

PAGE 229

209Table F-1: EMPA data for LMSX-3 Scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 73.63 4.12 3.92 0.97 0.78 2.71 13.86 72.55 3.60 3.88 3.01 2.45 8.23 6.28 73.05 5.10 4.80 1.67 2.48 1.54 11.35 69.27 4.29 4.57 4.97 7.47 4.50 4.94 72.84 6.01 4.91 1.65 3.00 1.51 10.07 68.03 4.97 4.61 4.83 8.89 4.35 4.32 73.26 4.27 3.85 1.02 0.84 2.99 13.77 71.61 3.70 3.78 3.12 2.59 9.01 6.19 73.52 4.75 4.06 1.40 1.68 2.16 12.44 70.78 4.05 3.92 4.22 5.12 6.41 5.50 72.93 5.49 4.22 1.20 1.47 2.46 12.22 70.36 4.69 4.09 3.62 4.51 7.32 5.42 73.01 5.15 4.11 1.46 1.91 2.22 12.13 69.69 4.35 3.94 4.38 5.78 6.54 5.32 72.57 5.71 4.74 1.57 2.87 1.84 10.70 67.82 4.73 4.45 4.61 8.52 5.29 4.59 73.41 4.91 3.61 1.13 1.02 3.24 12.68 70.60 4.18 3.48 3.42 3.10 9.62 5.60 72.65 5.85 3.96 1.18 1.39 3.00 11.97 69.42 4.95 3.80 3.52 4.22 8.84 5.25 72.70 6.73 4.63 1.40 2.51 2.12 9.92 68.11 5.59 4.35 4.10 7.46 6.12 4.27 73.06 5.87 4.48 1.45 2.24 2.30 10.60 68.68 4.88 4.22 4.27 6.68 6.67 4.58 73.39 5.68 4.16 1.38 1.82 2.65 10.91 69.31 4.75 3.95 4.09 5.45 7.72 4.74 72.80 5.92 4.47 1.60 2.91 2.29 10.02 67.15 4.83 4.14 4.63 8.50 6.50 4.25 1 73.55 6.00 4.08 1.43 1.94 2.64 10.36 69.06 4.99 3.85 4.20 5.78 7.65 4.47 72.60 5.68 4.55 1.34 1.69 1.97 12.16 70.19 4.86 4.41 4.07 5.18 5.87 5.40 73.31 4.76 3.92 1.01 0.95 2.62 13.42 71.95 4.13 3.86 3.11 2.97 7.92 6.05 74.19 4.27 3.82 1.21 1.20 2.28 13.02 72.44 3.70 3.75 3.69 3.71 6.87 5.84 72.42 6.20 4.71 1.72 3.11 1.63 10.20 67.28 5.10 4.39 5.01 9.18 4.68 4.36 72.64 5.40 4.62 1.48 2.35 2.05 11.47 68.72 4.52 4.38 4.39 7.04 5.97 4.98 72.46 5.80 4.26 1.51 2.27 2.11 11.58 68.60 4.86 4.05 4.47 6.82 6.16 5.04 73.59 3.19 3.24 0.92 0.24 4.17 14.66 71.53 2.74 3.16 2.79 0.73 12.50 6.55 73.20 5.27 3.71 1.11 1.35 2.89 12.47 70.38 4.49 3.58 3.34 4.13 8.57 5.51 72.15 5.70 4.37 1.73 3.29 2.10 10.66 66.31 4.64 4.03 4.97 9.59 5.96 4.50 73.03 5.21 4.18 1.60 2.58 2.33 11.07 68.07 4.30 3.92 4.66 7.62 6.69 4.74 72.26 7.21 4.89 1.28 2.45 2.14 9.77 67.90 6.00 4.62 3.76 7.30 6.21 4.22 73.41 5.21 4.09 1.37 1.84 2.78 11.30 69.23 4.35 3.87 4.05 5.51 8.09 4.90 72.79 5.62 4.71 1.65 3.51 2.05 9.68 66.45 4.54 4.32 4.70 10.16 5.77 4.06 73.01 6.29 4.41 1.58 3.05 2.23 9.43 67.09 5.12 4.07 4.53 8.89 6.32 3.98 2 72.98 6.35 4.74 1.69 3.82 2.04 8.38 65.80 5.07 4.29 4.77 10.94 5.66 3.47

PAGE 230

210Table F-1 (cont.): EMPA data for LMSX-3 Scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 72.88 4.14 4.14 0.93 0.87 2.73 14.32 71.91 3.60 4.10 2.90 2.71 8.29 6.50 74.41 2.72 4.82 1.74 2.18 1.81 12.31 70.69 2.29 4.60 5.17 6.57 5.31 5.38 72.46 6.26 3.77 1.57 2.08 2.06 11.81 68.98 5.28 3.60 4.67 6.27 6.04 5.17 72.68 5.32 4.83 1.64 2.57 1.76 11.20 68.49 4.44 4.57 4.85 7.69 5.12 4.85 72.46 5.35 5.18 1.79 3.21 1.61 10.41 67.14 4.39 4.81 5.20 9.42 4.59 4.43 73.28 5.12 4.89 1.47 2.45 1.86 10.93 69.23 4.29 4.63 4.36 7.33 5.41 4.74 72.60 5.80 4.61 1.31 2.27 2.09 11.31 68.93 4.88 4.40 3.90 6.84 6.13 4.94 75.18 3.37 3.36 1.37 1.48 2.60 12.63 72.05 2.86 3.2 4.12 4.49 7.68 5.56 72.30 5.96 3.82 1.46 2.19 2.44 11.83 68.27 4.99 3.62 4.32 6.56 7.11 5.13 73.85 4.85 4.17 1.11 1.50 2.80 11.71 70.60 4.11 4.00 3.33 4.54 8.26 5.15 73.17 4.69 3.97 1.43 1.50 3.05 12.20 69.33 3.94 3.77 4.24 4.52 8.89 5.31 72.53 5.74 4.54 1.79 3.44 2.09 9.87 66.13 4.63 4.15 5.12 9.94 5.88 4.13 71.08 7.38 5.11 1.38 2.16 2.30 10.58 67.12 6.17 4.84 4.08 6.48 6.71 4.59 72.66 6.49 4.37 1.51 3.24 2.08 9.63 66.88 5.29 4.05 4.34 9.45 5.91 4.08 3 74.08 4.58 4.37 1.64 3.48 2.32 9.54 67.22 3.68 3.98 4.65 10.01 6.48 3.98 78.86 4.29 4.41 0.91 0.70 1.78 9.05 77.47 3.74 4.35 2.79 2.19 5.38 4.10 73.35 5.17 4.79 1.76 2.67 1.41 10.89 69.16 4.32 4.53 5.20 7.98 4.10 4.70 73.96 5.00 4.45 1.38 1.90 1.70 11.60 71.26 4.27 4.30 4.18 5.82 5.04 5.14 73.27 4.78 4.31 1.16 1.27 2.23 12.97 71.59 4.14 4.23 3.56 3.93 6.73 5.82 72.81 5.24 4.36 1.23 1.23 2.25 12.89 71.09 4.53 4.27 3.76 3.80 6.76 5.78 73.18 4.39 3.99 0.97 0.79 2.64 14.04 72.30 3.84 3.96 3.01 2.47 8.04 6.37 74.15 3.30 3.61 0.91 0.68 2.81 14.54 73.39 2.90 3.59 2.83 2.12 8.57 6.61 73.75 4.57 4.39 1.60 2.49 1.60 11.60 69.99 3.84 4.18 4.76 7.50 4.67 5.06 72.97 4.69 4.84 1.89 2.90 1.50 11.21 68.27 3.89 4.54 5.55 8.60 4.33 4.82 73.19 5.44 4.56 1.51 2.05 1.75 11.51 70.04 4.61 4.38 4.52 6.21 5.17 5.06 73.04 5.26 4.68 1.62 2.43 1.57 11.41 69.40 4.42 4.46 4.81 7.34 4.59 4.98 73.68 4.78 4.28 1.36 1.49 1.92 12.49 71.62 4.11 4.17 4.15 4.60 5.77 5.58 72.93 5.37 4.35 1.20 1.30 2.19 12.66 71.16 4.64 4.26 3.66 4.01 6.58 5.68 73.22 5.40 4.85 1.76 2.88 1.51 10.38 68.47 4.47 4.55 5.15 8.54 4.35 4.46 4 73.64 3.92 4.00 0.93 0.84 2.71 13.96 72.57 3.42 3.96 2.88 2.63 8.22 6.32

PAGE 231

211Table F-1 (cont.): EMPA data for LMSX-3 Scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 79.00 4.21 4.09 0.64 0.42 2.20 9.44 77.99 3.70 4.10 2.00 1.33 6.69 4.30 73.05 5.32 4.32 1.19 1.30 2.29 12.54 71.11 4.54 4.22 3.62 4.00 6.86 5.61 72.92 5.25 4.74 1.29 1.98 1.89 11.94 70.15 4.47 4.57 3.87 6.04 5.61 5.28 73.62 4.81 5.05 1.53 2.26 1.60 11.13 70.14 4.06 4.83 4.57 6.84 4.70 4.87 73.38 4.98 4.66 1.79 2.64 1.45 11.09 69.22 4.16 4.42 5.29 7.90 4.20 4.81 73.83 4.65 3.97 1.08 1.11 2.33 13.03 72.39 4.04 3.90 3.30 3.46 7.03 5.87 72.45 6.02 4.42 1.26 1.42 2.13 12.30 70.43 5.18 4.31 3.84 4.37 6.38 5.49 73.69 5.20 4.70 1.69 2.56 1.45 10.71 69.64 4.36 4.5 5.01 7.67 4.22 4.65 73.13 5.16 4.57 1.52 2.10 1.67 11.83 70.10 4.38 4.41 4.56 6.39 4.95 5.21 75.06 4.72 4.65 1.65 0.00 1.71 12.20 75.09 4.18 4.67 5.17 0.00 5.27 5.61 73.22 5.88 4.42 1.07 1.54 2.02 11.86 71.25 5.06 4.32 3.27 4.74 6.06 5.30 73.80 4.88 3.96 1.01 0.92 2.54 12.89 72.40 4.24 3.90 3.11 2.87 7.67 5.81 72.76 7.08 4.60 1.37 1.93 1.70 10.56 69.85 6.02 4.43 4.12 5.89 5.03 4.66 73.56 5.41 4.73 1.33 1.71 1.73 11.52 71.19 4.64 4.59 4.04 5.25 5.17 5.12 5 73.07 5.35 4.93 1.71 2.78 1.45 10.72 68.74 4.46 4.65 5.03 8.29 4.20 4.63 78.48 4.74 4.60 1.15 0.88 1.50 8.66 76.73 4.10 4.51 3.52 2.73 4.51 3.9 72.57 4.75 4.36 1.50 1.86 1.86 13.09 70.11 4.07 4.23 4.55 5.70 5.53 5.81 72.63 6.35 5.22 1.08 1.72 1.82 11.18 70.47 5.46 5.08 3.28 5.28 5.45 4.98 73.98 4.30 3.99 1.21 1.10 2.22 13.21 72.54 3.73 3.93 3.71 3.42 6.71 5.95 72.98 4.82 4.59 1.69 2.29 1.54 12.09 69.69 4.07 4.40 5.06 6.95 4.52 5.30 73.01 4.82 3.95 1.06 0.73 2.60 13.83 72.12 4.22 3.91 3.27 2.28 7.91 6.28 73.11 4.99 4.67 1.46 1.74 1.72 12.30 70.79 4.28 4.54 4.43 5.35 5.13 5.48 73.13 5.02 4.60 1.43 1.69 1.82 12.32 70.82 4.30 4.47 4.32 5.18 5.42 5.48 70.70 7.87 5.10 1.17 1.65 2.06 11.45 68.44 6.75 4.95 3.56 5.06 6.15 5.09 73.56 3.98 3.89 1.27 1.14 2.25 13.91 72.18 3.46 3.83 3.89 3.56 6.81 6.27 73.56 4.69 4.50 1.60 2.13 1.73 11.78 70.22 3.97 4.31 4.78 6.45 5.10 5.17 72.90 4.80 4.57 1.92 2.51 1.52 11.78 68.89 4.01 4.34 5.69 7.53 4.42 5.12 73.04 6.30 5.61 1.80 2.99 1.09 9.17 68.29 5.21 5.26 5.28 8.86 3.15 3.94 72.19 6.19 5.61 1.89 3.50 1.09 9.55 66.81 5.07 5.21 5.46 10.26 3.12 4.06 6 73.29 5.09 4.53 1.67 2.60 1.59 11.23 69.21 4.26 4.29 4.95 7.80 4.62 4.87

PAGE 232

212Table F-1 (cont.): EMPA data for LMSX-3 Scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.21 4.22 4.61 1.21 1.00 1.49 9.25 76.38 3.70 4.50 3.70 3.11 4.48 4.20 73.56 4.80 4.00 1.16 1.37 2.21 12.90 71.73 4.14 3.91 3.55 4.23 6.65 5.78 74.53 3.94 3.83 1.27 1.10 2.24 13.10 72.90 3.41 3.76 3.88 3.40 6.75 5.89 73.66 3.09 3.35 1.04 0.39 2.94 15.53 73.34 2.73 3.35 3.23 1.22 9.02 7.11 73.35 4.29 4.17 1.61 2.17 1.87 12.54 70.00 3.62 3.99 4.81 6.57 5.50 5.50 73.56 4.13 3.97 1.54 1.49 2.06 13.24 71.27 3.55 3.86 4.68 4.59 6.16 5.90 72.61 4.91 4.65 1.86 2.94 1.42 11.63 68.20 4.08 4.38 5.46 8.75 4.11 5.02 72.18 5.94 4.40 1.17 1.41 2.27 12.63 70.20 5.12 4.3 3.56 4.36 6.82 5.65 72.72 5.26 4.03 1.08 0.98 2.50 13.43 71.44 4.58 3.98 3.31 3.05 7.57 6.07 73.52 4.58 3.87 1.23 1.04 2.41 13.35 71.96 3.97 3.81 3.77 3.22 7.28 6.00 74.04 3.79 3.86 1.53 1.53 1.94 13.31 71.87 3.26 3.76 4.66 4.70 5.81 5.94 73.66 2.78 3.27 0.77 0.07 3.58 15.87 73.40 2.45 3.27 2.42 0.21 10.99 7.27 73.37 4.51 4.25 1.66 2.00 1.78 12.44 70.32 3.83 4.08 4.97 6.06 5.26 5.48 72.01 5.85 4.88 1.53 2.45 1.78 11.50 68.29 4.91 4.65 4.55 7.38 5.21 5.01 7 73.87 4.29 4.21 1.44 1.51 1.88 12.80 71.83 3.69 4.11 4.37 4.64 5.63 5.72 78.60 4.47 5.18 1.20 1.38 1.27 7.89 75.98 3.83 5.03 3.65 4.23 3.78 3.50 77.14 4.99 5.01 1.65 2.05 1.09 8.07 73.23 4.20 4.77 4.90 6.18 3.19 3.52 77.55 3.95 4.30 0.86 0.48 2.12 10.73 76.73 3.46 4.27 2.68 1.52 6.47 4.88 76.94 4.54 4.37 1.47 1.13 1.42 10.13 75.02 3.92 4.27 4.49 3.48 4.28 4.54 76.50 4.33 4.71 1.45 1.12 1.38 10.51 74.84 3.75 4.62 4.43 3.47 4.16 4.73 75.04 5.44 4.97 1.87 2.01 1.09 9.59 71.57 4.59 4.75 5.60 6.07 3.21 4.20 74.02 6.25 5.07 1.32 1.18 1.50 10.63 72.56 5.43 4.98 4.05 3.67 4.52 4.79 73.94 5.88 5.46 1.68 1.98 1.22 9.85 70.81 4.99 5.25 5.03 6.00 3.59 4.33 74.32 4.37 4.23 1.41 0.95 1.91 12.81 73.12 3.80 4.18 4.35 2.97 5.79 5.79 73.26 5.55 4.60 1.17 1.11 1.82 12.49 72.30 4.85 4.56 3.61 3.46 5.55 5.66 72.71 6.85 5.73 1.34 2.07 1.26 10.04 70.04 5.84 5.54 4.06 6.33 3.75 4.44 71.79 6.83 6.05 2.09 3.63 0.89 8.72 66.01 5.56 5.58 6.03 10.59 2.53 3.68 73.35 4.99 4.98 1.83 2.75 1.33 10.78 69.02 4.16 4.70 5.40 8.21 3.84 4.66 72.90 4.87 4.87 1.91 2.80 1.41 11.24 68.48 4.05 4.60 5.61 8.34 4.07 4.85 8 72.45 6.11 4.77 1.45 1.89 1.76 11.57 69.71 5.21 4.60 4.36 5.78 5.22 5.12

PAGE 233

213Table F-1 (cont.): EMPA data for LMSX-3 Scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.49 4.40 4.50 1.260.79 1.539.03 76.78 3.80 4.40 3.902.44 4.634.10 73.90 4.06 4.22 1.381.37 1.9913.08 72.07 3.50 4.13 4.224.24 5.975.86 73.96 3.97 4.05 1.301.31 2.0513.35 72.35 3.44 3.98 3.994.05 6.176.00 73.20 5.42 4.55 1.371.93 1.8711.67 70.33 4.61 4.39 4.115.87 5.535.15 73.62 4.10 3.99 1.391.42 2.0913.40 71.69 3.53 3.90 4.234.38 6.276.00 73.65 4.06 4.01 1.641.78 1.8213.04 71.05 3.47 3.88 4.965.43 5.425.78 73.67 4.23 3.79 1.561.75 2.0312.97 70.92 3.61 3.66 4.705.35 6.045.74 73.42 5.22 4.51 1.582.36 1.5811.33 69.86 4.40 4.3 4.727.13 4.644.95 72.07 6.10 4.36 1.351.69 2.0112.41 69.72 5.23 4.24 4.085.20 5.995.52 73.65 4.98 4.21 1.241.48 1.9512.49 71.76 4.29 4.12 3.794.59 5.855.59 73.70 4.05 3.69 1.030.64 2.7114.18 72.90 3.55 3.67 3.192.00 8.256.44 73.20 4.40 4.21 1.251.17 2.1113.66 71.98 3.84 4.16 3.843.64 6.396.17 74.17 2.36 3.09 0.690.08 3.5516.05 74.09 2.09 3.10 2.160.24 10.947.37 73.54 3.93 3.78 1.101.16 2.6013.89 71.85 3.40 3.70 3.373.60 7.836.24 9 72.95 5.86 4.68 1.331.76 1.7711.65 70.56 5.02 4.54 4.035.39 5.285.18 78.99 4.98 5.20 0.981.06 1.337.44 76.98 4.30 5.09 3.003.29 4.003.30 73.03 5.17 4.15 1.592.20 1.8512.03 69.60 4.36 3.97 4.746.64 5.425.27 73.00 4.24 4.11 1.812.24 1.7512.86 69.56 3.58 3.93 5.416.76 5.135.63 72.44 5.69 4.71 1.502.10 1.7111.84 69.46 4.83 4.53 4.506.40 5.065.22 73.27 4.13 3.75 0.870.63 2.7514.61 72.84 3.64 3.74 2.701.98 8.426.67 72.87 4.52 3.89 1.241.14 2.3413.99 71.49 3.93 3.83 3.823.54 7.076.31 73.28 4.68 4.15 1.501.38 1.9713.03 71.32 4.04 4.06 4.564.27 5.925.83 72.74 5.36 4.61 1.732.31 1.5211.72 69.31 4.52 4.41 5.176.99 4.465.13 72.80 4.99 4.48 1.641.96 1.6812.45 70.01 4.25 4.32 4.955.99 4.985.50 71.89 6.16 4.65 1.311.79 1.8312.40 69.71 5.29 4.53 3.975.49 5.485.53 73.33 4.21 4.34 1.531.63 1.8313.12 71.15 3.62 4.23 4.665.03 5.465.85 72.84 5.08 4.66 1.822.95 1.5811.09 68.07 4.20 4.37 5.328.73 4.554.76 72.31 4.72 3.91 1.060.90 2.7714.32 71.08 4.11 3.86 3.272.80 8.406.47 72.81 5.82 4.62 1.492.18 1.5711.51 68.80 4.94 4.45 4.486.64 4.635.07 10 73.64 4.29 3.84 1.050.83 2.5413.76 72.55 3.75 3.80 3.252.60 7.836.23

PAGE 234

214Table F-1 (cont.): EMPA data for LMSX-3 Scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.56 4.15 4.14 0.90 0.46 2.08 9.70 77.37 3.60 4.10 2.80 1.44 6.32 4.40 72.64 6.00 5.40 1.79 3.67 1.17 9.33 66.94 4.90 5.00 5.18 10.72 3.32 3.95 72.67 5.00 4.31 1.30 1.57 2.05 13.10 70.69 4.31 4.21 3.96 4.83 6.14 5.86 72.22 6.02 4.59 1.10 1.38 2.17 12.53 70.52 5.21 4.50 3.36 4.27 6.53 5.62 73.34 5.45 4.83 1.62 2.79 1.34 10.63 69.21 4.55 4.58 4.78 8.36 3.91 4.61 73.94 3.33 3.83 1.13 0.70 2.62 14.46 73.06 2.91 3.80 3.51 2.18 7.98 6.57 72.68 4.83 4.29 1.71 2.25 1.78 12.46 69.25 4.08 4.10 5.10 6.79 5.21 5.46 71.45 6.69 4.80 1.16 1.51 2.12 12.28 69.52 5.76 4.7 3.55 4.65 6.36 5.49 73.34 4.29 3.71 1.17 0.76 2.53 14.20 72.44 3.75 3.68 3.62 2.37 7.69 6.45 73.37 4.62 4.42 1.30 1.56 2.03 12.69 71.23 3.97 4.31 3.95 4.81 6.06 5.66 72.77 5.07 4.21 1.46 1.65 1.95 12.88 70.48 4.35 4.09 4.43 5.08 5.83 5.73 73.05 5.23 4.88 1.67 2.55 1.43 11.18 69.27 4.40 4.65 4.97 7.66 4.18 4.87 70.00 8.60 5.48 1.03 2.11 1.89 10.89 67.39 7.33 5.29 3.10 6.45 5.61 4.82 72.69 4.93 4.76 1.66 2.23 1.63 12.11 69.45 4.17 4.56 4.98 6.74 4.79 5.32 11 74.13 3.62 3.77 1.38 1.15 2.16 13.78 72.60 3.14 3.71 4.25 3.57 6.53 6.20 77.96 4.44 4.97 1.43 1.25 1.36 8.59 75.36 3.80 4.82 4.33 3.82 4.05 3.80 73.23 4.80 4.39 1.49 1.89 1.70 12.49 70.72 4.10 4.26 4.50 5.80 5.07 5.54 73.03 4.75 4.45 1.78 2.62 1.60 11.76 68.93 3.97 4.22 5.26 7.86 4.66 5.10 72.38 6.00 5.26 1.87 3.46 1.25 9.77 66.92 4.91 4.88 5.41 10.14 3.57 4.15 73.48 5.21 4.72 1.55 2.11 1.60 11.33 70.30 4.41 4.53 4.65 6.40 4.72 4.98 73.23 4.95 4.12 0.97 0.80 2.54 13.40 72.29 4.33 4.08 2.99 2.51 7.71 6.08 72.66 5.40 4.89 1.71 2.66 1.59 11.08 68.44 4.51 4.62 5.05 7.95 4.63 4.80 72.36 5.75 4.82 1.58 2.10 1.55 11.84 69.50 4.89 4.64 4.76 6.39 4.59 5.23 72.55 6.54 4.95 1.23 1.93 1.78 11.01 69.86 5.58 4.79 3.71 5.90 5.30 4.87 73.38 5.90 4.98 1.28 2.12 1.53 10.81 70.55 5.02 4.81 3.85 6.47 4.52 4.78 72.96 4.56 4.25 1.24 1.20 2.11 13.68 71.70 3.97 4.19 3.82 3.75 6.39 6.18 73.00 4.63 4.61 1.86 2.77 1.54 11.60 68.61 3.85 4.35 5.46 8.26 4.45 5.01 72.29 6.65 5.04 1.29 2.02 1.83 10.87 69.30 5.65 4.85 3.87 6.14 5.41 4.79 72.31 5.89 4.39 1.26 1.50 2.11 12.54 70.26 5.07 4.28 3.84 4.63 6.32 5.60 12 72.66 5.23 4.86 1.85 2.86 1.43 11.11 68.20 4.35 4.58 5.43 8.52 4.13 4.79

PAGE 235

215Table F-1 (cont.): EMPA data for LMSX-3 Scheil analysis. Atomic Percent Weight Percent Pass Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.72 5.08 4.50 0.95 0.94 1.42 8.38 77.22 4.40 4.40 2.90 2.92 4.30 3.80 73.91 4.65 4.08 1.38 1.68 1.99 12.31 71.36 3.97 3.95 4.18 5.15 5.92 5.46 72.98 5.48 4.81 1.43 2.43 1.74 11.12 69.28 4.61 4.58 4.26 7.32 5.09 4.85 73.08 5.03 4.71 1.67 3.09 1.47 10.95 68.39 4.17 4.42 4.91 9.17 4.24 4.71 73.64 4.26 4.06 1.34 1.45 2.00 13.24 71.82 3.68 3.97 4.10 4.50 6.00 5.93 73.81 4.16 3.75 1.02 0.73 2.70 13.84 72.76 3.63 3.71 3.15 2.28 8.20 6.27 73.70 4.64 3.96 1.23 1.21 2.34 12.91 71.82 4.01 3.88 3.74 3.74 7.04 5.78 73.92 4.15 3.74 1.33 1.14 2.29 13.43 72.22 3.59 3.7 4.06 3.53 6.90 6.03 73.21 4.88 4.10 0.86 0.94 2.69 13.32 71.97 4.25 4.05 2.64 2.93 8.15 6.02 73.71 4.09 3.84 0.88 0.67 2.76 14.05 72.96 3.59 3.81 2.72 2.11 8.42 6.39 73.27 4.88 4.07 1.30 1.32 2.07 13.08 71.59 4.22 3.99 3.97 4.10 6.24 5.87 73.24 5.00 4.49 1.73 2.58 1.56 11.40 69.22 4.19 4.26 5.13 7.72 4.53 4.95 72.38 6.02 4.48 1.23 1.30 2.18 12.42 70.55 5.19 4.39 3.77 4.01 6.54 5.56 73.38 4.94 4.12 1.28 1.30 2.14 12.85 71.59 4.27 4.03 3.90 4.01 6.44 5.76 13 71.58 7.11 5.17 1.19 1.92 1.80 11.24 69.11 6.08 5.01 3.60 5.87 5.35 4.99 78.57 4.64 4.37 0.80 0.53 1.95 9.14 77.44 4.05 4.33 2.47 1.64 5.93 4.10 72.86 5.53 4.42 1.26 1.35 2.10 12.46 70.99 4.78 4.33 3.84 4.17 6.32 5.58 73.30 5.51 4.32 1.27 1.71 1.92 11.97 70.94 4.72 4.20 3.84 5.26 5.72 5.33 73.16 5.43 4.23 1.33 1.66 1.97 12.22 70.80 4.65 4.11 4.03 5.09 5.88 5.44 73.38 4.93 4.77 1.61 2.24 1.57 11.50 70.01 4.17 4.57 4.80 6.79 4.63 5.04 71.77 6.25 4.76 1.27 1.57 2.10 12.28 69.57 5.37 4.63 3.85 4.83 6.28 5.47 74.31 2.89 3.20 0.86 0.29 3.32 15.11 73.65 2.54 3.19 2.68 0.92 10.14 6.88 74.45 3.80 3.43 1.31 1.09 2.15 13.77 73.16 3.30 3.38 4.02 3.40 6.52 6.22 73.32 4.73 3.90 0.96 0.96 2.54 13.58 72.20 4.12 3.86 2.96 3.01 7.70 6.15 73.14 4.55 4.50 1.86 2.68 1.49 11.79 69.00 3.80 4.26 5.49 8.01 4.32 5.11 73.21 4.90 4.31 1.36 1.67 1.88 12.66 71.04 4.21 4.20 4.14 5.14 5.62 5.65 72.59 5.64 5.04 1.72 2.54 1.49 10.97 68.66 4.73 4.79 5.08 7.63 4.35 4.77 73.46 4.71 4.34 1.53 1.90 1.86 12.21 70.54 4.01 4.18 4.59 5.80 5.49 5.39 72.49 5.89 4.02 0.78 0.76 2.69 13.36 71.75 5.16 4.00 2.42 2.40 8.20 6.08 14 70.47 9.66 5.58 0.97 1.87 1.73 9.71 68.15 8.27 5.42 2.95 5.73 5.17 4.31

PAGE 236

216Table F-1 (cont): EMPA data for LMSX-3 Scheil analysis Atomic Percent Weight Percent Ni Cr Co W Re Ta Al Ni Cr Co W Re Ta Al 78.11 4.50 4.28 1.04 0.50 1.80 9.76 77.12 3.93 4.24 3.23 1.57 5.48 4.43 73.26 4.88 4.03 0.91 1.05 2.74 13.13 71.62 4.23 3.95 2.80 3.25 8.25 5.90 71.20 7.88 5.40 1.30 2.37 1.63 10.23 67.88 6.65 5.16 3.87 7.16 4.79 4.48 72.96 5.46 4.50 1.15 1.39 2.13 12.41 71.11 4.71 4.40 3.51 4.30 6.41 5.56 72.49 6.34 5.31 1.81 3.25 1.19 9.60 67.44 5.23 4.96 5.26 9.59 3.42 4.10 72.83 5.37 4.83 1.61 2.41 1.49 11.46 69.37 4.53 4.62 4.80 7.29 4.37 5.02 74.16 3.03 3.29 0.91 0.46 2.98 15.16 73.70 2.67 3.28 2.84 1.44 9.14 6.92 74.03 3.77 3.81 1.27 1.04 2.25 13.84 72.76 3.28 3.76 3.91 3.23 6.81 6.25 73.33 5.21 4.67 1.75 2.70 1.39 10.95 69.19 4.35 4.42 5.18 8.08 4.03 4.75 72.66 4.68 4.52 1.84 2.69 1.57 12.05 68.54 3.91 4.28 5.42 8.05 4.58 5.22 73.81 3.93 3.93 1.50 1.68 1.84 13.30 71.62 3.38 3.83 4.55 5.17 5.51 5.93 72.97 5.01 4.67 1.68 2.21 1.57 11.88 69.70 4.24 4.48 5.04 6.69 4.63 5.22 73.02 5.03 4.27 1.72 2.40 1.70 11.85 69.24 4.23 4.07 5.10 7.22 4.97 5.17 74.06 2.57 3.24 0.73 0.10 3.49 15.81 73.91 2.27 3.25 2.28 0.32 10.72 7.25 15 74.10 2.69 3.26 0.96 0.23 3.36 15.40 73.42 2.36 3.25 2.99 0.72 10.26 7.01

PAGE 237

217 APPENDIX G SCHEIL ANALYSIS DATA AND GRAPHS FOR CMSX-4 This appendix contains the data and graphs that were used to evaluate the accuracy of the analysis used in this study on a co mmon commercial alloy whose properties have been widely examined.

PAGE 238

218 Scheil Analysis for Ni in CMSX-40.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ni Ni Figure G-1: Scheil curv e for Ni from CMSX-4. Scheil Analysis for Cr in CMSX-40.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Cr Cr Figure G-2: Scheil curv e for Cr from CMSX-4.

PAGE 239

219 Scheil Analysis for Co in CMSX-40.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Co Co Figure G-3: Scheil curv e for Co from CMSX-4. Scheil Analysis for Mo in CMSX-40.00 0.50 1.00 1.50 2.00 2.50 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Mo Mo Figure G-4: Scheil curv e for Mo from CMSX-4.

PAGE 240

220 Scheil Analysis for W in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% W W Figure G-5: Scheil curve for W in CMSX-4. Scheil Analysis for Re in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Re Re Figure G-6: Scheil curve for Re in CMSX-4.

PAGE 241

221 Scheil Analysis for Ta in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ta Ta Figure G-7: Scheil curv e for Ta from CMSX-4. Scheil Analysis for Al in CMSX-40.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Al Al Figure G-8: Scheil curv e for Al from CMSX-4.

PAGE 242

222 Scheil Analysis for Ti in CMSX-40.00 0.50 1.00 1.50 2.00 2.50 3.00 0.000.100.200.300.400.500.600.700.800.901.00 Vol%wt% Ti Ti Figure G-9: Scheil curv e for Ti from CMSX-4.

PAGE 243

223 Table G-1: Scheil curve data for CMSX-4. Ni Cr Co Mo W Re Ta Al Ti 69.09 15.16 7.57 2.24 1.84 0.00 8.89 7.26 2.42 69.02 13.04 7.68 1.55 2.26 0.17 8.89 7.19 2.27 68.81 12.25 7.70 1.22 2.42 0.19 8.66 7.13 2.17 68.77 11.98 7.74 1.21 2.52 0.31 8.26 7.09 1.94 68.67 11.18 7.75 1.16 2.56 0.36 8.08 7.08 1.90 68.33 10.24 7.88 0.93 2.62 0.46 7.85 7.08 1.88 68.09 9.66 7.91 0.92 2.66 0.64 7.63 6.97 1.85 68.03 9.53 7.95 0.90 2.68 0.72 7.52 6.95 1.83 67.99 9.18 8.02 0.89 2.72 0.75 7.51 6.94 1.80 67.93 9.09 8.05 0.87 3.00 0.76 7.29 6.90 1.77 67.65 8.96 8.08 0.86 3.03 0.78 7.01 6.88 1.72 67.61 8.93 8.16 0.85 3.04 0.80 6.96 6.87 1.72 67.59 8.83 8.20 0.84 3.06 0.92 6.94 6.86 1.69 67.53 8.67 8.21 0.84 3.07 0.92 6.91 6.86 1.63 67.41 8.00 8.23 0.83 3.14 0.95 6.88 6.82 1.61 67.39 7.90 8.27 0.81 3.16 0.95 6.77 6.81 1.61 67.37 7.78 8.27 0.81 3.17 0.96 6.76 6.79 1.60 67.35 7.72 8.32 0.80 3.18 1.02 6.70 6.77 1.60 67.26 7.66 8.42 0.79 3.22 1.05 6.60 6.73 1.59 67.22 7.59 8.42 0.77 3.23 1.13 6.42 6.63 1.55 66.84 7.56 8.50 0.77 3.31 1.30 6.37 6.61 1.53 66.56 7.53 8.54 0.77 3.37 1.46 6.32 6.55 1.53 66.48 7.46 8.87 0.75 3.37 1.49 6.28 6.54 1.50 66.45 7.35 8.88 0.75 3.38 1.52 6.12 6.54 1.49 66.38 7.31 8.90 0.75 3.42 1.55 6.03 6.52 1.48 66.11 7.28 8.92 0.74 3.51 1.56 6.03 6.47 1.47 65.90 7.26 8.93 0.73 3.59 1.66 6.00 6.46 1.42 65.87 7.16 8.98 0.72 3.69 1.70 5.86 6.46 1.41 65.72 7.16 9.00 0.72 3.72 1.74 5.85 6.42 1.40 65.70 6.98 9.00 0.69 3.73 1.75 5.80 6.42 1.36 65.61 6.97 9.04 0.69 3.76 1.77 5.70 6.39 1.35 65.53 6.88 9.05 0.68 3.76 1.77 5.62 6.39 1.32 65.47 6.81 9.13 0.67 3.77 1.81 5.57 6.38 1.31 65.47 6.60 9.14 0.67 3.78 1.86 5.57 6.37 1.30 65.41 6.54 9.14 0.66 3.79 1.92 5.53 6.37 1.30 65.40 6.50 9.15 0.64 3.82 1.93 5.41 6.36 1.28 65.32 6.45 9.25 0.63 3.83 1.94 5.37 6.36 1.27 65.30 6.41 9.26 0.62 3.86 1.97 5.34 6.32 1.25 65.28 6.29 9.32 0.62 3.87 1.97 5.29 6.24 1.25 65.25 6.26 9.32 0.61 3.91 2.02 5.29 6.21 1.24 65.10 6.23 9.34 0.61 3.93 2.05 5.26 6.15 1.24 65.09 6.20 9.35 0.61 3.94 2.10 5.20 6.15 1.22 65.07 6.19 9.39 0.60 3.95 2.13 5.19 6.12 1.22

PAGE 244

224 Table G-1 (cont.): Scheil curve data for CMSX-4. Ni Cr Co Mo W Re Ta Al Ti 65.06 6.18 9.40 0.60 4.04 2.13 5.09 6.10 1.20 64.84 6.16 9.41 0.59 4.04 2.19 5.03 6.04 1.20 64.82 6.08 9.43 0.59 4.06 2.20 4.92 6.02 1.20 64.75 6.05 9.49 0.59 4.07 2.36 4.90 6.02 1.19 64.75 6.03 9.62 0.58 4.14 2.39 4.87 6.01 1.19 64.56 6.03 9.67 0.58 4.14 2.41 4.87 6.01 1.19 64.47 5.90 9.79 0.58 4.17 2.48 4.86 5.99 1.18 64.22 5.89 9.82 0.58 4.18 2.50 4.84 5.95 1.17 64.08 5.87 9.85 0.57 4.19 2.55 4.83 5.90 1.14 64.04 5.79 9.90 0.57 4.21 2.57 4.81 5.85 1.13 63.66 5.71 9.91 0.56 4.21 2.63 4.79 5.81 1.13 63.61 5.70 9.96 0.55 4.22 2.64 4.69 5.78 1.12 63.55 5.66 10.03 0.55 4.23 2.72 4.59 5.76 1.11 63.55 5.64 10.08 0.54 4.24 2.73 4.57 5.74 1.09 63.54 5.53 10.08 0.54 4.26 2.74 4.56 5.73 1.09 63.39 5.44 10.09 0.54 4.27 2.83 4.51 5.72 1.08 63.35 5.42 10.13 0.54 4.32 2.83 4.49 5.72 1.08 63.33 5.41 10.13 0.54 4.33 2.93 4.48 5.72 1.06 63.26 5.41 10.15 0.54 4.36 2.94 4.36 5.70 1.06 63.04 5.38 10.18 0.54 4.39 2.98 4.24 5.63 1.02 62.84 5.30 10.19 0.53 4.48 3.05 4.20 5.59 1.00 62.63 5.29 10.20 0.53 4.49 3.16 4.19 5.46 0.96 62.58 5.27 10.31 0.52 4.57 3.32 4.05 5.45 0.96 62.50 5.22 10.56 0.51 4.57 3.33 3.87 5.43 0.95 62.18 5.15 10.59 0.50 4.64 3.44 3.85 5.40 0.95 62.06 5.11 10.59 0.50 4.70 3.54 3.85 5.37 0.94 61.83 5.08 10.62 0.48 4.75 3.60 3.77 5.30 0.93 61.77 4.62 10.73 0.48 4.83 3.71 3.73 5.09 0.88 61.69 4.60 10.76 0.48 4.89 3.71 3.66 5.06 0.87 61.68 4.58 10.90 0.48 4.90 3.72 3.65 5.01 0.86 61.64 4.44 10.95 0.47 4.90 3.80 3.52 4.98 0.85 61.62 4.40 11.10 0.46 5.20 3.95 3.51 4.96 0.82 61.62 4.38 11.10 0.46 5.21 4.00 3.45 4.96 0.80 61.45 4.30 11.19 0.45 5.32 4.02 3.43 4.92 0.79 61.42 4.26 11.22 0.44 5.69 4.20 3.38 4.90 0.71 61.20 4.17 11.27 0.44 5.89 4.41 3.17 4.87 0.70 61.07 4.04 11.31 0.43 5.96 4.43 3.01 4.87 0.69 60.48 4.01 11.54 0.41 6.19 4.69 2.98 4.83 0.66 60.43 3.86 11.56 0.41 6.19 4.89 2.93 4.83 0.64 60.40 3.80 11.56 0.39 6.26 4.91 2.93 4.82 0.63 59.89 3.49 11.64 0.37 6.35 5.05 2.89 4.81 0.62 58.91 3.39 11.67 0.30 6.48 5.10 2.88 4.73 0.62

PAGE 245

225 Table G-1 (cont.): Scheil curve data for CMSX-4. Ni Cr Co Mo W Re Ta Al Ti 58.18 3.16 11.78 0.30 6.50 5.15 2.84 4.63 0.61 57.94 3.11 12.32 0.27 6.53 5.22 2.80 4.60 0.61 56.63 3.09 12.36 0.25 6.55 5.36 2.66 4.04 0.58 56.42 3.03 12.47 0.25 6.56 5.41 2.34 3.97 0.54 54.26 2.88 13.19 0.21 6.57 5.77 1.97 3.91 0.51

PAGE 246

226 LIST OF REFERENCES 1. Hartman B., http://www.luftarchiv.de/motoren/junkers.htm last accessed April 19, 2004. 2. White S., http://www.simonawhite.pwp.blueyonder.co.uk/jumo004.html last accessed April 19, 2001. 3. Meher-Homji C.B, Anselm Franz and the Jumo 004 http://www.simonawhite.pwp.blueyonder.co.uk/Anselm%20Franz.htm last accessed April 19, 2001. 4. Davis J.R, Heat Resistance Materials ASM Specialty Handbook, ASM International, Metals Park, OH. 5. Dardi L., Dalal R., and Yaker C., Advanced High Temperature Alloys, Processing and Properties edited by Grant N., ASM Intern ational, Metals Park, OH, 6. Sims C.T., Stoloff N.S., and Hagel W.C., Superalloys II John Wiley & Sons, New York, NY, 1987. 7. Chandley G.D., Method for Improving Grain St ructure and Soundness in Castings U.S. Patent 3248764, 1966. 8. Piearcy, B.J., Single Crystal Metallic Part U.S. Patent 3494709, 1970. 9. Erickson G., Single Crystal Nickel-Based Superalloy United States Patent Number 5366695, 1994. 10. Pratt & Whitney F-119 stat us brochure, TS-7/99 9000 11. Fuchs G., and Boutwell B., Modeling of the Partitioning and Phase Transformation Temperature of and As-Cast Third Gene ration Single Cyrstal Ni-base Superalloy, Mat. Sci. A333, 2002, 72-79. 12. Darolia R., Lahrman D., and Field R., Formation of Topologically Closed Packed Phases in Nickel Base Single Crystal Superalloys Superaloys 1988, TMS, Warrendale, PA. 13. Pollock T.M., Murphy W.H., Goldman E.H., Uram D.L., and Tu J.S., Grain Defect Formation During Directional Solidification Superalloys 1992, TMS, 1992, pp.125-143.

PAGE 247

227 14. Phase Diagrams, Al-Ni ASM Handbook Vol 3, ASM International, Metals Park, OH, 1996. 15. Pollock T.M., The Growth and Elevated Temperature Stability of High Refractory Nickel-base Single Crystals Mat. Sci. and Eng. B32, 1995, pp. 255-266. 16. Fela, F.J., Influence of Chemical Compositi on Variations on the Elemental Solidification Partitioning in Nickel-Base Single Crystal Superalloys Masters Thesis, University of Florida, FL, 2000. 17. Wukusick C., Buchakjin L., and Darolia R., Heat Treatment for Nickel-Based Superalloy United States Patent Number 5100484 (1992). 18. Kearsey R., Beddoes J., Jones P., and Au P., Compositional Design Consideration for Microsegregation in Singl e Crystal Superalloy Systems Intermetallics, 2004, Article in Press. 19. Duhl D. and Cetel A., Advanced High Strength Single Crystal Superalloy Composition United States Patent Number 4719080, 1988. 20. Grosdidier T., Hazotte A., and Simon A., Precipitation and Dissolution Processes in - Single Crystal Nickel-Based Superalloys Mat. Sci. and Eng. A 256, 1998, pp.183-196. 21. Hopgood A., Nicholls A., Smith G., and Mart in J., Effects of Heat Treatment on Phase Chemistry and Microstructure of Single Crystal Superalloys, Mat. Sci and Tech. Vol. 4, 1988, pp. 146-152. 22. Tawancy H., Abbas M., and Al-Mana A., Th ermal Stability of Advanced Ni-Base Superalloys, Journal of Mat. Sci., Vol. 29, No. 9, 1994, pp.2445-2458. 23. Harris K. and Erickson G., Single Crystal Alloy Technology United States Patent Number 4643782, 1987. 24. Giamei A. and Anton D., Rhenium Addition s to Ni-B ase Superalloy: Effects on Microstructure Met. Trans. A, Vol. 16A, 1985, pp. 1997-2005. 25. Walston W., Ross E., Pollock T., OHara K., and Murphy W., Nickel-Base Superalloy and Article with High Temper ature Strength and Improved Stability United States Patent Number 5455120, 1995. 26. Pollock T., The Growth and Elevated Temperatur e Stability of High Refractory Nickel-base Single Crystals Mat. Sci. and Eng. B, 1995, 255-266. 27. Qiu, Y ., Effect of the Al and Mo on the mismatch and morphology in Nibased Superalloys Scripta Met., Vol 33, No. 12, 1995, pp.1961-1968.

PAGE 248

228 28. OHara K., Walston W., Ross E., and Darolia R., Nickel-Base Superalloy and Article United States Patent Number 5482789, 1996. 29. Murakami H., Honma T., Koizumi Y., and Harada H., Distribution of Platinum Group Metals in Ni-Base Single-Crystal Superalloys Superalloys 2000, TMS, Warrendale, PA, 2000, pp.747-755 30. Brooks C., Heat Treatment, Structure and Pr operties of Nonferrous Alloys ASM International, Metals Park, OH, 1995. 31. Caron P. and Khan T., Evolution of Ni-Based Superalloys for Single Crystal Gas Turbine Blade Applications Aerosp. Sci. Technol., Vol. 3, 1999, pp. 513-523. 32. Gell M., Duhl N., and Giamei A., The Development of Single Crystal Superalloy Turbine Blades Superalloys 1988, TMS, Warrendale, PA, 1988, pp. 205-214. 33. MacKay R. and Nathal M., MicrostructureProperty Relationships in Directionally Solidified Single Crysttal Nickel-Base Superalloys NASA Lewes Research Center, Cleveland OH, NAS 1.15.88788. 34. Vander Voort, G., Metallography Principles and Practice ASM International, Metals Park, OH, 1999. 35. Tin S., Pollock T., and King W., Carbon Additions and Grain Defects Formation in High refractory Nickel-Base Single Crystal Superalloys Superalloy 2000, TMS, Warrendale, PA, 2000, pp.201-210. 36. Gungor M., A Statistically Significant Experime ntal Technique for Investigating Microsegregation in Cast Alloys Met. Trans., 20A, 1989, pp.2529-2533. 37. Pollock T., Murphy M., Goldman E., Uram D., and Tu J., Grain Defect Formation During Directional Solidificatin of Nickel Base Single Crystals Superalloys 1992, TMS, Warrendale, PA, 1992, pp. 125-134. Noted as X9 38. Lecomte-Becker J., Sutdy of Solidification Features of Nickel-Base Superalloys in Relation with Composition Met. Trans. A, Vol. 19A, 1988, pp.2333-2340. 39. Giamei A. and Kear B., On the Nature of Freckles in Nickel-Base Superalloys, Met. Trans., Vol. 1, 1970, pp. 2185-2192. 40. Argence D., Vernault C., Desvalles Y., and Fournier D., MC-NG: A 4th Generation Single-Crystal Superalloy for Future Aeronautical Turbine Blades and Vanes Superalloys 2000, TMS, Warrendale, PA, 2000, pp. 829-837. 41. Eric W. Weisstein. "Curvature." From MathWorld --A Wolfram Web Resource. http://mathworld.wolfr am.com/Curvature.html Last accessed April 19th, 2004.

PAGE 249

229 42. Karunaratne M., Cox D., Carter P., and Reed R., Modeling of the Microsegregation in CMSX-4 Superalloy and its Homogenisation During Heat Treatment, Superalloys 2000, TMS, Wa rrendale, PA, 2000, pp.263-272. 43. Caron P. and Khan T., Design of Superalloys for Single Crystal Blade Applications: A 20-Year Experience Materials Design Approaches and Experiences, TMS, Warrendale, PA, 2001, pp.1-14.

PAGE 250

230 BIOGRAPHICAL SKETCH Eric C. Caldwell was born in June 1969 in suburbs of Los Angeles, California. He graduated from Glendora High School in June 1 987. After graduation he then enlisted in the United States Navy where he attended the Naval Nuclear Power School and earned his qualification to operate a naval nuclea r reactor engine room. He was honorably discharged in 1995 after eight years of service with the fi nal rank of MM1/SS and serving on two fast attack submarines and one submar ine tender. Upon receiving his discharge, he immediately enrolled at th e University of Florida, and joined the Department of Materials Science and Engineering in 1998, and readily began an internship with Pratt & Whitney GESP in West Palm Beach, FL. He gr aduated with a bachelors degree in this field in May 2000, and began a co-operati ve employment program with Siemens Westinghouse in Orlando, FL. In January 2001 he returned to the University of Florida to pursue a graduate degree in materials science and engineering. He is the recipient of the 2001 International Symposium on Superall oys Scholarship. He is currently scheduled to graduate with a Master of Science degree in August 2004 and will begin working for ExxonMobil Development in Houston, TX, shortly thereafter.


xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID E20110113_AAAAEH INGEST_TIME 2011-01-13T22:14:30Z PACKAGE UFE0006302_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES
FILE SIZE 6723 DFID F20110113_AACTQC ORIGIN DEPOSITOR PATH caldwell_e_Page_223.QC.jpg GLOBAL false PRESERVATION BIT MESSAGE_DIGEST ALGORITHM MD5
12625c5346afc4af7bd5167589e119ec
SHA-1
1e0bbe251cb8d6dbefafdb12400c44808736cd24
2611 F20110113_AACSTJ caldwell_e_Page_167.pro
6520a48f24f9b8b0327b1a4048a3702b
951f888b33aab5bb8e1ca747445a1c584c060eb1
1779 F20110113_AACTQD caldwell_e_Page_067.txt
9f3a04b98c96baebaae4cd7000ebcaa4
bafe6f648a5ce3002d3c486bffaf65cd62f68b42
3219 F20110113_AACSTK caldwell_e_Page_221.txt
97a0493313109d4bb0ede9ef8df88a67
38d8ed0b11c5f91df25367a5a839562de5deae87
88702 F20110113_AACTQE caldwell_e_Page_190.pro
f486edead88c56a2605ea3e348002d58
17dc4349fe7c77a6e193a7808b1d0e47d2786cb1
25271604 F20110113_AACTQF caldwell_e_Page_175.tif
9ba41c77988be8b08524a9cb4271572d
6e46018d76b7341ab27dec0a6e5621b2afc744d1
14020 F20110113_AACSTL caldwell_e_Page_003.jp2
ce591ad76453b2a729959c734d8f85a6
1e989d388d98c7ab594a5a7a2d54960899fe075c
81382 F20110113_AACTQG caldwell_e_Page_016.jpg
61891ace06e458fe080a4ce60d4c17a1
d5c225ff622eaf2b14827c9e49796466afcb5809
50294 F20110113_AACSTM caldwell_e_Page_100.pro
5e41e8be6093ff1f0a1180ba583d13ef
1def61bb3d35194385badb1687e07b6b8cb26606
307198 F20110113_AACUNA caldwell_e_Page_117.jp2
c2d8ab2ad641b8fd1d24870db12314cc
bd9fde4a8a290a1adddfe62b34fb88b1641c5cfa
6347 F20110113_AACSTN caldwell_e_Page_025thm.jpg
d69b2b63fdb6d0d5c010b19e03b02a06
14a9bc524c7b6a15687595cce00bd34ec23b773b
644 F20110113_AACTQH caldwell_e_Page_045.txt
45cb09d7764ba1a2ffdcd3f5ae283fc2
0a1d1118a77b36b832812f4ebc22300d5ce11d7f
111499 F20110113_AACUNB caldwell_e_Page_126.jp2
2b67b7e5cde287aefe659f2d2d4a8ba3
ed567742e87ed9a2f119d7def7f728d1ad706c9f
81577 F20110113_AACSTO caldwell_e_Page_133.jpg
27b754cf50d3bf9ce82022219e310798
45b3509d8333b01384ee5a1217b1c3a1f1c1afde
1437 F20110113_AACTQI caldwell_e_Page_002.pro
1f5108707581dc86d624c27ce02b6fad
ecd445e8c859518b1edc474eee7739635eecfedb
100851 F20110113_AACUNC caldwell_e_Page_129.jp2
5498993cb8b2b395ea07b25e80f798d7
aff2da021f5fa5a28ed9afeca11d86a5b6b27637
3043 F20110113_AACSTP caldwell_e_Page_193thm.jpg
d17958b26a5dc804575df7330046288a
bc5391956204c065e481adad6e4293078a417aec
60289 F20110113_AACTQJ caldwell_e_Page_187.jpg
2150b2f84d6b6aaa535f25ed363775e3
1fe1b8c50fe5a3cfd867c6ae4fed68848e6ad565
335492 F20110113_AACSTQ caldwell_e_Page_217.jp2
62db5657c75a822dce54a9425724ca8f
6bf810a02713a9201b62c87dab05bc89ff20357e
1051983 F20110113_AACTQK caldwell_e_Page_011.jp2
4d078dab75855ecbc2e2ddda3117b223
a937975e877861ba34a5d996fc2faffa02d862fd
114999 F20110113_AACUND caldwell_e_Page_130.jp2
608517f65879cc0238d43c5f4ee7173a
38e5d0047f61056fc2e99741f1ea7d9efe8fb91d
2766 F20110113_AACSTR caldwell_e_Page_234thm.jpg
24f1cf8774654f9abe4297c5cfb2b9f8
d68923177c609f9fd7d8ad93ea01aa565715b2c5
687 F20110113_AACTQL caldwell_e_Page_004thm.jpg
fd4e51629f18365776c9c956c048ddc2
cecd9d2ccfe264a046b4b8fa0aff8d08b09b3625
104746 F20110113_AACUNE caldwell_e_Page_131.jp2
f1ce3737d43076c9869e5e44989499f6
ca5413b98ddd403e583a796ac6b3bb627b03cc67
2639 F20110113_AACTDA caldwell_e_Page_173.pro
7701514f2f95afd3284df1b16e40a5e5
34ab08bedebfeae9f7124105204feb02be3b4838
79993 F20110113_AACSTS caldwell_e_Page_111.jpg
b99ec3a67a8e3c719ff47f40828d1ee9
438c8d9258e2c32590b8a12ccd3760027d6a2509
20369 F20110113_AACTQM caldwell_e_Page_089.QC.jpg
d5c620d8b82d07640e4b713a4e821108
01a0fcec5e4ab4685926f451603b6bae3f1aca19
104399 F20110113_AACUNF caldwell_e_Page_135.jp2
c1c407e7f3c2268415e70a779f1bfe37
9712e583219ccb84d12997a9d1804d94b50bb39e
1053954 F20110113_AACTDB caldwell_e_Page_067.tif
7c731387828345bd781d961e155a6da9
086231bdcf6c958322c8821b9117438ae809cdb7
F20110113_AACSTT caldwell_e_Page_156.tif
8ae7add1df55e643e6d166e85a3e0754
7a63ba08bd7dab64a83701c3142f17c14bb23429
6088 F20110113_AACTQN caldwell_e_Page_047thm.jpg
354462cfe95705ec667cb3a9eb733dc3
d3878f26389811ae1ecf4ec5b8fd6a19b067d80c
107945 F20110113_AACUNG caldwell_e_Page_144.jp2
66f537c1eb980ac3c1108d3e1e8e6df9
f2e7052ae238c21a80cc27851201ef2a63a81a86
6352 F20110113_AACTDC caldwell_e_Page_221thm.jpg
59879f272a4fd4cbc7cc4cfcde0f32f4
61f94e5e75dc3a4e87a58d483ddb53a26df966b8
33767 F20110113_AACSTU caldwell_e_Page_156.pro
b4051ee06869ec44ddae5587fd5f674e
02c680c7345746590727213bcc23c38085225423
101328 F20110113_AACTQO caldwell_e_Page_120.jp2
8f783d0a564f73df22b4b366dabd474e
5c71f7eab367aeca423ffa9cf8e31db68089728c
108578 F20110113_AACUNH caldwell_e_Page_145.jp2
aa01373b26811936976d52448739c3cc
8bc813c5add4c4e956dd93739b32cbb9253d9e23
888373 F20110113_AACTDD caldwell_e_Page_123.jp2
6deb808b3f5a5648f6b3e688e12a1a46
be2c596966047909698f2d19f90e73e77343dab3
503261 F20110113_AACSTV caldwell_e_Page_082.jp2
19af18cd257e9b23d8b3a3d6514302d8
b1961316dc1d9f87273a589a62e3bf337933f601
2190 F20110113_AACTQP caldwell_e_Page_236.txt
478efe4e4ad529bca8d45fa20067b59d
67e6272c2f553d7c4e84285f5c57f7cccb4d2a76
102253 F20110113_AACUNI caldwell_e_Page_148.jp2
ec8f587bd3e2a37284ddd5f0bfdbc657
a066b9d60a2721624f1ee4b5881d360d95cd5a93
75250 F20110113_AACTDE caldwell_e_Page_059.jp2
c363deb4777323c41585a747f0baa2fc
722320079b42c93ce524febe07ed36641442aef5
2030 F20110113_AACSTW caldwell_e_Page_138.txt
9a1b6e0082e66c594579e2b16b29a006
5c96bfe09003d8916aacf5d50c212cd1d87c60bd
F20110113_AACTQQ caldwell_e_Page_100.tif
0a62eb276e264fb39062c99c5304ba5d
4af16ce21efa157ebca41ad465672adbdd6283d6
67238 F20110113_AACUNJ caldwell_e_Page_156.jp2
0bc10d3c9c46d71b2447fc188ea8a644
05e713ce3fb6a7896406b14761c332d3d06cc9cb
2058 F20110113_AACTDF caldwell_e_Page_040.txt
aab01c4440601fdb41b93a1444c98853
5ee300ae697fe23428420457db73e7b9e24c5f25
4228 F20110113_AACSTX caldwell_e_Page_227thm.jpg
cc7246f25084482916fadc87bf185f62
f62050d7a91610603513b6aa6bb3085980b739bf
14247 F20110113_AACTQR caldwell_e_Page_060.QC.jpg
c67a6e0a0023b0d6d4da372ea1d862bf
b7f3779f5af89e29b3069ff2aaeae82ef5a98edd
927195 F20110113_AACUNK caldwell_e_Page_159.jp2
95b7835d923fd6c9171c39e54e39dd6e
2a2d2970fa4d02852846a745c42b6b131e6e23c3
1051898 F20110113_AACTDG caldwell_e_Page_047.jp2
7c54702ac3209e6979bf83bcfa1d28fb
d521f68e83d048f1c4c6fe2e68de37ff07a390f3
2997 F20110113_AACSTY caldwell_e_Page_212thm.jpg
86397135c8ee2a19c2940ac3d3a692ba
2406118ec470d0409b95c50d7089a14d31895e15
F20110113_AACUAA caldwell_e_Page_249.tif
e7e814fd02c998289b5c163727ddf20a
4223797da4e6d749d3ebc3caf1d2f5676c40f3a9
731743 F20110113_AACTQS caldwell_e_Page_018.jp2
64409c3f37544d1bfa2726c1c8889155
f2d05dfb877ea8a2070cc9b94c1d6a72deb9120d
577821 F20110113_AACUNL caldwell_e_Page_160.jp2
0b2da3e44f69faa84380395cc9f0bb63
7c18a8955e953b57da9b3080875aee1c2b29c15e
23434 F20110113_AACTDH caldwell_e_Page_161.jp2
4bc419705e16c5173f6baba8b5727459
e8ee3f326903e2bbfff6850fc6b35ed4c5e9c130
F20110113_AACSTZ caldwell_e_Page_045.tif
d45655c309a6b0a647e5b65208b71135
dbc443652f3e9fb860870aea3bd6951c817b2d28
5334 F20110113_AACUAB caldwell_e_Page_099thm.jpg
92542989714e91a921f575e2ea095593
65a25e6f51eabc067d7ca1a4516cce3ac7972c10
1518 F20110113_AACTQT caldwell_e_Page_073.txt
2b94ba41c985501595d27157d4a28831
61a40df3b89c209cc099ddae9e76770de4824100
1051899 F20110113_AACUNM caldwell_e_Page_162.jp2
706d8d08a820b470b2a5a2a17a7f2f3f
fd6e42781d4449f135e96883d42c397199f27aa6
50718 F20110113_AACTDI caldwell_e_Page_146.pro
303a4cb21e53764fa8867f7e22609e7f
d8ae7518837f881c0e61cd9bf97f7795acdb6b50
4115 F20110113_AACUAC caldwell_e_Page_086thm.jpg
833b428714b793c4d061e5596986477e
559ec628881d9fb34083732c1d2ae9b25511baa6
1655 F20110113_AACTQU caldwell_e_Page_049.txt
fcf8210a22edb0f339a86ce7c7db5414
05f38a76f8a1487b532165ebfbf4dd3e933232a2
1051833 F20110113_AACUNN caldwell_e_Page_168.jp2
6bb09bf289ece42e850829aa21434d53
f476e3f9740741b78ea2b4db28728d00416b5c73
5243 F20110113_AACTDJ caldwell_e_Page_028.pro
b927b4205b8348de94d6fc9e5f5617f1
7799da7ef488331b8506cb6aee2adca65c05826d
3289 F20110113_AACUAD caldwell_e_Page_160thm.jpg
c6e69636b7db5a03718edec883000e42
a7d2da7e0fb3f7bb88e4a98086d8b045dc43acde
98172 F20110113_AACTQV caldwell_e_Page_118.jp2
61b8c1f5ff3c048b421b714f75100efe
80e5df63a377acb38da3526eba21cb70700a9cfe
1051930 F20110113_AACUNO caldwell_e_Page_171.jp2
3185268662d593e951250a893ac192ee
f612e925b5cfa840439f1f27f1519b090002c510
7048 F20110113_AACTDK caldwell_e_Page_014thm.jpg
0f705a97a6fd8253f9aa0df7b644f1ae
78b1b216dfc4e24062a9d2a5c2d78fcb171e61aa
4145 F20110113_AACUAE caldwell_e_Page_205thm.jpg
76163433c0e76b05fa028935f79381c7
270fafbd218b9c20ab576458ced52e4848e798b7
3917 F20110113_AACTQW caldwell_e_Page_076thm.jpg
9b09bbab8004e84f9cdd5b27893eed23
8dabeddc58680e0a3de2a1ffb9a06bb45d627b0b
1051883 F20110113_AACUNP caldwell_e_Page_172.jp2
f9fefd45e8a3d52e55d87840447bb354
304b6ef16de068abbd8f5e9643d6fcba6fd92c6e
8425398 F20110113_AACTDL caldwell_e_Page_198.tif
bd603888102f2d59e673a711d6fe96bf
db4187bc5c9cf0eb73fd282be9756c80cddcd9cb
64527 F20110113_AACUAF caldwell_e_Page_210.jpg
64a634fecfc600b46660c757ed117ff1
90139ba6c9584f5cc0f901e022085f0dfe522448
152 F20110113_AACTQX caldwell_e_Page_175.txt
4ee0ca1aba1526fb0fce4629026fcbdd
2f3404bb9cec4abfc50d74895db64406729d600d
F20110113_AACUNQ caldwell_e_Page_173.jp2
2cdab1826f6cfecfd5f90167849916f3
77d263075843d216c11cb659a6e6cbcc968f5266
22032 F20110113_AACTDM caldwell_e_Page_021.QC.jpg
6b5f59b8e1d536493dba9ea5d8c5049a
3802d6691e0165e3c8560b8ce148c48ea2a677aa
79110 F20110113_AACUAG caldwell_e_Page_164.jpg
98d7284e967a2a2997bda8f101892b06
72d415cca96d38a8f128e48ae37e6ff1eb23e426
F20110113_AACTQY caldwell_e_Page_192thm.jpg
7b3cdfda29b0e980bd81c493e833d585
d4e58a77340175ea7a7cbf5647cfaa8ce039f0da
1051943 F20110113_AACUNR caldwell_e_Page_177.jp2
2ba4be9ef6e8e49de1f4f6efd6b6625c
f78af15d448616d43e83c125e6123e49756af135
909 F20110113_AACTDN caldwell_e_Page_060.txt
d283b58d10a94933ad432e42941a7e96
4a1476befca83a6589c11e04a1df70cfa44ad855
615226 F20110113_AACUAH caldwell_e_Page_151.jp2
2d4549dc3c1121ffe03f863b932024c1
b39ef93ba7ace085b9075c9326df4d6352549a91
F20110113_AACTQZ caldwell_e_Page_103.tif
be5978a40aee0e3ec05ea0995512441f
9a6115ad4c934a205843d421d6887f91773cc988
1051980 F20110113_AACUNS caldwell_e_Page_184.jp2
444e712152a85436baca1eb3c964376a
9e5fd79447a6676bddfdb1c9ed0d571846f3d805
19175 F20110113_AACTDO caldwell_e_Page_178.QC.jpg
ace00505a501aacca611d86445d2a980
675a32fdf101f4887a753fbadb994ef4fc9c135b
4957 F20110113_AACUAI caldwell_e_Page_123thm.jpg
3a1fe2ff9043d73cfcb77e020a7947b9
26b3d9f75638e0d601dac1403ddb4f694c7ce617
1051933 F20110113_AACUNT caldwell_e_Page_185.jp2
b8f718ae14f080303605b924ed5252bc
b2e20f92ef7464a902adb85ac2ac9ec072bb1b89
6136 F20110113_AACTDP caldwell_e_Page_137thm.jpg
8e69d07c0454873a7d1f5852e6a65492
16244715771971ebbb85a88ba0d57d4b877ef1b5
14217 F20110113_AACUAJ caldwell_e_Page_187.QC.jpg
cac8ec9f1cc41a66eeb1d71e96b9f544
2d2e8bdda0e66e49e2ab73b0e3d4961e6f13e53f
1051940 F20110113_AACUNU caldwell_e_Page_187.jp2
850dfdd10992996087db83a34643c5e2
cc7c003fab2ce8a031fb212736efc8500a8b546d
5203 F20110113_AACSZA caldwell_e_Page_050thm.jpg
efa8d2b8b773b5ed23f10899fd4cb775
d5354dffe2636b8c18e7f9c4fd41f31acb8b76aa
13863 F20110113_AACTDQ caldwell_e_Page_045.pro
b1b0f863022427d8b8bd8e75a2d352b1
3c433cce171e56943dfa37c2e64fe1a6fa29f80c
16674 F20110113_AACUAK caldwell_e_Page_202.jp2
ef85f9970931001b52e6f884787cebd5
4cf25d5a1a6b8ce303f5caed8718541c4c59f4e9
1051954 F20110113_AACUNV caldwell_e_Page_189.jp2
22091037e905314a5e4dce77a8a5ce89
bb778c7b1457af270e8fa56667f55359d3208b25
5979 F20110113_AACSZB caldwell_e_Page_007thm.jpg
13668cc05ee05f165aeda4676a554c07
c465ffe269960df27f6feba0a0003dea165cf88b
681130 F20110113_AACTDR caldwell_e_Page_048.jp2
3751b8933753b2eaee03e284fbe6e1e3
d9e6cbf4652896ed5ac9f971117b7426bf284947
1051672 F20110113_AACUAL caldwell_e_Page_169.jp2
ec04db2ecad6036b02f1ddce59230efe
5122129f4e22cea6bd819d176256985699229b3e
1051969 F20110113_AACUNW caldwell_e_Page_191.jp2
871a99a4abe45dbf00cb5f327fd74632
9a07b83af84939de309353bc0bb1a8585024ae31
F20110113_AACSZC caldwell_e_Page_190.tif
0af1b92d53a716aba7ea9aa8e7243479
763bd49d77bb8941fabe4ae84aa5ceec5be87ada
111594 F20110113_AACTDS caldwell_e_Page_077.jp2
e8cc931caf833ff58f51379122a1cdf8
c382b9f84e453bfebc2c3f569a53a820eb558fc3
F20110113_AACUAM caldwell_e_Page_163.tif
abae30f9637220adb2fe67cb7558855c
b768f230d575156d0c1e18f9153737ba0b3a4bab
1051977 F20110113_AACUNX caldwell_e_Page_192.jp2
aa9258f2b5fd2210a4f597ca4e8ceeec
1dde8f54e563347005d998dbd0ece1e54e4c3675
F20110113_AACSZD caldwell_e_Page_230.tif
3adeba12fd4476e059287e63cec9e083
c5ea091cbb43f882b7470bc1378ccc8e0f923ea8
3048 F20110113_AACTDT caldwell_e_Page_185thm.jpg
37dad9432274780ccb340347d31e7408
f0d77f06a01a126c25992e13747bdb63777c2646
25374 F20110113_AACUAN caldwell_e_Page_131.QC.jpg
b4740e285607493e21347493f17b5848
0bcb585f000c9932407665c1442ad551735a9e3a
1051925 F20110113_AACUNY caldwell_e_Page_193.jp2
7047af87308837a62cf5fa8c635c0631
0e45bc2d299f05e0bd492224f3763636680f31ea
950327 F20110113_AACSZE caldwell_e_Page_031.jp2
e8188dc2143f4c0972285170df011bde
e56e9b45c721e7c096136041062182377c4e4320
5831 F20110113_AACTDU caldwell_e_Page_148thm.jpg
b5be6279066432c28fc7bff5bed8991d
6daaf2665a2c2647d54efadfac4b4922e14e099d
F20110113_AACUNZ caldwell_e_Page_197.jp2
3ae9a5de112ee1b36711af49094be72c
c97e2158401c5716deb9901d965dfba638467796
F20110113_AACSZF caldwell_e_Page_126.tif
f8e5d245a426083cf11d7be27820b1e0
a15703ad51030dde92ad5e90aed2861a2814f5b2
17921 F20110113_AACTDV caldwell_e_Page_218.pro
28ccf140888af6eeec8c975940bcf40c
bc6ed282adc8b974201cd69e82094bff98d1905b
48570 F20110113_AACUAO caldwell_e_Page_132.pro
7dff6a96589763b2caad147e38290b1d
01377d78d7edba17263998719a40f77724338bc7
43816 F20110113_AACSZG caldwell_e_Page_074.jpg
ac7c2e6477a5625da460b07329dcb745
f56ef7acef4f8b7a383c9570868990a91fa04239
5394 F20110113_AACTDW caldwell_e_Page_159thm.jpg
922f36bbd14d9fc0b8cc45fa34e7077c
88e763e661b436b2496e814eb60a153953283644
131924 F20110113_AACUAP caldwell_e_Page_221.jp2
55efff79aba36cb2f0bc048f78e47b02
683698d800139e4e0f28f3f8c342b8666873983a
8743 F20110113_AACSZH caldwell_e_Page_094.QC.jpg
8f35605745fe9ebd90186a3c7eee413d
b8510722626865a00ce2c0e4f34a5221f7bfeaed
1863 F20110113_AACTDX caldwell_e_Page_088.txt
ff7b03b454e0d21e6c920cd3667101de
b71b7538ae92efb19a06b72aa0786a13c4422472
F20110113_AACTWA caldwell_e_Page_070.tif
1bfd96b3cbab92113e86b499a2c93596
e7e498ed0c0f0fe9a9cf02b40886219d99d93b60
64198 F20110113_AACUAQ caldwell_e_Page_089.jpg
f456aaf0e6ab1fc9d8612f8a23fd2762
50e2f8449aa84a10b2688b4a24d16b163e9b64fa
F20110113_AACSZI caldwell_e_Page_143.tif
4b9cf7cbea8fd65baabf5033fc60b2b6
ebec385f7ae8fcda2023555f9abd7a50f0fc935d
3345 F20110113_AACTDY caldwell_e_Page_213thm.jpg
e32f475aef72e8a50ec67cb822072caa
b27e334175d4159ebcaaa432089d33011bf702c0
4018 F20110113_AACTWB caldwell_e_Page_074thm.jpg
aa94af36c30a5b05e5a9c1f7ac66faa8
8196cbdcfe363d947bb8b5c3ce482bc9a0459c11
643360 F20110113_AACUAR caldwell_e_Page_152.jp2
ed000201b18707445bcd25b1436eb201
5dc9b37fe288b035b93b15c034ba3b5e9695907d
1945 F20110113_AACSZJ caldwell_e_Page_236thm.jpg
8034ef2bfc2ab8c4414cb734e7c52a67
28bcc056e368cfec4fa040f59af9712f9eb898e1
13146 F20110113_AACTDZ caldwell_e_Page_070.QC.jpg
38804dd54284a02740ee6f7dce4e2f80
dad8d0f2179879725e2cffc4708842edd2baa128
27432 F20110113_AACTWC caldwell_e_Page_051.QC.jpg
c3eec157254d71f5d6f1786a0ce9084c
f5a584236ffb1f791144f56b435cbb87cbc99340
1051893 F20110113_AACUAS caldwell_e_Page_174.jp2
eacb68b541059e0ad4c0a1119e455518
ab3807e3f223894d860879c16ba3554dc584ecf0
106360 F20110113_AACSZK caldwell_e_Page_071.jp2
a821e5dddd4a5db1f859cda6ca28e7bb
5eeede12f6d72bb9d50075e168020b8bd3f88515
16766 F20110113_AACTWD caldwell_e_Page_177.QC.jpg
9a5fde39dc60165a1e0a082169a6288f
292e2547a6816668c2f9db7063f1b962f7664dc9
25265604 F20110113_AACUAT caldwell_e_Page_042.tif
84334527b7866a4b9958806d69efe23f
74ea2007965ade053ec2cd39c680e3a828446431
12754 F20110113_AACSZL caldwell_e_Page_010.QC.jpg
bcab4d0e76e874d028d7cbc7a8e9bf5a
7d782573909679615d6cbcb2ff99f5471a250115
46377 F20110113_AACTWE caldwell_e_Page_105.pro
f79f71b355e966d6b263c84d9d6a0a36
c806cff9f83797c28783f4d0c5af9a6eaefc1bd0
11471 F20110113_AACUAU caldwell_e_Page_216.pro
102d71f86a5df7946e63f06caea2d91e
12a66b0ba3047058c1020b0a4b5c9f15c42ac0c8
92979 F20110113_AACSZM caldwell_e_Page_092.jp2
4b0970145d01fe768226a1cc6a9b9168
c0cb5f233c0060697aef07ae79021194af345053
47420 F20110113_AACTWF caldwell_e_Page_080.pro
262cc155d29aefc111f3542b48dd6ef0
5fe5f548e9c91f089524288d7734c1d46cc71e49
110560 F20110113_AACUAV caldwell_e_Page_079.jp2
3b49cea84f25bbb1ddbc3bf6a7c22a1c
1316bb9ac3fefd0f5705af844ba9b7205f9fbca8
843 F20110113_AACSZN caldwell_e_Page_020.txt
0ff650ec681646dd29b732f41345ce03
dfacd391939a6929a558820e0ca2ec7e70a5dd50
46276 F20110113_AACTWG caldwell_e_Page_129.pro
853a46bf2ec4ac95cf5f5ee01f171be9
9c9bc921d9cfd15f5b488f27e90255aa600d84da
48236 F20110113_AACUTA caldwell_e_Page_136.pro
6c0a2af565b2c6098037c4b828751ef9
da03aecabfad65c150188c0fcc1a72e337d9e35c
F20110113_AACSZO caldwell_e_Page_103thm.jpg
ed5d713fd2b9cdfe00031f1efae558ed
94169d5ed41268ad91baee470712bd68e181f137
3464 F20110113_AACTWH caldwell_e_Page_008thm.jpg
d1cc3068c5247679878f2e5e0eb8a5fc
d31fe870c7a14f6ba8886a036c10075f81821f0d
1919 F20110113_AACUAW caldwell_e_Page_132.txt
f55b3b1ad5afe0496dd6738e7ded350e
9a9aa5b8933429d0a8bfcdcfc5438eb94e02ab06
47782 F20110113_AACUTB caldwell_e_Page_140.pro
5f3a3b607ae854206b1d010a15a5852b
8c0ddc467ac9c5de579236dcb78d24727e14757b
67505 F20110113_AACSZP caldwell_e_Page_083.jpg
5443f64b3db70f5a819eec26f906985c
556ca74bb959d288314a5814cbc4ccc19639816f
6317 F20110113_AACTWI caldwell_e_Page_041thm.jpg
d4319ee552fdc51a0df38b89b4a1946d
4abfdbdc49435a87e9db095c36accdbd56e27fbf
66558 F20110113_AACUAX caldwell_e_Page_199.jpg
bbb3ed12f78f910f6298d1d70b8f6106
39777e64efd4c40900283e18153edd1dd12bcd62
44199 F20110113_AACUTC caldwell_e_Page_143.pro
4478660d6dd4db2a221940b3bab9028d
23a0f5e8a8375b563419be226d81e0dd89d019ce
20226 F20110113_AACSZQ caldwell_e_Page_149.jpg
ad43588677b8872e931099fde5e96f1f
5d53e7e905f26789eae78f86b6f39f7e1b66f139
52475 F20110113_AACTWJ caldwell_e_Page_235.jpg
4ad803d0195ebba11760d5ffd4776047
ce949fb477b08ab6d89381f29856438221c0f7a9
1051917 F20110113_AACUAY caldwell_e_Page_170.jp2
c6c4bcfa3e07bbfcf26e2d90adf84e5f
4b6e05beda95a201da8e405f59c3cc91f5794cb6
50754 F20110113_AACUTD caldwell_e_Page_144.pro
5cd3a1e0894e024c26017128e17a7a84
ef53bd0d6224990458feb36639c1100be48fce2e
13504 F20110113_AACTWK caldwell_e_Page_152.QC.jpg
7866b1d3aa5585d79ad8148d455ad407
b2d6b278914994463d30683b25fdeb2bed2c0888
F20110113_AACUAZ caldwell_e_Page_020.tif
08e7ab3f341be5944c400719206d1213
5706055d15d860a28f60b703620c13daf377a6c7
50850 F20110113_AACUTE caldwell_e_Page_145.pro
75951e4225eca0d475b14707d31482bc
952094b4efd7634df79d43b6d171dc7723f8b793
1135 F20110113_AACSZR caldwell_e_Page_021.txt
b56211c6c9764c04944f1ee050556a73
e769c0b75c723ff800da41c69ea77042ae84ed6e
6341 F20110113_AACTWL caldwell_e_Page_107thm.jpg
8bce0447a131b4f8462b920026959ea1
b3556118056a33383d1b2d9c619a8c37c297bb1d
41846 F20110113_AACUTF caldwell_e_Page_147.pro
25c8fa771a2d59acbe7c8de173d95962
892e8267499695b115926d255a687c147f07cb73
106907 F20110113_AACTJA caldwell_e_Page_075.jp2
71b7e38ca27d236c07a8f12f52109db7
dc13c3268045651490bf64ea49cdc3e1eaf3441b
1140 F20110113_AACSZS caldwell_e_Page_074.txt
96777a1c0356eff1fdb88a4ddf13648c
69fbcc17b4aaefb20885df69102563cf2b515cbc
1335 F20110113_AACTWM caldwell_e_Page_180thm.jpg
fc5bddb74dab387af622fec4da2e9ea7
e41addcccc57eb4600c343553d209716c0f673aa
47122 F20110113_AACUTG caldwell_e_Page_148.pro
3995a32f6e853898a300aa3ba116fe0a
0dfe9f52d50bb838e0c47e106994dbb07dd3a8b9
1445 F20110113_AACTJB caldwell_e_Page_010.txt
15e82f40ea120532d7ff1899dd53b745
094845c7bf3a149fe75cb11fbb4ff1c969ec3dc0
3328 F20110113_AACSZT caldwell_e_Page_209thm.jpg
23c972e35cc2f686a86ce1395bfdea7d
cb216f6e159ff8af7c590c7f0cbb51002429bd26
10443 F20110113_AACUTH caldwell_e_Page_149.pro
988ae7289f48446f1b60292e7da45d6b
db1453110479be782a4139c8d55f7cd8e7b61871
76157 F20110113_AACTJC caldwell_e_Page_250.jp2
32e433d6bbfd47d3ccd7551d7634b778
c103d1733df7d42156b27a224bd65e2c5f6f1ea1
4647 F20110113_AACSZU caldwell_e_Page_215.QC.jpg
ba61ca06ddad902a1ce74f6a20ff2629
3c1c258b0f895c772d122cf96b1acc0606b82a28
77665 F20110113_AACTWN caldwell_e_Page_185.pro
319e9cccfbbda694616e78db06e155fc
faaa820cc7ccfecc6175c9274170c98b584d91ec
18764 F20110113_AACUTI caldwell_e_Page_152.pro
d475e53589392f96810069802b26fe7e
bd420a57fec2e6316727175cc20d6c3213ba05c2
4085 F20110113_AACTJD caldwell_e_Page_157thm.jpg
1577a9a9fbf6dc4480dbda189122ea6d
e1ffe6d2602f48e543c3dfa30d14592cf702b5b2
752 F20110113_AACSZV caldwell_e_Page_238.txt
9816da16965821d63ff2a481bcf7db0f
2accc4052ff43bee0920873d51316d455da1e918
53504 F20110113_AACTWO caldwell_e_Page_095.jpg
1868ca875609812458aef322ddeebdfe
d255e7c8b78b69a43ea04b94f5e0d1cbaa890cc5
1908 F20110113_AACTJE caldwell_e_Page_075.txt
ead0bc6c0e8f6b5a9833ecd09647cd6d
ff08b45917ed460c777611a30798819330b7d618
81459 F20110113_AACSZW caldwell_e_Page_022.jpg
bc209cfc46b4fec9924afb5e66932715
64c43681d228bca8cbfdd4419805c35f624b82cf
1686 F20110113_AACTWP caldwell_e_Page_110.txt
abc2feff5d704e825a4dbca72e7764d4
cce53b3f8784cb904e476b037851ce9927d0f8a7
44990 F20110113_AACUTJ caldwell_e_Page_153.pro
cb102caddb996d435e6a012f606f7778
1fa0d554655a5fef4b52964e60f9994dced7a237
F20110113_AACTJF caldwell_e_Page_168.pro
9e8d7786ee5ef5523dc4309c4ea5291b
f1547ee3db9d09c3511a68fdf1b172b04e9e785b
4310 F20110113_AACSZX caldwell_e_Page_191.txt
56e180082a92304dde3afcf651a17394
03e0f05afbdf155f25bd020bff658780f3350a98
76333 F20110113_AACTWQ caldwell_e_Page_155.jpg
7f4edba5ecdc2668755c98c2b6f15798
3fea9948b32edd5f0979e44feb45adbba62aa0e2
22360 F20110113_AACUTK caldwell_e_Page_157.pro
6f9b7ab6ba4d4c50136818f8f8a11400
92423efd4a05cb34755bad136a4c4b4c8c1b2363
49175 F20110113_AACTJG caldwell_e_Page_024.pro
f6ff6619ba7c104b6e88be4744e31288
814c38590d40c23ab9ede5324adb1f644f8cb7ea
1051970 F20110113_AACSZY caldwell_e_Page_045.jp2
02243a8f696d9aa37bd81b73cd9fa8f0
5449092ac30fb42f14c6e4800d1053f63eb26760
57982 F20110113_AACTWR caldwell_e_Page_059.jpg
e3459cfb9c6d9c6acb6c48d30e701387
aa7337284fbdaa7c31323c181a4a277bc961b632
27350 F20110113_AACUTL caldwell_e_Page_158.pro
7d7620618159f7efd821b05dfdbb8fe9
2e9476991a01d29be292110d432ee54ff21c0a3e
75426 F20110113_AACTJH caldwell_e_Page_153.jpg
b84cbfa7f4b723fe72a32c137aded376
145d7bc406c93c79dcb18df51f3008dfcfc27473
57611 F20110113_AACSZZ caldwell_e_Page_054.jp2
b4e8be1059c8427ef9af028b69fdadf3
53541aeec7366a3618f7d34ea8699448884a6660
60776 F20110113_AACUGA caldwell_e_Page_184.jpg
f9bb64adc84a4b2ac229bf0216b005a1
08dbd411e38536aa93066cb5c38460fa69e8d293
1861 F20110113_AACTWS caldwell_e_Page_159.txt
30a0c04f9a82ca076dcb8797a82e7b3b
e2131498ab1f56045d3fa7fc1ca85cbed312dbff
2557 F20110113_AACUTM caldwell_e_Page_162.pro
94d0372c5b60d6575298e6ada3ce9d10
3e3de0c7017fddfaada155a0c6b67075c3b576d0
91153 F20110113_AACTJI caldwell_e_Page_029.jp2
3caa7b8f9470d56a04edc0428418f3de
891ef7f536026b64ec787ad2e69c8309129ae879
2964 F20110113_AACUGB caldwell_e_Page_006.txt
87688425ae96d5c05fc2aac2193abc96
490bc3c23115e382a07a6f143e40aa27f7175b7c
869580 F20110113_AACTWT caldwell_e_Page_034.jp2
951028771ab3e4cb1601c55b4a9e21bd
1b09ef658e96f767721cfb5df40b401d1557865a
2005 F20110113_AACUTN caldwell_e_Page_169.pro
9f0826dd8cdf9d408b35dee914df3929
aac9340147922e6f7592632578875986c693926a
53549 F20110113_AACTJJ caldwell_e_Page_093.jpg
069850e5d77f0d5e89e60a63726103ce
74c09e7e77f046d81f5576a73f3a03ee870f6e06
110433 F20110113_AACUGC caldwell_e_Page_138.jp2
0be5659b5c705adc0c31bc18f5640b7c
2dd26e9c82c4c57789fa5fcde7f7be39c30355c0
1225 F20110113_AACTWU caldwell_e_Page_181.txt
096225195504aacdb840f933d5d3641e
8865d8a0846596e3936fa26f23df5034537c9334
3405 F20110113_AACUTO caldwell_e_Page_170.pro
966bc40d8fa742d22361634c99d71562
19ff66185ae02a50e516b826306c3fae5b2aba5b
78122 F20110113_AACTJK caldwell_e_Page_189.pro
e66b0d85c737aa8520ece80d31a610fa
f815a8a0bb07f9820de7fe48941f8b654c5fd9c2
F20110113_AACUGD caldwell_e_Page_189.tif
24da296244800ef1abca6b7b758483ac
288baf0c19bc18b5dd556f502221810541e99c5f
2003 F20110113_AACTWV caldwell_e_Page_146.txt
9914e598464f7893a410b36a4edc7118
bc10a8f10867d34c06dc66ede2ba95d87b137e2b
2665 F20110113_AACUTP caldwell_e_Page_172.pro
15f30e5d61cddf2fba7cb6521c266a1b
0fd6428073ad4c0d5969cc376c53383b6d9ae582
1007797 F20110113_AACTJL caldwell_e_Page_233.jp2
810b8a8e78a73c9c402c33e2ac846590
9df12b7280bef11baf4d435a4f0671a748dd224c
F20110113_AACUGE caldwell_e_Page_200.tif
645dfcb7f165a40cde8ea918f0dbac1c
5b8d017d7ba2dfa9a9d1f9c758da73760b983403
26673 F20110113_AACTWW caldwell_e_Page_130.QC.jpg
3b0b8f0f9930dc040b217f39cbefa8a3
6e836f6281488a52950e61e42753195a0cffadb7
F20110113_AACUTQ caldwell_e_Page_177.pro
43660a22a4ebc96b03924ee78e1597c8
fa6f79bbc6a31b69dd560bf82f3cd3b5a284d0ce
F20110113_AACTJM caldwell_e_Page_107.tif
957f246863c612bc0a7584a1f042e32f
00f46551482af2822d00cac45e2332219ad7d632
29424 F20110113_AACUGF caldwell_e_Page_012.QC.jpg
12546a9b64c15ae3c340be26200d0569
6db6d4ad693910cfbac32dd87a9a462aa6ac8810
72785 F20110113_AACTWX caldwell_e_Page_125.jpg
2012adb90aca4a3b50aafe57de2efcef
09a338cceea5695ca5b4b0d305b986ff8aa87050
F20110113_AACUTR caldwell_e_Page_178.pro
5e386803fef52e15c9b07502378d6ea4
07c241d696cb50a2d6d38ad312ce8bf3c9fa37a3
F20110113_AACTJN caldwell_e_Page_225.tif
14cabcb87f548e750a2957804c027859
75e5e0ecf72b71c4c470243db476d6405766362f
6216 F20110113_AACUGG caldwell_e_Page_002.jp2
d452c9f42578fe2ce689f2353a4d3a5b
c9033d8c6bb9dfd366c4d699d0a65b0bcf0f895d
F20110113_AACTWY caldwell_e_Page_023.tif
b8fd93224c7d3a5d0c9072512c8230c0
e4517cafbb7b830d303fd204289e0f474e06f5b8
10849 F20110113_AACVDA caldwell_e_Page_241.QC.jpg
01c89c20c2eb3bf69d2d3aa5bd839ed2
e84e942907312208bc231487e8dd36b030af803a
19456 F20110113_AACUTS caldwell_e_Page_182.pro
8e68e0a02d196a63e8847c3b6e4f933b
5e1a3b722c9146d16703a4289fa84786e26eafae
20407 F20110113_AACTJO caldwell_e_Page_206.jpg
48bd754846a184b6eef0935dd6c7d774
f1cf5744ce27562a87a0ff8a4c41e4ec25fd4871
38280 F20110113_AACUGH caldwell_e_Page_056.pro
cc815417f7c4bb8ac6a35c2995d890a9
fe36421fc21bfe551cd9ab759a2b6e01013a4fd0
3529 F20110113_AACTWZ caldwell_e_Page_054thm.jpg
8e0b0ef99050a8e3cebdec366836f224
fd2973d75c87913c17e8cd311d2f4dc30d967fe1
22580 F20110113_AACVDB caldwell_e_Page_246.QC.jpg
75c08e5a7168544a98a69ba6c1498e32
125c23cb46b97f133d85a81c2b61945b4b27f8ff
78848 F20110113_AACUTT caldwell_e_Page_184.pro
616c95c8fbac7616fa00319bb76ced6e
b5ddf83f724bf2e19c33306ca1180db1c55f6d60
3177 F20110113_AACTJP caldwell_e_Page_239thm.jpg
ef759738d7898fdcd2c59fc8fc3739f4
ba4163e0dca5b8f2fa5c26c9f75824a121e6d6cb
86746 F20110113_AACUGI caldwell_e_Page_116.jp2
e534c31d04f148ebb5b0936bdf6c32fa
3656034f6a712adf1b2d834e7e557c7d0b52dfee
27530 F20110113_AACVDC caldwell_e_Page_247.QC.jpg
280b458b891f74d1bda37c0a1afc4958
7ee29fac7100bf524ea1466254e3834fec0580f5
77577 F20110113_AACUTU caldwell_e_Page_186.pro
4c53e368183b52a2e3c7e1aa937f24c9
c3ca44f573330a0e1b266eaf0d889c6367a7865e
66704 F20110113_AACTJQ caldwell_e_Page_055.jpg
769cafac9b1f8ee4df199fd7d28e180d
678c46eddfd75a2f66cfc8d59378aa57a7f64bdf
3260 F20110113_AACUGJ caldwell_e_Page_199thm.jpg
7b59a90429ac19685f2c0c3097759088
6e1c2858df79efd847f0a4efac836d180b1cf60b
18581 F20110113_AACVDD caldwell_e_Page_250.QC.jpg
258f7c29a3276a7fad3c36034c3012fb
d5e3cd483e365b147919d837c9bfce2366655738
77732 F20110113_AACUTV caldwell_e_Page_192.pro
0d0a47d17c106ecd076b2b1d8a0b25b3
4a459e34ffbb07ecff25abb0148eaf2d00e5ae6c
4291 F20110113_AACTJR caldwell_e_Page_006thm.jpg
16d1ab0f450bad74503df28fe96786fb
db16618d269cb7781da304f99058fc1671f57dc5
71418 F20110113_AACUGK caldwell_e_Page_134.jpg
4e1c924e7cd0d9350f36a4215cb79c35
d043b514aaeaec92bc3159b6093ec1cb95913877
289091 F20110113_AACVDE UFE0006302_00001.mets FULL
20cb824820ec67a2cdf240684eb380ae
bcfcb69c353302e82c6af63ca094adbcc1a65aff
78951 F20110113_AACUTW caldwell_e_Page_196.pro
98f9da5c8d6c943e3a9a95be4ae55dd9
1c373e1f0fcecf08ea67abe9899468868b4f572f
14110 F20110113_AACTJS caldwell_e_Page_061.pro
51ae13a4402e1dc6aa3139989b73adfb
a70b47d98fe6ae1a21bd53af2269a8a666f5c142
12980 F20110113_AACUGL caldwell_e_Page_226.pro
fe579f9c0fe712e4d620b4b647183e52
fcd0e29c20314e81d9d332bb8456f71da5c74735
87761 F20110113_AACUTX caldwell_e_Page_197.pro
4df793bbb6c92ffb7ef55a251f4adf37
549b5cda9d2f741d3e2a35de70d3d7bc032f1f30
45722 F20110113_AACTJT caldwell_e_Page_102.jpg
51d9cf6c02335bd14cebca5e354402d0
5d6bd3c5494e5ed6d5096fcdc5e611c5c2899d6f
14086 F20110113_AACUGM caldwell_e_Page_185.QC.jpg
7fd081e95d753ab2fd88aa6cd4c9d7b7
918bcedf163a57076657f62ab1f94645d54091f8
87743 F20110113_AACUTY caldwell_e_Page_198.pro
c8f7865b34bf789e1b90826f315caa15
37f5d1e0a55cfb1fd23493b7532819d891a62dbd
4854 F20110113_AACTJU caldwell_e_Page_061thm.jpg
5a5e9a01bdaf115931f1a50ffed815fd
06045e13f9608efc69731f5773f8d70789ea68d3
80987 F20110113_AACUGN caldwell_e_Page_154.jpg
3debd6f3e273dca7997e1b204d4a976c
ef05488de07101b698a2a4c7a2192ad519fdc23f
13239 F20110113_AACUTZ caldwell_e_Page_203.pro
a879c04a03634bf5a525287736ea2546
368d0a0a29fa29560f0b4aa3ed353c560c93b8b0
59349 F20110113_AACTJV caldwell_e_Page_250.jpg
13b1ef9b74cff92bd6afdd6c22d383c0
f93f682f138429f7ca546c97a40522ad351d652f
354390 F20110113_AACUGO caldwell_e_Page_219.jp2
afbb754374bfbabfacda915ac8525d7a
12c3b241aa8eaeede8f6768a7c3da25b1f4f165e
F20110113_AACTJW caldwell_e_Page_164.tif
9f7e7dfe82dd2204e984ee1f6f78ae44
ed2cdd060bdf2ec0d59a8f9f15c0f8d0c9bb06d3
948 F20110113_AACUGP caldwell_e_Page_225.txt
47d23566716c7eefa89a83ff3910aa81
611dec22ba0b1901dc106ee500cb43b259a45be8
13292 F20110113_AACTJX caldwell_e_Page_082.QC.jpg
5559872e4e4f8e9ff2908bfff0682fbd
56f4799daec2533dc0a3ed7f4a35f88c2a07f9da
F20110113_AACUGQ caldwell_e_Page_184thm.jpg
11bca70b1af78a1bd41cbb3bd5eb7d08
186f68c04cbac4d742a224ca6d79347d14f43f03
F20110113_AACTJY caldwell_e_Page_153.tif
bc25356dd7fe36b256576a520872b978
ba1d0003981f2fb41ae1f219f88f6f401dbe68a4
105418 F20110113_AACUGR caldwell_e_Page_015.jpg
7933910805df7a155a971b8b6b69ab05
98f2bcdcf93faaeac922cf29cda51addee5c5338
3344 F20110113_AACTJZ caldwell_e_Page_241thm.jpg
a76961ac82a59cda69b716a9d8930dc5
b21b8b8a600021b766943fe55b3937eb3150ca1c
556711 F20110113_AACUGS caldwell_e_Page_236.jp2
c39ed3ee38d391f3c5d02db418d57036
4e20b0558d4fd8ee20726cb27b31303a6293747e
48238 F20110113_AACUGT caldwell_e_Page_020.jp2
1e75b9ed620cef50545036293301b234
e7acc046cba7480f4555af40f1195039830505c8
F20110113_AACSSA caldwell_e_Page_185.tif
0f8b6767d46630761afc259aa7fb8461
50c07d6651397143c7df00f8eaf99ccf9e3ea396
13407 F20110113_AACUGU caldwell_e_Page_160.QC.jpg
5c4d2f42e3670d521bec9d7272fd52b7
690ec9620e634a6195c40c9a3d39655cfdf583a5
F20110113_AACSSB caldwell_e_Page_073.tif
65635eb936407592f506a4aed8db0546
583d880504ded33b74f07d12d63c3c688d70d239
3277 F20110113_AACUGV caldwell_e_Page_216thm.jpg
7cae9c542b148cd33e165bea0ddd5880
7a45e5ea15715d595dad812baaafd0a20d724b0b
81250 F20110113_AACSSC caldwell_e_Page_194.pro
1a0c58ab26a3a7e214f0408b4c5755c4
869dc30bf576730024a3e61d39718de7e1deb55f
1221 F20110113_AACUGW caldwell_e_Page_089.txt
4764b9c93c8cbac7c6fbec7a14b777ae
d9cf33fe665707fc6954d7dbdd8185e61c35ec36
75032 F20110113_AACSSD caldwell_e_Page_035.jpg
ebc5f89b4020ddfb91c98e8268c4005e
5a38ca7dff0b7b257bb960326359c22481f4ce7e
283 F20110113_AACUGX caldwell_e_Page_183.txt
2546e267cffbd30233464b6650f10808
187c93bcb2678d75e0fbd639eb3af3f016c61ffe
4608 F20110113_AACUZA caldwell_e_Page_056thm.jpg
9af5eef3dd6d8d0b129b79b4873f0329
8272d1d72fab6678b2f7e79346bcbc293aff3a79
51345 F20110113_AACSSE caldwell_e_Page_138.pro
8cdfd5fc4132ef9ef8d73e3f82a8140d
9669bd2589db89498a3e5012300d13fbb64b80ed
102582 F20110113_AACUGY caldwell_e_Page_127.jp2
3c2e2bb1b9f5a153b8544b299d027fb6
e2ed5517ae46713db51ef7be8016126bd6427006
4336 F20110113_AACUZB caldwell_e_Page_059thm.jpg
a1f6143847c7973427c2d56dc9f1b10d
115e83622bc34867727614e0868e641afa3df3b1
14303 F20110113_AACSSF caldwell_e_Page_166.QC.jpg
30b06b11fb64cdab369da59d07a38ae9
f3e898b93d017f2a34ca7c73eceea17eefa2ddf9
66243 F20110113_AACUGZ caldwell_e_Page_243.pro
3358cc480584309d93859ff26e3cd94a
90b7c55457eafa06865a5587e37a813a0b2b3687
4371 F20110113_AACUZC caldwell_e_Page_062thm.jpg
fe1f1ed8b3a1be1163d9bef342c85d7e
8e4c17cf56e51d9ce2d026a93c1b7de385601ea7
6270 F20110113_AACUZD caldwell_e_Page_063thm.jpg
aea019ca062457ba824d53ade7c66b11
7de81cd2640f70c1391113d81c687a2900fbb279
F20110113_AACSSG caldwell_e_Page_132.tif
e2c1f862846f591dc407c9f676c4a152
0a7077a0d2aa8ba91122340aed2d0b816dc9b79a
2032 F20110113_AACTPA caldwell_e_Page_214thm.jpg
aacba31dc68847531a4cb2ecc084e332
d390b90cb9859fd2119a8f454f242906273df59c
25188 F20110113_AACUZE caldwell_e_Page_063.QC.jpg
b3c8c766f9111b42c6816875aeaad2f0
858331527babc7ccd9153e03c2ee9fcc851eb4a1
88574 F20110113_AACSSH caldwell_e_Page_199.pro
c503b62694a7256d08b3c30b30bbe266
abadece1acf7a703a0447fffb47e2ab8dac08b46
85918 F20110113_AACTPB caldwell_e_Page_049.jp2
7dca460ba83c603b910ad438b0d9f2fc
f9d18d6fad6b624bd9d64598148b6d1bb2ee5854
4119 F20110113_AACUZF caldwell_e_Page_064thm.jpg
50527d74c2046cbac123efb9fae2f713
a94071e230a9235f6fb4067f03b4c56e9f9b6b38
2999 F20110113_AACSSI caldwell_e_Page_231thm.jpg
0266b02d764dcc361f294fce4c5468f4
ddb927fd7872073f09ec4cd04dccaaa0b0d8dc65
14053 F20110113_AACTPC caldwell_e_Page_087.QC.jpg
a0e6bcf4c419054ac233b0c0bfdd1e37
1a6dd290038800e6124b56ad969b8827f84aecad
4039 F20110113_AACUZG caldwell_e_Page_065thm.jpg
eb35789d1405e6b92057fc3e06c407d6
af33ce58bd20af124537ef62bb7ee8aa53223e76
12899 F20110113_AACSSJ caldwell_e_Page_106.QC.jpg
276df05efdec86067de2b9f337c2506f
a6bef0270fd63b6ee1ce588907e0fcfd91dbe1f7
1449 F20110113_AACTPD caldwell_e_Page_094.txt
193206aa92e3ea1ff4877e13bdadd02d
245a82fe8d8cc75c1bb7d82fd994e96e034dd8cc
3825 F20110113_AACUZH caldwell_e_Page_069thm.jpg
6fcbd5f12124817b6f60cc6564d30972
101dbb819b85a9231940dd967f5d3230ca4df4cc
55384 F20110113_AACTPE caldwell_e_Page_048.jpg
0dbdd5139cfdf9c63c8b4db49687adaf
c4576bb927d8a37832f4a2b90806adb5b5cff87d
12759 F20110113_AACUZI caldwell_e_Page_069.QC.jpg
77e71c5245de26485753220fd2211b41
d37348852cb5d341e597b64f94572bbb5263cf4f
4643 F20110113_AACSSK caldwell_e_Page_250thm.jpg
b13a6c9e0a2002e9a1619882d021b561
5adc1a23a81a72fc6d53e2802a3e8fb22d092b9b
19137 F20110113_AACTPF caldwell_e_Page_165.QC.jpg
ea2f5bb0ae09c37957d1feab05df0417
b01ca16a878c4a21857485a2b7fba7c6dd0979ce
6224 F20110113_AACUZJ caldwell_e_Page_071thm.jpg
50ad9e25ce2de812be1386404f92d9c1
6e6e2e074ee330f4e562c8e64d1daa998d7e0111
22593 F20110113_AACSSL caldwell_e_Page_047.QC.jpg
60d50cd7798206d90820f34dc021adac
b87eee7f7dff2a276612b2d6ae306ea3b063a970
25203 F20110113_AACUZK caldwell_e_Page_071.QC.jpg
223dc5ac7e38126d2e2c2d7cdab41f34
bc9eaf86c578e5585839acae99f37e5844163ab4
4615 F20110113_AACSSM caldwell_e_Page_171.pro
4b8503f2f75b50d423fb3a59996ce8cb
4a694cea2ec953c3dd3edf7b6672b2d412c6ada9
25325 F20110113_AACTPG caldwell_e_Page_025.QC.jpg
0d4d4d5027e48c966343a0da9a8defaa
dcaf90a4de0275ad038c537e35072b39cda6fce2
107647 F20110113_AACUMA caldwell_e_Page_025.jp2
62029d45f71e536097589af7d11a19ce
8813b5c2e782e9695a3b006baaf6b68d01c91c1c
6275 F20110113_AACUZL caldwell_e_Page_072thm.jpg
a374487b84c1ca57393ddc7dff47a1c9
349e17bc0780b2e03ce33b62cf8011255b72ea9e
3583 F20110113_AACSSN caldwell_e_Page_210.txt
f8a08aa297600db1a94b2c9f8e323ae4
ab2a126f585aee6f19acffcc7d4c5f499ee36a87
110332 F20110113_AACTPH caldwell_e_Page_119.jp2
b5d1eb97042ba82fd0067a0bd3a16afc
935c06eff6564a4fbe71bd4d1ee81bc315c02167
134902 F20110113_AACUMB caldwell_e_Page_033.jp2
169bb8123651fcf7175ca79bcd46c9f1
f20f65663d280691fe6b15507aa0cf10eed135b9
6446 F20110113_AACUZM caldwell_e_Page_075thm.jpg
8c4aa95d407848062a1fd95b1d07a5f3
f523e72862ff18ee5cd06072e08a503157f228cc
562 F20110113_AACSSO caldwell_e_Page_242.txt
b80d9f3852914e1176d176fa19b9c45b
3e4f06a153b5c6234dc1464845efdafa62f30edb
106176 F20110113_AACTPI caldwell_e_Page_133.jp2
21f1a0738523ae59eb5a8bfd1c0b0cfa
d843f989aad34d42666d0de9f60509dab48bc83f
6573 F20110113_AACUZN caldwell_e_Page_077thm.jpg
aa872ce6c6299c6adef9e2112a330d39
32af6e3e94f2902abfca779f51ce968fa57b51f4
2006 F20110113_AACSSP caldwell_e_Page_144.txt
2c0c2618a2e89196ccc3a190b10fe60a
a9d03d850cdb94c5dda77b8b2ba8207cf2c05e0e
6147 F20110113_AACTPJ caldwell_e_Page_023thm.jpg
485cb26afea1a55a6191942bdc9604c6
2ee9954c140f71c3e906cb098610f3b883363a5f
95293 F20110113_AACUMC caldwell_e_Page_036.jp2
9f23f771723bfb08210e21ac576b3991
1917070d7082b3609e7cefc956f8a1352464374f
14382 F20110113_AACUZO caldwell_e_Page_078.QC.jpg
3bf8b1076a48c197c2c8f66a4a2e5e35
9b08d103e5d802e10c1b1e4feceb03c6cf4cec4f
3264 F20110113_AACSSQ caldwell_e_Page_038thm.jpg
e1dc22d3eb7bc62c012d365fb78e3bf4
f76600cfa1db29dbdf92991c387868458f73a63e
F20110113_AACTPK caldwell_e_Page_062.txt
277c2719319dd57e6ad86d0f21a2385c
3063390888c1ff9dd1345071d3e3965f9926ef1f
106084 F20110113_AACUMD caldwell_e_Page_041.jp2
c8e76106928e65dc824d0c939f7483d3
09d0ebcc943b1d786876dbd1f8cf7da2972ab15b
13958 F20110113_AACSSR caldwell_e_Page_189.QC.jpg
b75b508eaa258c6d271d52e1c907bfbc
31b976666791c14fe6c59ccd88ca830803bee66f
24947 F20110113_AACTPL caldwell_e_Page_141.QC.jpg
56f1deefcf362f94a4a163daf4c5d08b
a0a124a725a04632dabac3ac7abba5c85e28cd34
1051905 F20110113_AACUME caldwell_e_Page_042.jp2
2fcf625cb5e8b536d31bcabfdb0b920b
6b32115c9ab05bf2d1ee0a446c2cdec04ae83263
F20110113_AACTCA caldwell_e_Page_058.tif
90cdfe04278814f189c01bfa384de530
4d4684b801f333b757eac2dc25caeaf573eeced5
24958 F20110113_AACUZP caldwell_e_Page_080.QC.jpg
8c513c483d3af98d23c2a0a20eacda9b
30541075f445799a4d2ea5a3b2819c2d7311710b
1874 F20110113_AACSSS caldwell_e_Page_120.txt
286c4a54ece8c27be231132af18d9d6c
7aaa77cbc74745bc6277fb86495ad15dabfe10fe
6095 F20110113_AACTPM caldwell_e_Page_105thm.jpg
b0cfbc37fe36dd82bce352df1c37eb55
4b31ca3db8ff73ab61226dbdad1e4ec50368c55b
107459 F20110113_AACUMF caldwell_e_Page_044.jp2
2db9b0135e3488dfa37de11a28d9c52d
cd6de68d429ccb6cfa20f35f78be05ae646d667e
616591 F20110113_AACTCB caldwell_e_Page_062.jp2
d4961eefb7280b803e33574c88a20449
391861cec98017867c3be26978e3fe65fb324000
4010 F20110113_AACUZQ caldwell_e_Page_082thm.jpg
f35caadb6a2936c38d04916e7ff64eb5
4426c8e6b7a2461cff83f21b93f9be6928d3d1a1
F20110113_AACSST caldwell_e_Page_169.tif
3eeab23636a10d8b3dd1479cf85ab789
135d6a80597fffeb935789d77a3c32c86286a699
23652 F20110113_AACTPN caldwell_e_Page_153.QC.jpg
2e36dd8a98a056f11e69fa23e995fbd5
d7a1098f1ff350d23c74f4a84b4cbf24952ba28d
1051962 F20110113_AACUMG caldwell_e_Page_050.jp2
f7fd826049a21e10e03f4e3d9e74ed69
37f8b5b67559ab9b68e2aec071de4f160511bb20
1051964 F20110113_AACTCC caldwell_e_Page_014.jp2
7aed0a3f842993e4b7177e61e6c0e6b4
965fdc5b980023712a604c1a338581c7bacd95c7
5515 F20110113_AACUZR caldwell_e_Page_083thm.jpg
e1a0933fdece20f33eb5d781935d9c84
9e597e5910ca1b3815b076dd82e4cbb328b007c3
F20110113_AACSSU caldwell_e_Page_085.tif
f7c5312a11adf5ab8516c46cd9cb01b3
3c20e439ce67f82d84df886050beba83e5d808ed
F20110113_AACTPO caldwell_e_Page_237.tif
baeb75197a70d6b849ce79de592748fc
ede41d9847824775ea480cde7ceb5a57bf86c27c
1051960 F20110113_AACUMH caldwell_e_Page_051.jp2
1691ae5121aa5ca626e11979faed7efd
9093706ecb62953d8dc788f10541b328c17ee7d9
26151 F20110113_AACTCD caldwell_e_Page_094.pro
98da7e8e51998eaf1f526525c945e933
6c8b25648b00d23543782820ffdaed75f2bcc9d8
4109 F20110113_AACUZS caldwell_e_Page_085thm.jpg
e046b7c3e484f19d66d3559d9d68f79a
990fdfc1291dd8eb6313dc8a8b343d6f4279e7fa
F20110113_AACSSV caldwell_e_Page_127.tif
9e5f9491c7eff140bd4ea2637bc2a726
7cd44f1a0112921fc4249d863c1f57af6869a6e0
45794 F20110113_AACTPP caldwell_e_Page_068.jpg
6a3b15f25664798bec2ae88bf5ba1b60
239079dcdb736a08596c3600ce00de33d20a7617
381659 F20110113_AACUMI caldwell_e_Page_060.jp2
995d323528441f561c81f8e0143c7eb9
b8eb493eeb78ea0b63d7209b7265a8b5d24427b0
1051979 F20110113_AACTCE caldwell_e_Page_167.jp2
8ce37c0c0db0419004b5fbeb4a403074
843e06604910a19df80c8dded8a1818290d20103
24223 F20110113_AACUZT caldwell_e_Page_088.QC.jpg
4965a21e5a9b8b1d8f36d6d6b2d008e5
8f33947ef613a91c5452655bb4818b418c8ac044
19737 F20110113_AACSSW caldwell_e_Page_124.QC.jpg
2190aa724af88c03b6d778fc4bb3cb71
f7e05e51d9cdaa5ef47ee72cfa4dd1a78374a6f0
5983 F20110113_AACTPQ caldwell_e_Page_156thm.jpg
210e3adcd0d319a48c6a38e67e02d26e
d43b774ed1ac120778aaed03cba15663c97e2beb
416240 F20110113_AACUMJ caldwell_e_Page_061.jp2
4e36f0833423d38d9bf98720fb330fde
cce52962e2fe37b6792fcfdd0018fefe2c004117
309 F20110113_AACTCF caldwell_e_Page_165.txt
83c9e2bd1e2edf54374bedbc3eb10055
9cc846970b883726259580e5704ffa2599fe6af6
23175 F20110113_AACUZU caldwell_e_Page_090.QC.jpg
412a3eddec1b49c3d688ba3e45f7c653
9b339712d3661d1bdb7338a92b3a0e464b2d28e4
F20110113_AACSSX caldwell_e_Page_145.tif
654ace73a41ba85e6f7bb2bdf9c7e9b3
b437411f7302c2ea284614bb7fef8ec052b93488
5111 F20110113_AACTPR caldwell_e_Page_009thm.jpg
766f78b24c69dec350885de5b096cf28
85e9adeaa2e40fdefbedd0ebe0f176fab892a59b
493623 F20110113_AACUMK caldwell_e_Page_064.jp2
b15def903eacea8b065d06c12dc032c9
3886ec7dd277d0db71a86be5e2991988b8c3de2f
1051944 F20110113_AACTCG caldwell_e_Page_164.jp2
1c8a3deeb5a1ae302e039a430a00edaf
f0ba9037ea1a0af2b3a66db08124ba2bbb0c32cd
6468 F20110113_AACUZV caldwell_e_Page_091thm.jpg
ee5d2493b4732c6e2ed96824565da499
0d98c77b3581dccab759b5fbd1eb5d6d9dc251ea
4136 F20110113_AACSSY caldwell_e_Page_225thm.jpg
4f7dcdc71c879d2e2d2920371be29c1d
440f1f0a0ea2d809075ae90210e95c12e15efc9d
65932 F20110113_AACTPS caldwell_e_Page_222.pro
cb4a1df53435abd9fda836ac7a55bee5
4457b38d3a3b107c7176f07441fe4762b1802fa4
539673 F20110113_AACUML caldwell_e_Page_081.jp2
8672d908a21d5ebd3cf0c2c9cc8a44f7
612a8dbed2da2836c405aa94c5f6436232ac850b
4106 F20110113_AACTCH caldwell_e_Page_232.txt
42704df8116d830127db489672380e9b
9dfecaa9ea64a6563e576297eeb8f70714e4be4d
26737 F20110113_AACUZW caldwell_e_Page_091.QC.jpg
b1cd818e17562659e3e122caeafa671d
f2d27cceecd6666b2dba596b5b12be55e21b5257
3940 F20110113_AACSSZ caldwell_e_Page_187.txt
81c4228c678052b89746d05a6e49179a
fb2ea70ac73ff6f1c4b4bcf56028bcb9fc1f0bf5
5513 F20110113_AACTPT caldwell_e_Page_036thm.jpg
fd1ec7ff510801fba27e9b58c7e84514
fa1f664413669cd123ec47fde94a932d70a4e4da
824935 F20110113_AACUMM caldwell_e_Page_083.jp2
96b70037c720b23e3e0e8c9d606b2e39
355c71fbdcf0d3d61ad36e6f0c585778a19bbfbd
5212 F20110113_AACTCI caldwell_e_Page_173thm.jpg
c3ca970c86fa2355e23b51b5e0a72502
79ccf70e8976d30add21219039b36c6e961a9b6f
5201 F20110113_AACUZX caldwell_e_Page_092thm.jpg
9ede0235c4d19a4ad6320954dd6532cf
d965c33322e22bdefd2be8fdad850efcad70a724
F20110113_AACTPU caldwell_e_Page_158.tif
0027b8343716f9f0de2ddb279bb297c9
24ba0d7f56c32bc3c85d613c621e6d4711632776
105290 F20110113_AACUMN caldwell_e_Page_084.jp2
4cebd6324364c92519b423aa926cb817
51955f54c610b1ee02a6868f36c2a858838a142d
5475 F20110113_AACTCJ caldwell_e_Page_162thm.jpg
812371e939f691f9ce3af3045663e615
0761b326367d83dc2674978aef7f3242ae84bcdc
3647 F20110113_AACUZY caldwell_e_Page_093thm.jpg
42e9813eff13dd2d3218cd6d37be228b
1f2f3300587c69508156aacc62be3d155e5977c4
F20110113_AACTPV caldwell_e_Page_162.tif
a33b17d8dcc40b48229e7851cfd105ed
b646d97ea3a7b68894e3cbee88d00e92e9f93012
450697 F20110113_AACUMO caldwell_e_Page_087.jp2
cf37495d313e6e35956fc5731ea452d9
476fe394dffaa152cbdf7b8f2ab3f0cebe622c44
25156 F20110113_AACTCK caldwell_e_Page_135.QC.jpg
d1a945367bdcd6df24ff4034c33f51e4
1e07ad1fb1f3dbf7f5262b26f30fdd261c92f208
2226 F20110113_AACUZZ caldwell_e_Page_094thm.jpg
134eb76b0b3dc46bc705cdf7a9e87b49
fa1c050ed02eb1959fa9dd03700693eb5da934d7
1629 F20110113_AACTPW caldwell_e_Page_083.txt
7071598b182d5511eac58cd4984f07d7
241150e7225de749a5d173dfca3d3aedd87f311d
892547 F20110113_AACUMP caldwell_e_Page_089.jp2
306fd8221ceb1806a14a13cd2f517763
8b2c48308b715bd7a8f520c32467a7bcab23b5cd
1034162 F20110113_AACTCL caldwell_e_Page_231.jp2
e092d4053d51f086c41b8dfde43b21ed
3a7926ed3c6bde0c0c03f5e821654138b1d84741
25647 F20110113_AACTPX caldwell_e_Page_140.QC.jpg
d57a2343975ec91b5d65c2b34b734d59
af23b1bfe84e228126d7d42487fbc1789661fd33
96083 F20110113_AACUMQ caldwell_e_Page_090.jp2
5f922cc87eca24e1b98b0c860bc3e748
b1a2d8307b16ad1b1e141fa8893341825aa12ef8
6407 F20110113_AACTCM caldwell_e_Page_174thm.jpg
4adbe0425afb9172438d662f6c57c6ba
5c8c5ccaa07cdc3966016324a024bf7cca29ccdf
1924 F20110113_AACTPY caldwell_e_Page_071.txt
9d4084375424d1eca3a56c2616ecaf52
3b158e3165c2c0295ce3565585205bee41c7134f
111621 F20110113_AACUMR caldwell_e_Page_091.jp2
031dcb8b9b6e7de18d36176b5d92dd46
30f9a1ce91211a0f75fbfcd958040d5b65804c94
30665 F20110113_AACTCN caldwell_e_Page_094.jpg
bff45f1ef1e71fa7eaac3d3c50492cfb
ebd8182c9b5e52d3cb74ae2fbebe811964642002
76633 F20110113_AACTPZ caldwell_e_Page_046.jpg
524c3da05a9d7879eb8cd106ed3618aa
366496e3f5e2352ad4cf194bdf9c27384ac9aea1
849334 F20110113_AACUMS caldwell_e_Page_093.jp2
820cf312ad1ecafbb7dad142275dae6f
593c70b78a38524719451bba8752a3ec33b4d8a6
14903 F20110113_AACTCO caldwell_e_Page_113.pro
2ad8bb901db7e76e1c70256efdef4d59
8305ec9c6f3031c4c323508c376d8acfd4052480
908461 F20110113_AACUMT caldwell_e_Page_096.jp2
ba4d4edc98bd482d748e31fefd91e717
db39e40a2c2f46cf3be57ca602f74d80a654b8b3
12579 F20110113_AACTCP caldwell_e_Page_204.pro
a57e796e24de3f4b5e86935d776cc5f5
eab7fc5cdad240fa1b921a7385737ce7b880cc76
574302 F20110113_AACUMU caldwell_e_Page_104.jp2
10da599dbd4bebe32aa7e2fa964d9874
adbaa7b6c3f8863d5e10dae2ce17c1e66eddd042
111931 F20110113_AACSYA caldwell_e_Page_040.jp2
afeb5b8660279244d1c4b03ee17da20d
85fecec578d74af2d1297a1e765094ac354805f7
88444 F20110113_AACTCQ caldwell_e_Page_191.pro
7467b8df1d2e33ac55a2aae6886811be
74cd542e9b99f0882959493a4db653ad5a565876
104151 F20110113_AACUMV caldwell_e_Page_105.jp2
8ab8c0009bbeffe0137ca8b4908eb8a4
67d4609f046fc888ed4b65a0aea82ecdd9255fee
1895 F20110113_AACSYB caldwell_e_Page_140.txt
7f10577a5341e8a87f53ef5d6054bfb0
44914c11bb37baea8d47e465d0785586f99cf125
466517 F20110113_AACTCR caldwell_e_Page_205.jp2
5e63fcf06b0998a93f826263c3d637c6
c3ff18bd9d1dc055cf2b82060bcc1ba3ecd54b64
504946 F20110113_AACUMW caldwell_e_Page_109.jp2
39f389f03b42c2687977675beb9c446d
94eb09888988fad5dcc96da39057875528a898ae
33892 F20110113_AACSYC caldwell_e_Page_241.jpg
ee4320b7d5a1daa2755a0877017e8d85
92e333887bd6903443162eb96bfdf4fa06c1ab65
3870 F20110113_AACTCS caldwell_e_Page_087thm.jpg
5a8d0cc71ba0685a762a70c5fc2b9ab4
c94f92698cb9428c3d3b989eb0265637fa66de37
796719 F20110113_AACUMX caldwell_e_Page_110.jp2
01cc633502fc9ff3faa116362a8a1d14
9bf9a86b1e83cdf552f78353c9a197818c0fe522
18438 F20110113_AACSYD caldwell_e_Page_180.jp2
d22ef51edf661eabdfd0ee9718a9feee
baba249e10a1132562a1d271c98bb83d275a709e
26036 F20110113_AACTCT caldwell_e_Page_079.QC.jpg
6e2c8184e43ffb771b8e4b75998b58ec
5cfb20b427c5a0682524d07de5f9b952d910a7e5
105023 F20110113_AACUMY caldwell_e_Page_111.jp2
40b7219b85c776f53f130727558b00bf
e7a7f071fda54234299aa1e64d9e92942c75709c
21037 F20110113_AACSYE caldwell_e_Page_016.QC.jpg
4cdc21f6e81cadef5fe94eb91a987621
f940529c990c5ae134ef5682913032828dd10a69
2831 F20110113_AACTCU caldwell_e_Page_207.txt
58681c22dc93e1350adc7ab063eceefb
a50b00f0ca3914438f4c64efe04faf3b0e165167
87298 F20110113_AACUMZ caldwell_e_Page_112.jp2
326f9812759681b474b894fb5bd6ad8a
1aa3d8e8fa055b3faf0e18147b20c75b5072b0da
79934 F20110113_AACSYF caldwell_e_Page_080.jpg
b915f34717a69e6d2526a31dab2dc4eb
f02c95e95994d60edcbac296ad1388451a27bfd8
12969 F20110113_AACTCV caldwell_e_Page_232.QC.jpg
864f18f81fdaf5198258158f1fbce56e
8034d7f7d354c169dcff5042fab270d80bff4895
44886 F20110113_AACSYG caldwell_e_Page_090.pro
30610ab6fb5a613445427bf0fe5314ed
7dd29ab06f1c5ed55525fe346f4bd67b0203301b
F20110113_AACTCW caldwell_e_Page_040.tif
0d9be9a46c46dd8153aa846c2579dd39
908823b024ea6b45fb2155444c4ed958d36460a7
10359 F20110113_AACTVA caldwell_e_Page_223.pro
cf7a30de4fb5b2dce45a4ba4ee08a178
25f7d55c09eb6f0e5060e497f3bfc11cc29e9aca
1701 F20110113_AACSYH caldwell_e_Page_147.txt
af378afcddac26bdbce7452481099729
573109e0051adc762008900dfe90ceda3b28e140
10830 F20110113_AACTCX caldwell_e_Page_005.QC.jpg
3eacae09e95a6872b9517720aeb1e632
c5708131dcbb4d8f716c99c9f11fafdeb0a2eb83
F20110113_AACTVB caldwell_e_Page_168.tif
81e4a229c046969fce169dbd1299b514
ddce1d8559229f3dfeaae2ed1a79c9cf604f29e5
39424 F20110113_AACSYI caldwell_e_Page_116.pro
aae4d121f676171f91205da3d1fbedac
aa8e011b2a5e380c934c1a8498804be1a638cc90
F20110113_AACTCY caldwell_e_Page_072.tif
4715934da19e514b03806ec615d73137
c1c3a70cb3bffa5b654165cf058dcd6e8aaf1e9d
52152 F20110113_AACTVC caldwell_e_Page_181.jpg
e1db54ad4a15637f2f7dd95040135c99
b904e4bad25175ff7c58e437bd124b9399d91428
F20110113_AACSYJ caldwell_e_Page_059.txt
4cf5250cd2866ab0854ebe5326a7e7d1
cc8cffc6740f4c2ad7089cbc0235db5c3c5b175f
1424 F20110113_AACTVD caldwell_e_Page_161thm.jpg
4bfacf520c7cd42a04064197f627c394
2075ae59fed6564af29649e6079f3937aa40b4e9
15121 F20110113_AACSYK caldwell_e_Page_180.jpg
f59ce73c833f6f0aeaf07815aac1c5df
5c62b37e7315bd406aa42d422a9b8cbd8364908c
93342 F20110113_AACTCZ caldwell_e_Page_147.jp2
03822735f711eda8334d91b081839bb9
5f63af0bc42d4b40f17033b485393b7c1a7072c8
4684 F20110113_AACTVE caldwell_e_Page_095thm.jpg
7259d12e171ba525fbc1d22062433e25
2db8d18a93a1cebf6d2b2c0c6feb0c697d90bbc4
54316 F20110113_AACSYL caldwell_e_Page_037.pro
cea927d6456befb9a428cce0d7f55189
36eafd49ccf882c5875f0cf024b79e79497af609
F20110113_AACTVF caldwell_e_Page_110.tif
34ea0ba82abec3c6f94605b269514791
da38f78c0dc9eb11bbae6f6a1f3178a69cac85d8
1816 F20110113_AACSYM caldwell_e_Page_137.txt
f8d7d30b1c34ff4c04adde33425016b5
df7b1369950b1a0516da4c898ea775a0702410a9
25512 F20110113_AACTVG caldwell_e_Page_149.jp2
b5deef2703d80131cf62b20194e6769c
f9318cedcf3189c15bd40338d6af27bda8190a5a
5924 F20110113_AACSYN caldwell_e_Page_202.pro
46b721a55bf1a9f23514d327e760b8cb
4c91e8d27a0d67c948f79c11a800019a5bd53b36
F20110113_AACTVH caldwell_e_Page_053.tif
139ff4733a78e9446c32c73318de577e
a3b8dfe7bc5512214102253da48b87fc2534c7ef
49261 F20110113_AACUSA caldwell_e_Page_043.pro
a46122f7a24b80ca06293961f7e4307e
5dd99c9939cf4fc0981b2ed43a479b978dbbadb6
1330 F20110113_AACSYO caldwell_e_Page_008.txt
6ae186af45f6991f66d1b21947333db5
f9e1af51363de0283ab76def02632849789e0fa3
31130 F20110113_AACUSB caldwell_e_Page_047.pro
8728e4e4683880a7cfaceb6f4bcb9b6e
f68c431a049ac77112ed38f62aeb92232011d290
6909 F20110113_AACSYP caldwell_e_Page_206.QC.jpg
2fb5ddf6f27449895421cb6a42d054ba
c93127afd3e28fa93940e17b6e97478cbb8c6f61
1835 F20110113_AACTVI caldwell_e_Page_105.txt
8bf9354fb3d37b18e17bd8dc18103726
3c5e226841b375303bf60afb64a39e7c249dc290
31570 F20110113_AACUSC caldwell_e_Page_050.pro
b1e11c1dad0411d4e293f7b5ad3c50f2
8a82b149e8c600769e76af19ebae5d2b030bc937
1885 F20110113_AACTVJ caldwell_e_Page_118.txt
6450b37924abfc6675e47bc4c5702f05
d5f9b4cbc2ab14a98192aa4a646cc0e807bfd109
53990 F20110113_AACUSD caldwell_e_Page_051.pro
8a69a720d231e93a21e01bbc3869d7eb
3b41156e27a7bb689b882a6bea36b9f62b8353bd
4679 F20110113_AACSYQ caldwell_e_Page_183.QC.jpg
a5c95727fa11976f0986374c9dcbebb3
f0c040ccae05c726b9ff928fc25007fe6895fd29
105311 F20110113_AACTVK caldwell_e_Page_107.jp2
725a505c8dd4dcda129522610dbde1bd
35600df0eb9e13fd9f7c52645a15c1ee0cb8e919
42391 F20110113_AACUSE caldwell_e_Page_052.pro
8915e300d0ee2bcfa64a8ad02b3971b2
9ac1423b2c957d31e4f3402b3d17e4afcaed9e51
498606 F20110113_AACSYR caldwell_e_Page_065.jp2
eeaced1d02a63aeea31c8891b63c135c
5be7d459eab494645fcc046bdbff92442c774169
12756 F20110113_AACTVL caldwell_e_Page_113.QC.jpg
ee9ab0dd1dd462faa0f7005710fc473d
b99fc7c45c5f3b631cbc4c5655e47642e6115b61
33483 F20110113_AACUSF caldwell_e_Page_059.pro
371044762b259e05de195959f48afe09
17ffe0f574b92cacb5a068a37b31b4ede9f4949f
24815 F20110113_AACTIA caldwell_e_Page_127.QC.jpg
7164bbc7870c2e37b18534857099a080
6c60ea838b51ffd54c8e71166d4cd18b278792f5
128986 F20110113_AACSYS caldwell_e_Page_247.jp2
0d8c4bddf8ede32e3a3a164d06bfcef5
3745e4fd541f7dd6bc39d3d781cdbc84498a7ad9
21912 F20110113_AACUSG caldwell_e_Page_062.pro
d0cd7beaaec96b832b3237b5b2893cb5
79bcd706aedc792f5bd0440379145896f308887f
25847 F20110113_AACTIB caldwell_e_Page_058.QC.jpg
9de1feaf8bc81159b314084b1eaf31a6
b35c5900a561b784a9a8c986d508e722d168f8d5
12913 F20110113_AACSYT caldwell_e_Page_106.pro
31680d6ed94b780af6814badd7ba61f1
7e16bd5d2908873b0c5b48df72ecf472ee3c7645
108091 F20110113_AACTVM caldwell_e_Page_146.jp2
6477c49c18bad17f13e0f1e8505a386a
ba45fbfae07bf54f4e5f0f677953daba2a2dcd5a
19286 F20110113_AACUSH caldwell_e_Page_065.pro
02c6457ecf2147d520154ae1589945a2
fd8054365fcaea201919056491883b27b831dc7c
92055 F20110113_AACTIC caldwell_e_Page_125.jp2
d8d408962c7cf2358d7c150bbb196887
c79bc34999eb6df6a337aeea668e20f5cf80a7b9
6521 F20110113_AACSYU caldwell_e_Page_139thm.jpg
1ae982d38a56a563c91122a1078a8471
0ef98afa3f90869467e6043a58eb6378dd2459ce
46564 F20110113_AACTVN caldwell_e_Page_142.pro
8d5e31fda42617d6235b9f3cd56efec1
e07a9f4a6051f95d5b1ebef215e6e25a88e36e33
79453 F20110113_AACTID caldwell_e_Page_063.jpg
c8f2b4ca9cea699d0f997d179cd0932d
79718818c663012a5e5ac38194aa52920fc53583
95678 F20110113_AACSYV caldwell_e_Page_011.jpg
d71f10a734bcf3e3c61e4c4d72f3adc2
58bad41d6ff2fa730dbeab2c597c13551b88042f
77738 F20110113_AACTVO caldwell_e_Page_009.jpg
ee45d4c5233e08680243dedc85fe793a
cdc92e3c4e16f212bf9651f873b2bcef1a67fae7
48753 F20110113_AACUSI caldwell_e_Page_071.pro
d5ffff095925d05667d7f649af5f8fa4
6d3f2e43ee6b29d162a581f443174086cc0535cb
65400 F20110113_AACTIE caldwell_e_Page_124.jpg
c051ae3798c71342202b1dd5794681d9
5a84b597bd4a9eedd6f69c645f9cee2a5eb18915
3205 F20110113_AACSYW caldwell_e_Page_244.txt
eca44ecaede06f1d80513ca3dd0cfd97
171fa87a14633f0cfacffb6d8e510edc2fc96db9
1051800 F20110113_AACTVP caldwell_e_Page_208.jp2
3f16d6e7326f7cd5c02018920d04c39e
7fc1b466e3c8b3450b0b6d3ddf6f63c2d8a63550
49586 F20110113_AACUSJ caldwell_e_Page_072.pro
86bfc3b327a471194637f2820cecd03e
5e9edae4882015072ca59cc659f7d9ae6c39684b
23602 F20110113_AACTIF caldwell_e_Page_137.QC.jpg
739d5456b4cffda499b94d0f0b379930
db2fea1eaf5c4ee50aea84ac8a10d7d66cf5a924
F20110113_AACSYX caldwell_e_Page_201.tif
bc07a91a46177b3690471e6bde0dfcbe
a17faa6e35ce2d296964eb874861245fa9454dba
13926 F20110113_AACTVQ caldwell_e_Page_181.QC.jpg
dec8a9998f86c9ff2ae5527ab942a257
dc1419e54b40c5befc9089f9462fb4b2f8238cd0
14048 F20110113_AACUSK caldwell_e_Page_078.pro
a092bd30323d39ced42d7f08ac09b119
670295f6b8e19915c805587ac83db6c9d983611d
1113 F20110113_AACTIG caldwell_e_Page_239.txt
5ac32113de38abe6eac0ae04bbb2a7ba
9356cb845b9ca059a9b9113b862bb7db0170825c
5761 F20110113_AACSYY caldwell_e_Page_096thm.jpg
6bd48fd9eea85cf84c6bb58d22304b2f
b85d8773d6b32bec4228a124a80fbb053e668f8f
548115 F20110113_AACTVR caldwell_e_Page_106.jp2
3698061b8cea95ad2f560b1d4add6940
70deeb8b1b526c0799173e0f8ac9fe92cd0392ee
16425 F20110113_AACUSL caldwell_e_Page_082.pro
638d076b65b3c108927b6f964a6cc3a9
2fdb8fb0cd169a799578afe8e9bc534d967e397e
F20110113_AACTIH caldwell_e_Page_047.tif
5725feb7f4b0e34f89ef0527c696e82e
d3c71f68c4c7dd6b3de5aca9dd52fb7442b265e7
F20110113_AACSYZ caldwell_e_Page_128.tif
790b69f661847dd6f7d88f37000aa2cb
854b69a000d9d9bf562f8f7000a499302b3b7f81
5664 F20110113_AACUFA caldwell_e_Page_183.pro
262a75ec99713590d4624a50783eeb9c
ea63d2c34544ead26a20f91697f9c4402efe4f15
F20110113_AACTVS caldwell_e_Page_166.tif
680a6c095db23cc6eb5d522b14fc5ba2
d66730f2b42772843f884029179eb58a6912ec41
34388 F20110113_AACUSM caldwell_e_Page_083.pro
2588dd792f964c8289cd22b9860a7a0c
6a2796909701f8a32a38a5001b4699378e1e048b
F20110113_AACTII caldwell_e_Page_108.tif
352fbd47b795e5965001509b23936792
a55f8faaf68ef4bdfd492a0d31910f2274d47b78
24073 F20110113_AACUFB caldwell_e_Page_023.QC.jpg
5688b5fd1152987b134d4a07efe63fce
5109b50c34360039ae06a5c07d839f4199e37f79
67742 F20110113_AACTVT caldwell_e_Page_230.pro
ec14bdb6ea2136ac5bdd6dbe4bbd2d82
c7b18d2cb79a8ee4c6bcb6d67cc30fe4c934b2aa
49024 F20110113_AACUSN caldwell_e_Page_084.pro
391e4eaebc2e146704ae52b986c61c1f
3a1497d22a05837b9432259ebfb940ce179ea6d4
14458 F20110113_AACTIJ caldwell_e_Page_085.QC.jpg
5f92a11249932171f1b5e81d3b76c5d2
e0b42172ed9e6b31f513df1d92d8a78e9dbbfd61
13578 F20110113_AACUFC caldwell_e_Page_065.QC.jpg
be33e2b5144013a4998aab478cee8b08
c9537eb90d0824df2a5626b4b51b2fa86d74567e
2413 F20110113_AACTVU caldwell_e_Page_247.txt
579b1bf91c69cb6a3abe1d378f052993
ce56af9f9536caec77ceb1468ad1c801c15a98f3
44614 F20110113_AACUSO caldwell_e_Page_088.pro
239b474893917caaaf1174b2ea670958
8c23f6a5135e2d9c8a76b0c95bf662c7334e72f1
F20110113_AACTIK caldwell_e_Page_244.tif
0f5ce364c8f24561b5e25e90fd8b91e7
a300c5c43d6118afa2caecabdbd750a9057cebc6
14118 F20110113_AACUFD caldwell_e_Page_207.QC.jpg
60a4c8300580beb0f9366ae942863117
4052e788173a72f06880c64a91ed9173343f09d1
19704 F20110113_AACTVV caldwell_e_Page_069.pro
46e66f58dc6a74010e79104c2d02d741
7add5f7b10e8d4b536e51800094027d575538ee1
39171 F20110113_AACUSP caldwell_e_Page_093.pro
4244621cd637bb1b1541418f274c6331
00a78bf976e1bd598560dd3f943239d68f72d1a9
18314 F20110113_AACTIL caldwell_e_Page_123.QC.jpg
c5f90729a390e75587fd51b3520a860e
0ce22daf899efd6e721c64b1b9c54aa3aa69ebbf
9807 F20110113_AACUFE caldwell_e_Page_239.QC.jpg
acc9489d1cd324c488fb446a374c8b25
f8eee92ce52b84b78ba846c3eab3e54b4da6135c
F20110113_AACTVW caldwell_e_Page_172.tif
04516e5bb598d6662817d91245019c33
c91c0a5661a77ef764a7195743940eb48a6b69e4
25954 F20110113_AACUSQ caldwell_e_Page_095.pro
b1fae9d5056b940581ad344454c4389c
70d9a442c8508df47baddc92a421a78c937de35f
75173 F20110113_AACTIM caldwell_e_Page_246.jpg
f6c381bc5effeca03eae95d944e5d2d8
57d78c46e56474827ff09261832f83399213c52b
47819 F20110113_AACUFF caldwell_e_Page_155.pro
09e01f852590d1f7e5b6578c4597525c
6ffcf563e5fd8d15246033c859e56c24ee97ea06
129585 F20110113_AACTVX caldwell_e_Page_244.jp2
687713cbc1df181f75c4325035724246
d9953c75d824b12ef59c7083a2d7ffcc510442d6
34826 F20110113_AACUSR caldwell_e_Page_098.pro
ff7d61c947237d017e333f9522c42e89
d3aebfae2865c04ba26558fcc3c61f17ae1badf9
23697 F20110113_AACTIN caldwell_e_Page_117.jpg
5a2ab64a160068ab1e9fd7e40ea3b523
cc07a0947d20d59e351086005acab01a8c690067
20180 F20110113_AACUFG caldwell_e_Page_068.pro
b32b24ca45fe92b11140d326e587796c
52fa2b6e4a37b4efb665e3997bab3da2d881d7ba
F20110113_AACTVY caldwell_e_Page_188.txt
333f88172a28ce7ff7d832106f710b49
2eb20d5a5d9d54e498f7f85d1b22f49efd93b5e1
3223 F20110113_AACVCA caldwell_e_Page_191thm.jpg
9a0f7e8807eeaa9c61c05ddc08f8c1c8
59bdb7563d173f75fbcfdca00a2c370fcb058f9c
33641 F20110113_AACUSS caldwell_e_Page_099.pro
f626ff28b192bf704e6810cc51491f64
7d9d3408095cc35c8c3de162d535017c02c70976
F20110113_AACTIO caldwell_e_Page_093.tif
e89f89a495d639360981226f5e6553de
54b6c0669c21671a1ba947a5847fb57c94296afc
2026 F20110113_AACUFH caldwell_e_Page_032.txt
a5612764a2ff3aedb57e033c3324568f
85e19978d38f1fee48952fbae0b3af1280e6152b
81198 F20110113_AACTVZ caldwell_e_Page_024.jpg
1b92fc314a61614d19ece2a994927894
a8eab8a8366d582bec0874396b61c6ae6043df62
14639 F20110113_AACVCB caldwell_e_Page_194.QC.jpg
2f49dfbc4f6d8921e4e88b187be4e22f
fe9fb6c102596b3a1ec79a4a2e383b602646ab31
14732 F20110113_AACUST caldwell_e_Page_104.pro
2ac844a61c48245221a6fa6fcc10a846
0b37e3505d9cc46c02d5629cc562df2c97838d0a
9496 F20110113_AACTIP caldwell_e_Page_182.QC.jpg
bb6f2359a1ee9eed80ba38ff0ce18a88
842e422140f076214bfef0034386f1852c31f385
29988 F20110113_AACUFI caldwell_e_Page_048.pro
3d4504cc356b7985b58fc22b8920ac36
9b5a1e88ff3da8c7317cecd22dde1b523b433a5f
F20110113_AACVCC caldwell_e_Page_195thm.jpg
0cf01c864685764174e62514259a6bee
0218c84dc87fac410664deb34f843312fd55ec50
34048 F20110113_AACUSU caldwell_e_Page_110.pro
21447c52d38f5c03b1a89ebf321a4ab4
820b39eabf1dedd8cf594dd15b6339abc25c4bec
F20110113_AACTIQ caldwell_e_Page_150.tif
accc9c64cc60472f0b18f7d5091f00a5
bd9db0c80b8c925af784594bf4eebd496e9444db
172309 F20110113_AACUFJ caldwell_e_Page_242.jp2
d7eaccf7499dbf790169a143d30dd34d
ecd4f106dac21a3430fd3310ecad77706fe69d62
13935 F20110113_AACVCD caldwell_e_Page_195.QC.jpg
95a12bdad8036ebfec67154b15dae580
7e6047fd4ac65e2779d195625b0464fbc89f64c3
16034 F20110113_AACUSV caldwell_e_Page_115.pro
91c12772d2b162ea323f1e2ad3dcd36b
697eb299b0df9dd1b9fd2875e9a0db51ef679fbe
20203 F20110113_AACTIR caldwell_e_Page_034.QC.jpg
1e78f5cb2b790719c4ece41f338dd59d
9f969bb4f7b10f79f1eaf1a30ac2e0f25729b35c
98877 F20110113_AACUFK caldwell_e_Page_027.jp2
6a3c2f6701d71f3d9336a2a742fb3251
7376b1a077daf6047f39782d78d0859ccce7139f
15495 F20110113_AACVCE caldwell_e_Page_199.QC.jpg
d96e42bae0dc607f303ed717103db09b
7229efe3d8572030218c1a4d08d61e78c44a39ce
49455 F20110113_AACUSW caldwell_e_Page_122.pro
614574eddddc95b7064d58a13ac4790e
c45e3a11cb3d07509eae363a73351804a9926585
2192 F20110113_AACTIS caldwell_e_Page_182thm.jpg
32f9e390cecfc6438c618f2fb3da37fe
57968f808bcd4d8cac67c0977af42cb1e9c11d97
454 F20110113_AACUFL caldwell_e_Page_206.txt
f6fa31817d9ff27adb7067a8d609ae87
13cf6de8458063feb7e6774e0e21e97a046416ed
3295 F20110113_AACVCF caldwell_e_Page_201thm.jpg
214f2c9400a63fad6b546c0b60e044b7
c27175a69a597d9a9d1a8b8bbf55fb6cf75872f0
45896 F20110113_AACUSX caldwell_e_Page_125.pro
e5a587c9b24778f9adadbcc8c2bd918c
2e77d48abed22b9724f89b42684bdc083f603b99
F20110113_AACTIT caldwell_e_Page_081.tif
ef886578c7ba4f73291419273502a8c7
21043b65a762fa0f4a46cbfc333d7d52a29959fb
19699 F20110113_AACUFM caldwell_e_Page_173.QC.jpg
515a56fdb2aa3b93598159cdb22327ff
1d7fc438828d067143ff15512c328b184ba73652
4179 F20110113_AACVCG caldwell_e_Page_202.QC.jpg
0542eadc0347231727637c31f02e88cb
8d15eba6e8e7e206665972e82fd39bf583585b52
52130 F20110113_AACUSY caldwell_e_Page_126.pro
d59035cefc33c7cac20b027acc0eacfc
88c837827e950bfc054d4634d6b7bce47db4af27
3457 F20110113_AACTIU caldwell_e_Page_164.pro
4c25661d3b3a635d7f2861c95d3c79b9
83e3e9bf6e6cb06c2a4a7043f107144ec82646ef
1051978 F20110113_AACUFN caldwell_e_Page_190.jp2
688b402d4340d347119766ec0716fcb4
825e1c20733a6318f874f0bdbf5051348b04b663
13115 F20110113_AACVCH caldwell_e_Page_204.QC.jpg
fd3aa6583179239f93d64fc25d640724
84427d22f6572023f51c8d79ac6bec5fd18e64ad
51578 F20110113_AACUSZ caldwell_e_Page_128.pro
49086b804087d0e35085d35259797e4e
f8ab7f83f9d60636bfe0d5aa124e54765ca87447
827 F20110113_AACTIV caldwell_e_Page_003thm.jpg
06389af436a2aa2c5500a17002a2b010
02c7ac04f2e05e1aad890d4eda079c10cf36db3f
50271 F20110113_AACUFO caldwell_e_Page_058.pro
3168a205d0af2a9fadbb009fa4bfee9f
62f4bd47df450d5a769dbfd3cf92b7125132a65d
14241 F20110113_AACVCI caldwell_e_Page_205.QC.jpg
eca2676c1d17857253cc364ba59cc975
d43997b20449e7c6f0b7bb162c6a4e3f5e40fd8f
118295 F20110113_AACTIW caldwell_e_Page_243.jpg
dfd5a8ea8ba37a94099902e1c65767ef
9835a2c3701c3571b9f091fee6637d3dc5423cb5
1051973 F20110113_AACUFP caldwell_e_Page_194.jp2
40f2ccdbe2141160d99a8480feb1d717
2ae41779580dc2e2372820f723607c7e9640d7df
3234 F20110113_AACVCJ caldwell_e_Page_208thm.jpg
c73e2af5a9e00e439a27924b8868839e
4f99759d1b6c6c6f5e522241b0d889b1b20d85ec
75133 F20110113_AACTIX caldwell_e_Page_090.jpg
5926ddb3761b6b63abfd3453655c3806
3eb12b19c179aa3e001e618e24d98aab77842231
2114 F20110113_AACUFQ caldwell_e_Page_004.QC.jpg
c1c5996f3e7f430856bb7f1adb15e7c2
15f8cfdfc4e576b3722f2a53e739c694b6fba392
15115 F20110113_AACVCK caldwell_e_Page_208.QC.jpg
65e52244d0a1a76da04dc5cc45e15d8e
a7c7f013d2b0e9a4815cddc38ffe3eaf216d5fb6
6875 F20110113_AACTIY caldwell_e_Page_248thm.jpg
69432f87693ee0b014ab682b88304bfb
e6a673e89413f545b8dcd5b670e894c3f0b00a5c
80158 F20110113_AACUFR caldwell_e_Page_014.pro
96acea14f51d73742f1cbd77d9acfe98
ecd3735f41b4b54adb751a53ee9a80020433a2bc
15164 F20110113_AACVCL caldwell_e_Page_209.QC.jpg
481031657f5b0f68a78cd8ca05dc20c9
2d6743ec51839b6014ff06ba5517a002b6635e9e
3700 F20110113_AACTIZ caldwell_e_Page_150thm.jpg
271d1a9c3216120f50f61170686788d0
9f1d5f5a0c6d7ba26a360f3f4d9c732e650a75b3
5859 F20110113_AACUFS caldwell_e_Page_046thm.jpg
cc04889b51f3feebd0dd5eac982f456c
8c58639712c591e16512c2cbbe27cd1fa13059e0
3366 F20110113_AACVCM caldwell_e_Page_210thm.jpg
63ba9d455ddfd0962b05ebfcc40019f1
014e6775c4b784a1ea8813180ba7adacf534e773
F20110113_AACUFT caldwell_e_Page_210.tif
f609a8e829ad8440ee8b36f7845ab1da
4496415e25be693a9423509fe8a5ad5a57036995
15343 F20110113_AACVCN caldwell_e_Page_210.QC.jpg
6354263a90f85b93f5e28f87499b3925
2de74862f72c8c8141e7e8d049904d06c1018a34
67763 F20110113_AACSRA caldwell_e_Page_056.jpg
5fb13a182d049191dd0d5c4ebced7ccf
20827d1fab130a8185e6e102b2b66c37ab75ad0d
F20110113_AACUFU caldwell_e_Page_185.txt
e372326396eb9624b513266a6ca37609
84c1fcce1753ca4fba088b2b52ef26e7fca6058a
8802 F20110113_AACVCO caldwell_e_Page_214.QC.jpg
8247c86a70bd056c7646b13b78a6da5a
9b8c1501713d1a047953f7951b92fb966ae2ece9
1906 F20110113_AACSRB caldwell_e_Page_111.txt
73fdf49ffbe5eb3828115874882e8cff
1786560ba8921ab3b636d1117e9b1cf307e96351
5804 F20110113_AACUFV caldwell_e_Page_067thm.jpg
60422be9f454054bb1b370d14bba0787
04a0aeba7e621b7a7f3a8d69a3b049afb01c374e
1250 F20110113_AACVCP caldwell_e_Page_215thm.jpg
01a44123ced7a33d3a1abf42c679f25c
dfe7cb0ca7a43b2fcf3e8e583206c3aa629fdfe7
21992 F20110113_AACSRC caldwell_e_Page_092.QC.jpg
059ddedeca8f5f511613de8da4a08c34
ab702adc1ccf33dc6c304493b9fc2bcfa7cb75c1
15519 F20110113_AACUFW caldwell_e_Page_198.QC.jpg
a575cc75d27fbe967c11a96563b06426
c9c6b6262ff948b1628aafdbb7cde96cca264cd6
3176 F20110113_AACVCQ caldwell_e_Page_217thm.jpg
7cbe6938d9556363217ad6209c20a241
f79fecefa7c18b0ec927681c559672b63c80be8f
2969 F20110113_AACUYA caldwell_e_Page_020thm.jpg
9c0c48ea6a58b85f16454e4877ef46b9
9cad44025c0c31dcb5805b237148e3fc07dae573
71386 F20110113_AACSRD caldwell_e_Page_171.jpg
2301c751421e271e36b5f8c6c671df5f
9ead97ac0209e0f0f0b24049f3f0b37e4f08e5fe
39740 F20110113_AACUFX caldwell_e_Page_112.pro
2fb0ddfa72428074e2022bd688d4ef93
8ad392204c07941fb5d76b805ade300686e569ea
9823 F20110113_AACVCR caldwell_e_Page_217.QC.jpg
80e1eed337fa42f409e6f0355e77291d
3447b97dd19307469f947d5b698f642ba0d6b246
5926 F20110113_AACUYB caldwell_e_Page_021thm.jpg
212a051f12ef4d04212c0f84a0e7a5bc
a3a5aaec1e95b8cd65c534afdbc2b8405b1b1d55
5875 F20110113_AACSRE caldwell_e_Page_246thm.jpg
13556d770fe768b77e95ebcfda441f99
b4d0ca78072979ed39787c7f3451185db7893d97
1051919 F20110113_AACUFY caldwell_e_Page_186.jp2
73237dec3295541068bdca97fc9e98e9
2db419e783c15f3672b211d35194cda41acfaed1
5730 F20110113_AACVCS caldwell_e_Page_220.QC.jpg
ef7f41e20e3ce9a8430114bb0fb44b26
99134829789287e8d5af786ce6fc6f8b969d3559
6380 F20110113_AACUYC caldwell_e_Page_022thm.jpg
25676a42c8870d45c784f46ec1bcb817
f21e8794ebcbaf0af2c2a82271aefc86e9f05471
5233 F20110113_AACSRF caldwell_e_Page_003.pro
221bd678f0d11cf0a4b606db47273de0
b415075d658cf1e4ac0c8ca8dea5a59194eded46
11840 F20110113_AACUFZ caldwell_e_Page_020.QC.jpg
11aaa0b5b4ea1b864abcceaeab117ee3
78ffd8b79964c5be51aeeaf61d1eccc6ed4c2683
1243 F20110113_AACVCT caldwell_e_Page_224thm.jpg
812c10c1788b41c76faedbb3156711e3
f332fbfba06536209399d7b56d28dbcccdd5e917
24618 F20110113_AACUYD caldwell_e_Page_026.QC.jpg
6d65a35d45376d4958bd9e7bc4aa25b8
eb6431e00af9e1a51dbc22a0e84fefa3fc7e0fd1
1051830 F20110113_AACSRG caldwell_e_Page_030.jp2
0ee296bc0a3071a433da4e12a2d8ee49
8c769c42bf560071837817fe88689f244da06e15
12635 F20110113_AACVCU caldwell_e_Page_225.QC.jpg
e4fdff3a6c4bebc6e7971ed30fcca049
964a2863d9bcc5185056447337689ee89975a8b3
23863 F20110113_AACUYE caldwell_e_Page_027.QC.jpg
e273641229d555882f2a2a7a0c99f898
47b218d28c8ecf63ec93dd3bb1efc705aacb7df3
42739 F20110113_AACSRH caldwell_e_Page_134.pro
54bd77690740526980a9dcf01a74395b
ab76c36fe12314ad8de840f2862d46a496187fe8
66315 F20110113_AACTOA caldwell_e_Page_190.jpg
718e0b33f85358916037b499569dfee7
07826ef9dbc96fcaafa8a12bdd0a1a78c9b1111d
12660 F20110113_AACVCV caldwell_e_Page_226.QC.jpg
716b1a5d02bae8da78584e3c9832c917
18bee99a758f47ab64a52b61e086dc8b5ee84cdc
3970 F20110113_AACUYF caldwell_e_Page_028.QC.jpg
462b7485f9870460d31a397e7cf42caa
e9ef79ede6277209960d553a179813f7d542d458
96456 F20110113_AACSRI caldwell_e_Page_143.jp2
72747883bfd342fa230a13a498a7d0b8
9b5bc55cdccc3d5abcb7a061d2379d858350e661
66556 F20110113_AACTOB caldwell_e_Page_198.jpg
c2392cf4fa89b314aec66a9718ad9d8c
16577e968ae0468c0de0e6ef8c665cf4b9797b74
13693 F20110113_AACVCW caldwell_e_Page_227.QC.jpg
c66ea0c4741c1d2c3c9c3dc1983165b2
9bd0f0e068e531bbaf9618b9728170a37ad8bb04
21965 F20110113_AACUYG caldwell_e_Page_029.QC.jpg
a1e8219f2e35d073446b083c3d9793dd
0658a1dbb77162e4ff52cf18990207c3b59a4953
15979 F20110113_AACTOC caldwell_e_Page_087.pro
384e8eb39451eae41ff1e2396ee188ef
b3129659396796f7a28fe232029af12eabdfe9dc
6629 F20110113_AACUYH caldwell_e_Page_033thm.jpg
3de48c2f7dd0b670fb201fa777538caa
961710122231d62f2a58dfefe6adb87ce2079af3
1051869 F20110113_AACSRJ caldwell_e_Page_176.jp2
4cc441194a3f8450e062a5ce8941e599
cb3d9b4611280cfdbf89ba5a83016cb012baf362
48591 F20110113_AACTOD caldwell_e_Page_157.jp2
12855b8df2eb83b463a3c0c618014c4d
77a8dbc8d15d91fc405f70ac775f9dbd81f91690
12967 F20110113_AACVCX caldwell_e_Page_230.QC.jpg
cdd81cf89cd7a186a70c7148e0f01630
844d5bcc4e06a9ce98817f6a52e3edf9564f2898
28288 F20110113_AACUYI caldwell_e_Page_033.QC.jpg
0984d823d4c210fe915fad0f3f0d2fd1
281c0efcbafbd957c4e6be991592d08a61645157
6070 F20110113_AACSRK caldwell_e_Page_127thm.jpg
ac049b92bea479b21ac89a6a33b460a9
de051a20623d350d60a9deb65702cbd16274e107
8391 F20110113_AACTOE caldwell_e_Page_117.pro
9a1acca6b29e704b7e51cc0584cc85a7
779b6979e9caa7a52799b2f5b25d7562ce50185f
4665 F20110113_AACVCY caldwell_e_Page_237.QC.jpg
db26b9cc077145257b1db44e5a20d6aa
eb3604d73e81870e410cac2b1878ed0ac460b08e
5949 F20110113_AACUYJ caldwell_e_Page_035thm.jpg
45ba25212f6c68b835778f9b2fdc8788
5e61b83d03374d290d22ab0dceff902e5381e259
10632 F20110113_AACSRL caldwell_e_Page_219.QC.jpg
3541a297cb153823dfdbf80ab7c7acde
a5ccc7ebcc12e816719bbeff0d6b19c6102965a5
10429 F20110113_AACVCZ caldwell_e_Page_238.QC.jpg
7bc8bf410b582b19df311e698ca570cf
8995e4cbcb9b727139c4e0ab68cd9e1de61181df
45923 F20110113_AACSRM caldwell_e_Page_010.jpg
01c0f84886169bfa484f5a4ee3568ebb
1bc23a18e3fc782ff9c24f4506a7c6f18a729973
3572 F20110113_AACTOF caldwell_e_Page_209.txt
018031a1b1e61a4a875d9a9598af620a
27741ea3f175ddc72846ea3b2863f176a8759d11
23542 F20110113_AACUYK caldwell_e_Page_035.QC.jpg
8fb41db220dcd44bdffd53651d0bc6e8
53be5b3e8d8d1a01311b84b05846df220984558e
25445 F20110113_AACSRN caldwell_e_Page_075.QC.jpg
733b548f20a61ce92d4f7a6973649777
f208f5d0ae3f783822e8b66f087faea17aee6404
22676 F20110113_AACTOG caldwell_e_Page_085.pro
8037fd3864c35f63a329da3ab0e0246a
c353a23266ff1748e2629569d1be41a3e0fd3637
66584 F20110113_AACULA caldwell_e_Page_191.jpg
57646eabf45e13f03ebedc621294bc53
ce86094a751e3095681212c338e9f1c98f2f084c
23445 F20110113_AACUYL caldwell_e_Page_036.QC.jpg
4f05b9892ec5ed86c5125b402e0c7351
29c58ba796276fb71d824dcafbc8bd78d95f37a0
3183 F20110113_AACSRO caldwell_e_Page_190thm.jpg
2430f10a063564118401a0525cc29e7e
47f0f7495510cee9e58cfd90e020c2339bf77014
22446 F20110113_AACTOH caldwell_e_Page_245.jpg
e8c9700bc8ff29d98f65d8c1baa3b960
4559bbcd5817926dc0bab824ad4528ebcb0b193d
23238 F20110113_AACUYM caldwell_e_Page_039.QC.jpg
eddcc7e291f43a25716dcf5a55a018c0
add9ac6d81ee78720b5a51db25faf34f40e03282
37170 F20110113_AACSRP caldwell_e_Page_236.pro
63744af5e15ae5b7abef66c1084a264a
26e3a4e40a585ba18747efdccbeb1f618284a645
2330 F20110113_AACTOI caldwell_e_Page_206thm.jpg
3cb0d5d3908b0b8fbee7e7eb0d0fc838
844da7acb7c7768931d3ffcfab1ce02706d6ecf4
59569 F20110113_AACULB caldwell_e_Page_192.jpg
be54cbda8a189be56a618d2a7288f49e
b13c0e406f04125a5dd4d8bc9260ed51cb0f826e
6666 F20110113_AACUYN caldwell_e_Page_040thm.jpg
85d29a3714a0ed993aa07ad4bb552cee
47b78e88d30f7c1a98358f6139e5199d4f136c25
2744 F20110113_AACSRQ caldwell_e_Page_211.txt
03d0c7a8eb5ae5bd82f0a8eea8312712
63d99cf69e5780639cf8b91e8e49a421c0ad43d0
12012408 F20110113_AACTOJ caldwell_e.pdf
0435b2b8f1de652f36b75476a7a31dda
f46a0f9a33a9c387eb73559dba31759252bfebc0
61428 F20110113_AACULC caldwell_e_Page_194.jpg
3d28942246f0c4167a235918851f578a
8a625bc127fe30f7771a0dd0d76892db5b482024
F20110113_AACTOK caldwell_e_Page_250.tif
8064c2c9c8f3438336bb43605202abba
0e84925dd034f3419561655adbd440c8425f07b1
59638 F20110113_AACULD caldwell_e_Page_196.jpg
368caa1f62ee42eb6d64c07e67000957
3f20f88be17fdf775a212fda23e2c8c49c2ac707
25609 F20110113_AACUYO caldwell_e_Page_041.QC.jpg
52c4c3b2f35845f74c7bac13fab9e2fd
d472614f638101fe9e1e6d20c6cb7f787df2452f
131902 F20110113_AACSRR caldwell_e_Page_243.jp2
f26efe1100f3157fcc48b130d512c327
056384b4a5db7a255326fa5c213a000648c302d5
80499 F20110113_AACTOL caldwell_e_Page_136.jpg
de72a3c66ad7aa043a73e072f76211ef
06ad9a2bb19453e0bbd7512805dae5d409b453c0
66407 F20110113_AACULE caldwell_e_Page_201.jpg
a3e4b420f7fdd5d90ee2686f76656711
17275e8ad6e4a32c10a5c43b0f3cd2f46579e625
3283 F20110113_AACTBA caldwell_e_Page_013.txt
8ebee5f10b02da3acd335f49bdba794b
d33b25171ce9ef0ad2dfea21aa6fef884da8c067
18944 F20110113_AACUYP caldwell_e_Page_042.QC.jpg
20f5c924355dc6a7265c2ed707719fd8
1c206d8774e6dc1a25e7e136b3a5841a57160125
453204 F20110113_AACSRS caldwell_e_Page_069.jp2
68786704a326c43d15dcdb2ed91e560d
b41360ace837aa67eeaeecf7994970f4b0fbd3ad
5668 F20110113_AACTOM caldwell_e_Page_147thm.jpg
7e5eea36a50685bd9056cc74bbf6e7c0
68c774eae250902536be806d38d85165159498e9
37015 F20110113_AACULF caldwell_e_Page_203.jpg
efc0ca826ff501444da7a1b82cbd8a58
78f0452f76081da0b589fd9406596452bff96ef3
F20110113_AACTBB caldwell_e_Page_188.jp2
cb92c13b6134e20da8d1afeae4eeefa6
cfa27aeacb2a000d0482e82d32e1ebe9b245aa6d
6422 F20110113_AACUYQ caldwell_e_Page_044thm.jpg
797903b1d5b59c38b0540c6ed3adca50
767ac937d0d43287671bca7f61ca31c8fb8675c5
1960 F20110113_AACSRT caldwell_e_Page_165.pro
e68a68d3e56adcd3754a9fab078ca5e5
75d47024e5664276c4f215ebed5773c0f6518864
F20110113_AACTON caldwell_e_Page_055.tif
7e2f2083c8c83bd2b9c8e0e198cb9b57
ca60879a04e4e9bbef0f7305aa0f0e5a64de1011
62829 F20110113_AACULG caldwell_e_Page_208.jpg
73022c33f92e5d3d4a335e4b7ce4b866
7c3c425c88ac627ad9eb8db922901d1599ce3814
12937 F20110113_AACTBC caldwell_e_Page_234.QC.jpg
9917a3ae8956f1089787f0ad46de0ec3
0ad2505b14990c02c9a10268d5f43e4095956188
6089 F20110113_AACUYR caldwell_e_Page_045thm.jpg
3cbcf1ae5bf1ed41ca0eafe7e35ded02
28dee38c30d484736aa28985f39d10df12a5cd11
9343 F20110113_AACSRU caldwell_e_Page_018.QC.jpg
9a6e8e8f6d53315b94234b883154179a
56a3b12c378e7fe9db3f1f5b9c4cf55a7fea81f1
F20110113_AACTOO caldwell_e_Page_015.jp2
70949d2b1ea5c1723c45b22f9ed4b9a1
28f34cb36c1c82c7231ce0690a63a6b320cc96f0
32576 F20110113_AACULH caldwell_e_Page_216.jpg
377eb5d3c07e94ede9bff2703cffd5a6
0175a0519a1d3498581e7a2db0b4e16833288778
12478 F20110113_AACTBD caldwell_e_Page_233.QC.jpg
24f89c8ffb5a5d649c4ecf31a561a085
d1ed5861d6ba01ab06fb306f61deda06703d7677
21438 F20110113_AACUYS caldwell_e_Page_045.QC.jpg
ba635c23d2fe4c73beefab93647d4038
baafdd9c82a3167e020a6de3033a6d5061dd536b
F20110113_AACSRV caldwell_e_Page_182.tif
0119c25bf8768a5f0a78327de93ba79f
6a18c5eee2728c65b5f2ecbe0f05995080e1b159
67185 F20110113_AACTOP caldwell_e_Page_209.pro
e408eff54a2082865ba045180bb945bc
27fdc66ed5c3236f1b4c0bdc9d2bfef2e363c0a0
31425 F20110113_AACULI caldwell_e_Page_218.jpg
856f0572291d80ff95c445a5c424a304
146b3fcfbf981519de49069c8b356387539ab5a2
F20110113_AACTBE caldwell_e_Page_179.pro
b27600da6b1241bcae612b60bdbdbec6
d1086b0a9ce467f8e1147fd37ce093c59951e553
4199 F20110113_AACUYT caldwell_e_Page_048thm.jpg
fb217f7b812b58a7e0b8a67c8cf6bac5
6454ca15d409189a8793f886895fb54e945272ed
25605 F20110113_AACSRW caldwell_e_Page_044.QC.jpg
3566d430aa99bbe8dcba63abdab15d34
3fba8738e9baba8e2b700b1d5fe4f4292bcf3d1b
F20110113_AACTOQ caldwell_e_Page_246.tif
3a9348a77fbc43031a585110f660b7aa
4c09fc81772a256f2ede0ab4c22df5254e0fcf8a
17930 F20110113_AACULJ caldwell_e_Page_220.jpg
ba937c63f6c53e5acd3985710788579b
287a9f9e4e53a7dd80c51a032c3a78a02d15a329
6028 F20110113_AACTBF caldwell_e_Page_090thm.jpg
0b2b4fc5f5e9c572772f6cf03457dc0b
7884f1bd47f3226f9468f67f66d0633fe9faddbf
17393 F20110113_AACUYU caldwell_e_Page_048.QC.jpg
b662638e83bd55b302896ad817f47e01
c03a4d5ec26c7fd058bf9aaaddb9d546314e11c0
56648 F20110113_AACSRX caldwell_e_Page_211.jpg
4c722f19272acd39d8964f3f68ed7b3b
09f0a55c00c355b574bd5d1f2b1c5600a894d7f0
F20110113_AACTOR caldwell_e_Page_228.tif
6e6592c462076c4102f1c7b3c838edd0
e5a3055d95c1fb49662975b85fa597cf358138ac
20844 F20110113_AACULK caldwell_e_Page_228.jpg
35b03f5c451881372620fa271d312700
707a39d7f8caca89087d27c17daabf83124425c7
1054 F20110113_AACTBG caldwell_e_Page_028thm.jpg
c87be1bfbce307b87ec3e38f01f1d246
d6a09f5e3009c54d7dbb788c2ab5478e25865741
5327 F20110113_AACUYV caldwell_e_Page_049thm.jpg
b6d4fe52aefe33f13b0306af8c082dde
6aff85d10639918b89b2b160ec06b5eecb46c8bf
F20110113_AACSRY caldwell_e_Page_013.tif
2ea8f7ba8d3e08892d09ea76f278ca57
60f067dc9b83a942043dd9b504e3011463fae37f
1556 F20110113_AACTOS caldwell_e_Page_034.txt
a62f3f6388bf4221a5f213cccf1ec80f
67053e1328968fba2f833d90e13f8ba5d4e40217
54181 F20110113_AACULL caldwell_e_Page_231.jpg
23078864c6ce2ba8ebd612fb5863a70c
11154643af78bff5194de9ef2b8edb3e329618e0
39817 F20110113_AACTBH caldwell_e_Page_205.jpg
9f0b67463330d26cfdf7539f67adb88f
8500b3736e0f9e6a8cb855569ca9c9f13776023e
20730 F20110113_AACUYW caldwell_e_Page_050.QC.jpg
cc5122299216c446c947f61efc630862
63cfbb11688333b63cf725f6ce88d18e4c38a278
51997 F20110113_AACSRZ caldwell_e_Page_038.jp2
001a817fcd568f3fb494d18cc4d706ad
83fe35bf85feb83b53feb3595fbfc34bf63bbbce
F20110113_AACTOT caldwell_e_Page_028.jp2
f1528b994af526f4fa8aca1792ec8d41
9d5c169b2c31b3ce53670fde966fd709a56fe389
52978 F20110113_AACULM caldwell_e_Page_232.jpg
7e84a339aa521fb5a6df3d7ff1e7be21
5c6e5087459c3aa300b15109cde2401ac68a77dd
66923 F20110113_AACTBI caldwell_e_Page_208.pro
d4b31d1e9cfe0e871b0462298e689cb4
f206b73e66c5f26d1d0d42b1748a1ccb5439f034
F20110113_AACUYX caldwell_e_Page_051thm.jpg
86ae9bb7c86eec8b7dc7723eb58f41cf
139359c7a94243c0d98444be78cfd9aff2640fa7
F20110113_AACTOU caldwell_e_Page_205.tif
152e10e478f2e9f599e24437ee2630a6
91051300de6a39d383f37519d0c1901d64a65477
47892 F20110113_AACULN caldwell_e_Page_233.jpg
a459b247685374e68d6b8461791f338c
4adae07666b942c531943fb59a7621f85a400ff8
551845 F20110113_AACTBJ caldwell_e_Page_086.jp2
e8615832ba1faff6763ac2786bf0d004
d69138f5f50f81f355d6918c3583057d0ac12706
22493 F20110113_AACUYY caldwell_e_Page_052.QC.jpg
8c5f6735a8eae5b91b5fbca1bcbc4599
4aa214467bf6b2cc9b94d4ef1c3df14d6cf72a24
17854 F20110113_AACTOV caldwell_e_Page_170.QC.jpg
d50f9c42d79fb6c9a893f22c01ddf737
191c4d30acc3cbce16f9dc2b2ddae68c5486113f
29917 F20110113_AACULO caldwell_e_Page_236.jpg
135fdf9c58df1d102d6c098bcccfcbc4
d483348138a595aa4a4cb744f00753380970c8be
6338 F20110113_AACTBK caldwell_e_Page_043thm.jpg
33058ca28551d627343b60296d57bcd3
adb2e7d2dc3488edbcca7228a95bcdc629c915db
4594 F20110113_AACUYZ caldwell_e_Page_055thm.jpg
541f967427e30ab930af3bd77f009497
3993c1d1b7583dc26225a1876a72e4b78b00a14e
1853 F20110113_AACTOW caldwell_e_Page_153.txt
39e082a92adf6af1000f365f08493fb0
7d212a811fd1fef2897cb24256d5a4899c00c146
15191 F20110113_AACULP caldwell_e_Page_237.jpg
3097df57cc1b9b2e24825f71c2a565f5
49e4036d55342514bb89f83dc0f111fca49a83c3
1371 F20110113_AACTBL caldwell_e_Page_158.txt
4edc3f0c62b50f764c4fca03f9abd167
7461d40ec737cc89906d576346d981524305cb3d
F20110113_AACTOX caldwell_e_Page_234.tif
1f4282e8b3f9d1220928045324b200fd
d86c6d3451c01323708567708d646f56b0b57149
32598 F20110113_AACULQ caldwell_e_Page_238.jpg
48de311baab55364ab6846719d614a4e
0b8cd2c788b146d8c424e2bc54e5a59213cdc6d8
70174 F20110113_AACTBM caldwell_e_Page_101.jp2
33e35b97fb7a86e6e9d91d85f3d2b4c1
7359e444cd0f85fe2961377799e24c8cc4ad6cbd
1977 F20110113_AACTOY caldwell_e_Page_041.txt
acda22fc35ff3ed8dc4a52ddf6e6c904
f60f6ca1ac9d372622e885a0b3e6faab96de61bc
31912 F20110113_AACULR caldwell_e_Page_240.jpg
0726698e323eb17c75e33188888badbe
ac5367c4410a92c9bb300ba781674cb19eda7a8f
1046 F20110113_AACTBN caldwell_e_Page_018.txt
8c40bcfea7aa184309d7a859c707bb2b
0f98fc9fb462f2f2d351499832f658939d7e26be
F20110113_AACTOZ caldwell_e_Page_075.tif
69ae9011db5eeeb91a6defc24b316d28
7e762defbc1bda119c474a57883a764bd7604a61
95362 F20110113_AACULS caldwell_e_Page_247.jpg
fa4428f674b6e76efea0114db04cc866
64b9fce771162716e7afb30bf8b7a39a6b1f72ca
48426 F20110113_AACTBO caldwell_e_Page_078.jpg
8c296882d9cc6fecfd0955fb8df57ffa
87a0a4ba0674a778deaf17d88aefe104c4c634d8
104628 F20110113_AACULT caldwell_e_Page_248.jpg
7893d0d4889fac7b96b700786c15b034
2358269153939bf1f4c45c3558bad9130184f951
F20110113_AACTBP caldwell_e_Page_217.tif
521b867e32d68bb5adf37418c40570af
49c1d9a88519076590000e06f0b090a8be1707c6
27029 F20110113_AACULU caldwell_e_Page_001.jp2
b630a512142722ff7814e5dabd5da54c
42933568594d3351f3d754230c57cd1cfe9322ff
2780 F20110113_AACSXA caldwell_e_Page_230thm.jpg
80110757e91918513d8c0e1811e61a0d
62acc799c297e16246c4478cdfc3648d48dc68a6
82019 F20110113_AACTBQ caldwell_e_Page_025.jpg
b0ebfdbe7aaa7aa7b1a1051033729143
cfe1ceb29321b0d017c6d9472264c441dd1992b7
1051959 F20110113_AACULV caldwell_e_Page_006.jp2
d6445d2d76d36a211f4a1aab1d72e0e1
ef511936f3a35db5cdebe3de40ba9b99200edb62
65201 F20110113_AACSXB caldwell_e_Page_212.pro
b1e10ec70132a93bc34402bea762a71b
0842f466928c06576764926718a387871c11a487
48173 F20110113_AACTBR caldwell_e_Page_075.pro
7786dee2001bf59181896f64575f717e
23113f74dcf12b7af1aeb6ff4c2b2434625eb80f
1051965 F20110113_AACULW caldwell_e_Page_007.jp2
241f2f24b954fd206b6342344f183634
aa651bd8ebd3c9a7e309919a41bf4cab087eefa5
46645 F20110113_AACSXC caldwell_e_Page_120.pro
d7ae70a3dedd7e5143462f004ae66452
2d2ecf0bce5b0f26bec04acd939d786fc7f6b21f
898 F20110113_AACTBS caldwell_e_Page_081.txt
acb39089f5fb71ee149a322280d4ab76
2b4c304776908b4355553acd8e859fe75b51c793
1051981 F20110113_AACULX caldwell_e_Page_017.jp2
b5135feb05a67bf9cdc3ea7f46eedea0
570b37b80f54202d146798fb6d7dd724596828f0
4468 F20110113_AACSXD caldwell_e_Page_166thm.jpg
cc5b605d3de99a9ef84b6cca07a121c3
6a1d0d8e68a6537c545db86e7b367236669161a6
479589 F20110113_AACTBT caldwell_e_Page_115.jp2
f56d75f51957da143a54888306ff777f
21e9f0412fd8cbe85ebbedd3972d4784f13d85ae
1051911 F20110113_AACULY caldwell_e_Page_021.jp2
2914d3f81960a62bb8e106dd7e7454e7
27f17aee208903bf40aa887478d957a6d551ec77
6494 F20110113_AACSXE caldwell_e_Page_079thm.jpg
28614bbf979591647d6a5a986798a650
293478f17d3875e359ea53ffce3ad90ea1af4d66
17938 F20110113_AACTBU caldwell_e_Page_006.QC.jpg
658b9bc5248050af5d19c132fd1d532d
bbe1981d40bdebf96a09eacae412b1fc776511ec
F20110113_AACULZ caldwell_e_Page_023.jp2
c1199c49ccfd0c1da6c1a10379044b3e
a9b5499757e6b4c0a769036aa1d95ef4aacae85e
F20110113_AACSXF caldwell_e_Page_076.tif
31f8ee2e43710e5a4b839fe8d14aa612
d8b9e46db2f4727f8b40f06337ed32386cd97069
15488 F20110113_AACTBV caldwell_e_Page_197.QC.jpg
64a48a7b7c7fa0d1aaf1550e6987c00e
d7dd2015cc22812a10855932ee7f713b2462f887
23078 F20110113_AACSXG caldwell_e_Page_125.QC.jpg
aa976b8ad970fc0fd875520107bbbac9
24b8578d3e11efc2afb01b33aec19166fe682daa
F20110113_AACTBW caldwell_e_Page_239.tif
d80d66c8b732f419a3d81294a4267e10
4e943a3b4897f72e01a9d2da2c7190c65aa3959f
53510 F20110113_AACTUA caldwell_e_Page_130.pro
8041f0ee1a193ffa880484d21fefc130
dea77dc72d8e2a45b401d3a5642dc074695617ec
25731 F20110113_AACSXH caldwell_e_Page_107.QC.jpg
ea56dace71b5d010d31fddb6effc0e1f
6efc0104e1320e140c65f08d9c90b0c9e093ffe6
14792 F20110113_AACTBX caldwell_e_Page_086.QC.jpg
92f9b42e4ac01b78e2376a242d3365f2
e615540cfd9f98bc39313476d2d2b5ce414b2bf4
80832 F20110113_AACTUB caldwell_e_Page_041.jpg
a5a41b8f1ffa33f750befc6eb7aaab3a
80c98b90233e51c7650673de978517e8abb88066
33000 F20110113_AACSXI caldwell_e_Page_244.QC.jpg
732703b1540d804d926c83a2e0b8215a
626d0c3b925c8e4c96b6d297ea4558de2d64161c
13113 F20110113_AACTUC caldwell_e_Page_205.pro
8eace21d804f2b3386f791024ab56ebe
ce07488768ecac3190de6b138c01d54644d7a23f
6689 F20110113_AACSXJ caldwell_e_Page_130thm.jpg
2ed7595a06b1fc7e9a3d430dce54608e
844d7aa62a0bab367a34f59a236cc411a8e41ab0
43157 F20110113_AACTBY caldwell_e_Page_061.jpg
c58f7252d847b2e6f9934631fc9d2d31
1a7a3f5f90f91706aff2e6e80c3c5889e225e522
82176 F20110113_AACTUD caldwell_e_Page_075.jpg
d7f38c39455608dc2a8044bcb8e59d13
ba8e9744884d5916e8d02d9f4bb9b988f6d219e7
1051857 F20110113_AACSXK caldwell_e_Page_179.jp2
25f83261bbb242c612a2cd1cb737e9e4
5681bd923dddf8109a676b38a74a83e8fa606bc9
F20110113_AACTBZ caldwell_e_Page_114.tif
c9b9755514e9fb60767adf45938fb11e
7fdc21cef30de6411620704130372dd6cb7ac41c
4267 F20110113_AACTUE caldwell_e_Page_068thm.jpg
a1f894f4589aec6c99b5558e659fc4a6
03ae2dafe3484f255577469d2fae882f2c399f00
23762 F20110113_AACSXL caldwell_e_Page_118.QC.jpg
21f35bdd6a670383177985a00d3e172d
76fe034a3d2d03bc6937848c9aaf667af4993929
52210 F20110113_AACTUF caldwell_e_Page_234.jpg
cc9f60bf56e2402f5430da7155795dcf
2c50fb4f6abedc788589d597fda8ae35dcdb7328
6547 F20110113_AACSXM caldwell_e_Page_146thm.jpg
9243df430f5c675d76e573818afb4797
aea3bfb702c3fbfb4be4ade5df91da31cc8a2478
16394 F20110113_AACTUG caldwell_e_Page_081.pro
5674e7ba3cec25983fa6379ba33d2c9a
ad6b9f1e8bcbe015177c2a16a0b2fc81b53bced6
10312 F20110113_AACSXN caldwell_e_Page_240.QC.jpg
57773d713bf260a5fc84464d425afe03
d81a922a5244f41f0c864bf31dc70361f527e5f9
84426 F20110113_AACTUH caldwell_e_Page_145.jpg
92cc834c024c7782d8c1bca7b4ccc5d9
a121762e065dea36f3695df799a1e009fcd5bfac
F20110113_AACURA caldwell_e_Page_218.tif
582d7696ef3439e17f32ee04fe77859f
d842a0b3fb358864d344aa82b15c00c8dfdfb097
6362 F20110113_AACSXO caldwell_e_Page_058thm.jpg
8658970bb7c6c9d419a6d6e6db3c18c3
3816a6623df1796c78a25fc72e71e22810e25fff
F20110113_AACTUI caldwell_e_Page_063.tif
d07a756e2e7b03534bdaa41539e475a2
ebac316106a7adb3fff36bdf838cf9159bf110d7
F20110113_AACURB caldwell_e_Page_220.tif
0ad0a26592f72a2ac35087f117eb850c
be1078f450f995e230a625f37f344a665bb75c1d
7418 F20110113_AACTUJ caldwell_e_Page_013thm.jpg
32ff03debdb85ca18f30a92a8c6f1e1f
19eb22a69abeee7ec2c8e9e492a0b03b93ae2b7a
F20110113_AACURC caldwell_e_Page_224.tif
e14045b222d126a0039e6e44e6664e85
7f4f453b970cd235d9a0cccd6e04c17a141269cb
16706 F20110113_AACSXP caldwell_e_Page_172.QC.jpg
33bb3ab2633dac43b95f6b7092d37eeb
87ea39b36e24324114e9fc4cdb7d240c2bf120e2
F20110113_AACTUK caldwell_e_Page_032.tif
3b3afe99293cf710a91165b36a7b625a
ef41745bb1494bb7f1fc7e050e4251986d3adc34
F20110113_AACURD caldwell_e_Page_226.tif
5f571c89920e80c236e3398633080357
c0c3617b80f8b331a57ea133678fcfb2578b2b1b
66309 F20110113_AACSXQ caldwell_e_Page_213.pro
719e6b791ba652e70a435f7bd300d8f1
535124bb15767d0ee0e5f076154ed2b7661eec6b
F20110113_AACURE caldwell_e_Page_232.tif
b7e0e483dc74430ce07acb8e9b47f42b
8876c70778c41bb482d7ad1ccb15df2b822240b7
7540 F20110113_AACSXR caldwell_e_Page_001.QC.jpg
fc7f41ef7e966e21c4171024e839261c
9f658b3a75a2b6ac69a5c449bc2d25f751ec5edc
15183 F20110113_AACTUL caldwell_e_Page_109.pro
1d7c72e0d9785965e3ea31873663c63a
c33bc794e4fdba053ec78ad1c3ca347abbc63d49
F20110113_AACURF caldwell_e_Page_235.tif
403d0970cfbfbe4096b3bc00b022beb9
154c103c85251d9c1e466b20cba41bcc64d367b8
56540 F20110113_AACTHA caldwell_e_Page_168.jpg
e2bf4f225ea6d270aa8e9b90c76ece76
6c85d6133450d40f57f5016c2a049600104e70a4
45364 F20110113_AACSXS caldwell_e_Page_085.jpg
7f6bfc020cc175c1d89490ff3b033f1c
e8713457b3b9f1b484c4e92423db3d771c1ec1b2
3863 F20110113_AACTUM caldwell_e_Page_189.txt
3af65ef9d227897fa1c7bbaaf3668b4b
ca0c6195444cd53ee8edc6e46ff8c460b683d989
F20110113_AACURG caldwell_e_Page_236.tif
4fab294f56298b7858a29d30cfcae448
434934a3c9547086de1c26776778704669b6a507
44306 F20110113_AACTHB caldwell_e_Page_064.jpg
4052a078bd64ac4e350b28a2c8e5733e
ce26e0337667beaf57145a5e91a79004a8629113
F20110113_AACSXT caldwell_e_Page_004.tif
2c152e404c50d227dfdd8de3b68b5580
d17d50bdacdce8eebefe3f91f50aaf2e52da2794
29272 F20110113_AACTUN caldwell_e_Page_089.pro
0977e7f9a909a136ce85b0e22a256a84
db565ddf1437d1d6f1507f4a65eab293447aaa72
6459 F20110113_AACTHC caldwell_e_Page_180.pro
329f3b84210bf6b81f4bb568096524b8
980afb13827d90fe3b76f4b2bf17da94f0544166
44884 F20110113_AACSXU caldwell_e_Page_067.pro
ea74c0dc660dcf7b518392f311b9f5d4
b9b3481557c2f54ee6304f52382a05473652a3c6
552176 F20110113_AACTUO caldwell_e_Page_102.jp2
8486a4481ae33be7708b5d31b9fbd7d7
30a866bcc603d64f6910c76c38579d6c0519d3da
F20110113_AACURH caldwell_e_Page_242.tif
72d319d92df856eb072b7ac5c18ee8f3
8a9087d2c3d351ff02bace55a30b93ccd0d6d81c
6438 F20110113_AACTHD caldwell_e_Page_128thm.jpg
cb00958dbcedefa5d82b26039600d541
4ef1c740ea9b25dd42e7534d7c5dba1cf83f86a6
463 F20110113_AACSXV caldwell_e_Page_149.txt
179b73d0a6466c896285a7dd8eea1bed
9d40623d8bb51e7354b1c2338b71b4f019effc65
171801 F20110113_AACTUP caldwell_e_Page_220.jp2
0492df658d2f6a18221bc367aa65159b
9ea07a118a943acf815ef63e356befc9d667c355
F20110113_AACURI caldwell_e_Page_245.tif
cea0e7a6788fd6db42c1cb0a2966fac3
54dfa7f442ed1dc2e38a3f13ddcc1303429cc21b
F20110113_AACTHE caldwell_e_Page_151.tif
c7a26593dd84c3ea14b62e6a492000ac
6052cec04a4b66e40ca3d2ce30b084bc88edd3ad
F20110113_AACSXW caldwell_e_Page_012.tif
6a559f545f3b7b2b7d018970ea0874e3
12de99f68acf705947aa07fc5a1298d7c7eb57cb
6152 F20110113_AACTUQ caldwell_e_Page_132thm.jpg
5ec1faf40e9e13a57a89d55d100982a0
4ad6c84859a272a4a689da9027da01eb0be60277
F20110113_AACURJ caldwell_e_Page_248.tif
2544c6aabc168af7e321e57536cd5fa1
617ef29a53e7ae6de26f496dada12a695fa1f817
F20110113_AACTHF caldwell_e_Page_064.tif
9aa339d6d23012a94d6854c8e6497748
9423bc433abffe7c2028217f7ab450dc881f3a7c
F20110113_AACSXX caldwell_e_Page_195.jp2
e24311cc19ca83e9f426b44b78c69a8f
3b7322ec38f69e7404e21283de79edb84bb1b688
864 F20110113_AACTUR caldwell_e_Page_113.txt
bdbc2b4bece257ea33aee72914ff9b3c
3d207408fe7280300ca6837c46d04e53ceae09da
71383 F20110113_AACURK caldwell_e_Page_006.pro
746008176c268cc1a849bffb73ee9fdd
682ebfe32549c07311eee5dd6a72c512a6b53274
F20110113_AACTHG caldwell_e_Page_028.tif
60de95ccb0a9a4a2577dd0c67f391d5b
cbf7b576ee29c5bf1192bb7457c20f0d6081d924
1990 F20110113_AACSXY caldwell_e_Page_053.txt
73ae41b0428b421fcbd508859eb2b5ea
6cfb9262c1c6ff5a1762c51dbee45f4727da97a6
466232 F20110113_AACTUS caldwell_e_Page_227.jp2
72e942fbc39d8f74bfd56d7c675ffed1
b402eed4968d1e83d60fff7dcda6d0b8c95571a7
107532 F20110113_AACURL caldwell_e_Page_007.pro
d3a40805c09a64d1fe573573be173d02
73e266aec43ef3afc1221d91219e9c103a14b440
12918 F20110113_AACTHH caldwell_e_Page_038.QC.jpg
a0b17b542fb6df21a90bcd594655382c
563a24062addc332de5eceb76318cdebb2b0f6f7
3274 F20110113_AACSXZ caldwell_e_Page_240thm.jpg
3dc7b1842d5a6ed1a1c9453104593079
042aec2a344b49de04badcbaf26973886228b1c3
3220 F20110113_AACUEA caldwell_e_Page_243.txt
6634d0eb608c59fff8cb539b363453eb
d3f98efaa70bc53e48edf94e8cff87c43c2572d7
36842 F20110113_AACURM caldwell_e_Page_010.pro
a8f9ae80d00e20ebe88538fe3e442b4f
139087f2b4165906759524ecf36430918850b8f2
F20110113_AACTHI caldwell_e_Page_080thm.jpg
abde4057d7468211b10a5f9f5abb2558
3557ee9aa47d86e8586dea6a8d33e25156231e3d
1051982 F20110113_AACUEB caldwell_e_Page_210.jp2
f100ee88be8376e466206448f9ec2cfe
ec0c7d374e434b0789e3881a54a8fa160bddd539
43490 F20110113_AACTUT caldwell_e_Page_114.jpg
afe92dc67024b05512fc8fa25391a172
ac2999e56225df2cfa2602300423ee3fe09944d3
64687 F20110113_AACURN caldwell_e_Page_011.pro
d819acd0cace10e83033633ac3a48776
200b2855405bde60bccbfa8e7d3aa8af981091ef
1735 F20110113_AACTHJ caldwell_e_Page_029.txt
cbb122cf744e15520e5daa0fcd2144cc
020671a711a0e86c3f6bb3df29e105ef73d64585
5672 F20110113_AACUEC caldwell_e_Page_031thm.jpg
dfe156cb10bccb942a6d54d173dffddf
30531cb08e3a608014287e3c8f89af4463256c42
104039 F20110113_AACTUU caldwell_e_Page_155.jp2
b211c00230610b6e4eed9b107a42bab9
262f46b0e73a03d646acb833d308ea2e26aee2af
80619 F20110113_AACURO caldwell_e_Page_012.pro
427066ff0f9091a3a45e1070064095d4
46d423a86f6bbe57e891d47632843729a2ff3176
1883 F20110113_AACTHK caldwell_e_Page_035.txt
cd2aed210f91a983ab0e58e6590f41f0
1e65ccb0229fcdb4dd995c41bd0321e9602a1300
F20110113_AACUED caldwell_e_Page_090.tif
11739563df1792809c43bcf56262ca51
4684980cc2663342dd8a0a1b92b3f74a5fc9b917
13803 F20110113_AACTUV caldwell_e_Page_008.QC.jpg
84554be6e40e6d596609c3a5b9317f27
435201f3f692ee1a24a1b66c98a9762c042d47dd
82562 F20110113_AACURP caldwell_e_Page_013.pro
e30d1ee6fabe13e96452746839b98e5e
73ffedc15fb3bbcfaa7e6fb01271667627ab6959
47967 F20110113_AACTHL caldwell_e_Page_111.pro
839809fc2c5d847e7286ce85e7cd9b10
819175c1217e54e38e7abf530c3bd34ac371fb09
66658 F20110113_AACUEE caldwell_e_Page_197.jpg
a911ff91744ed288f27af4a075990174
18641f13ac135b1d0eb266a8e1d9107551770ab9
4070 F20110113_AACTUW caldwell_e_Page_204thm.jpg
79f82cc5a70dccaf8e81c8bccfc49e0b
c72241d180aa36b354553af61924b151845d4636
72269 F20110113_AACURQ caldwell_e_Page_016.pro
ccf451da5225f369e3585aceb40df277
f9377d4d549c6d988218097609713907675aacd8
67016 F20110113_AACTHM caldwell_e_Page_049.jpg
d7e3d1e75ba3301b2d6022f686820fd6
ab586ee6f4c54d01f4985b2c90ab7eb51fa901b5
2202 F20110113_AACUEF caldwell_e_Page_004.pro
9e4246447b6de789df7e3972c2c6ca00
bd2dbb80a6712ee2e59b6afdfb938ac1e685cd6f
F20110113_AACTUX caldwell_e_Page_240.tif
022298630d22059e0b0952bd62571785
cb5cf567cf3534af5e7e2e49d8da7f73a655ac35
26575 F20110113_AACURR caldwell_e_Page_018.pro
17ef14e2a4b1706dc57cfb444ea801bf
d14cacac49e2a11c0056091965f721b85aceef14
F20110113_AACTHN caldwell_e_Page_213.tif
029d5632e9341012ee859736282222c7
f08c40e746d2614683d6c32fb928bf98baebcf1c
21542 F20110113_AACUEG caldwell_e_Page_112.QC.jpg
2a6abb523e9ab6b684f706e11b4d1540
78e3b8afcff912ef36261d744332a4fd47bf2fc8
1051939 F20110113_AACTUY caldwell_e_Page_201.jp2
752e3565b128545312713cb48a124a81
76edccc2eb64c929180028cc0b15cb57088dc7b9
26666 F20110113_AACVBA caldwell_e_Page_138.QC.jpg
6e883ea747013173864039703965c312
f60cc2316171aab5a92550742a0e7b058deb99c4
20887 F20110113_AACURS caldwell_e_Page_020.pro
5834a97855430f12562e1d2967bc5311
b76b4a3c78a5f1519c0dd32ca30f207df8df7fa8
474 F20110113_AACTHO caldwell_e_Page_228.txt
4063c74f30112fe5c76d6b37504c9972
6232d7ddd6086b2cbbde8ce7b27a7403aefab9f3
4709 F20110113_AACUEH caldwell_e_Page_180.QC.jpg
1d4d422b725ac812d6fd0932f7e65764
cdf584844fe313439e356a07dc5f4700221bf844
F20110113_AACTUZ caldwell_e_Page_144.tif
dc2f2a19c89e3311fecf3066c3973aa4
a44ce8351a693401f4f418e202456c9777080d69
6332 F20110113_AACVBB caldwell_e_Page_140thm.jpg
41e5a0d0693e1181ab04dee2bc6e1724
2405ad674268b6c57149f007b440f11d9c506f69
61080 F20110113_AACURT caldwell_e_Page_023.pro
435c3d18e3b620860fc13d1d3b8fe372
5da59b0295dd5a09f9aa1faa5d4e64911c803bd6
15720 F20110113_AACTHP caldwell_e_Page_114.pro
b3cc7c69006f2a68b33b33a715098784
8a045312d558a91c05a7574ee7926ca9afb301ba
1266 F20110113_AACUEI caldwell_e_Page_150.txt
5df05f2573d79b36916c68148760fc88
00d65255e4bff5633a52cb2aa2be9927806e7f7b
6022 F20110113_AACVBC caldwell_e_Page_143thm.jpg
9cc6646b8b9f0a8ecf59bd05f8d0f280
e075db5defa856c26ee4eb872b643507f3b9c2e0
39339 F20110113_AACURU caldwell_e_Page_026.pro
62e1aff002bb70a380f0cd7eb50ade12
3085853f19d550b5e4e5e90be0808de6ab4dda6a
2822 F20110113_AACTHQ caldwell_e_Page_023.txt
03eb357d434804f420ae5ecca34efc9a
eac4a0e68ebd83106f6bbdf428a249bfb5ad9891
2962 F20110113_AACUEJ caldwell_e_Page_042.txt
258e1c695d100f80a5e4c3cc6bdf13f3
b9ec988bdd40dfa239d430f725a5d20b353ae917
25351 F20110113_AACVBD caldwell_e_Page_145.QC.jpg
75aaa3bf6895284846789cbe85d8de8d
45ba5edd5630e43699fe8cdcd27a5192fe3e749b
41529 F20110113_AACURV caldwell_e_Page_029.pro
664bbfdf09d98c9ab281511790f57c92
68e04416df49907bf18d4e2c3c2d1cbaebff4c13
122291 F20110113_AACTHR caldwell_e_Page_007.jpg
2d8229bd0a6bc29cc47f7a6b2e5a846c
60ae04fabe32ea1c562d403f04ffbabd7ccb83a7
F20110113_AACUEK caldwell_e_Page_013.jp2
66c509440967660579cd9baa581d1a25
9599e88eee3b313b6427966b608860b711126b18
26557 F20110113_AACVBE caldwell_e_Page_146.QC.jpg
94cd93afd3160874652c431abeaadc48
13b5d869771bfbdb6fe7f4007adc3419dbc5cb1d
29923 F20110113_AACURW caldwell_e_Page_030.pro
1b75f5474f709660596f8a1dd5afb0dc
d7b2da9bbd444b199768bb649f5ac0811b700ee0
42696 F20110113_AACTHS caldwell_e_Page_106.jpg
458387a6f0739217aff7e8564180d50d
1ff9dcff6ad4c7b2e3d32254bba6a118cb3feca0
F20110113_AACUEL caldwell_e_Page_216.tif
3f8e1635ff4528675f7bee6298b5a00a
56f4c6dd3ecf8e7d08d2c2012fbfdb7cc2de8392
24809 F20110113_AACVBF caldwell_e_Page_148.QC.jpg
d9860d366205e146017c5febe7b45d9e
0181792c4516be3d1886749dcfc8f064b8dfd51e
27414 F20110113_AACURX caldwell_e_Page_031.pro
4e84ddf052bf41f4cf826203c50658cb
5cc2dca749dc2a2225f88c6e0940ddeddbb875d5
6542 F20110113_AACTHT caldwell_e_Page_138thm.jpg
613f8077f10ec101008bc847734697bf
463eb7c53a896219f1fd62e7ea4ffce9770ebc09
103858 F20110113_AACUEM caldwell_e_Page_140.jp2
9911b152f0b60c4191a8cd697aab3418
fe0bbc895a0889c201b77c09532e03df5c6d97e0
1670 F20110113_AACVBG caldwell_e_Page_149thm.jpg
d816ca3abd66d0c46dbb028b85cc75d6
bcba0b178f906300d49acfdc041759ee47b92ba7
52665 F20110113_AACURY caldwell_e_Page_040.pro
c88696e41ad6c6ea747dbe561f0e89a7
91b8379fb41d6a033266368c0dcb41db8bdfdf75
47976 F20110113_AACTHU caldwell_e_Page_063.pro
e33b79011fcde5ab87a94bf23bedc1c7
e597c24a4cd68756a571781a3a70ba830999d4da
82570 F20110113_AACUEN caldwell_e_Page_066.jpg
b7de4d2f8d346aad1b4bc5ad23b8e35d
15c6021d708e74153c491a84b2d74527db7ad3a1
11441 F20110113_AACVBH caldwell_e_Page_150.QC.jpg
7a05201b883dc637f2d7ca4ed677b946
7ea1e407d32dfc6df95451d22bff613b356d7c65
55404 F20110113_AACURZ caldwell_e_Page_042.pro
a1202becdc338f7bd470364b781fee39
287e4c359d755212d4233b2bf362535fcdfb22f4
106393 F20110113_AACTHV caldwell_e_Page_053.jp2
a9b12663da68e886c68a66bb7e2c542c
0ad51c5db6adc182877d0d78064d4bc309ab57d4
F20110113_AACUEO caldwell_e_Page_038.tif
1ccca2ad019bafc857eff1318a06edf0
c6d96f161c37d8eca7f947cd8f34ba65a09ac9c4
14056 F20110113_AACVBI caldwell_e_Page_151.QC.jpg
d03c59839499d907425a98d6ac9af90b
3f70469e7adf9c9a720f1fd8903011facce14278
1305 F20110113_AACTHW caldwell_e_Page_095.txt
fcc3d44548e659b0d5ac78c48f2ac1a7
1d6bc1da1497ad61605a558e7935e99e0b3c35fc
15173 F20110113_AACUEP caldwell_e_Page_215.jpg
b5ea05bc55f78bf3df67a894c5f672fc
97afd23367267d7f770acff6da904d118eb32fed
22319 F20110113_AACVBJ caldwell_e_Page_155.QC.jpg
ef03b5879ec689fc3eb175c6704c3c61
c1555d4084e224773ab75051675aa01188bf99c9
25779 F20110113_AACTHX caldwell_e_Page_054.pro
4cbf4db48397992d53f7dad96372dd19
097a2cae791fad23255d01dd717ad0f6210cc97c
18471 F20110113_AACUEQ caldwell_e_Page_167.QC.jpg
9aee908f5f8ccdaedc1b171ead86dcc9
93e1d1bd23f9c6ab5abe56ebda17fd056a387795
22698 F20110113_AACVBK caldwell_e_Page_156.QC.jpg
006180e188881539ab7df9999a9747a5
a9d5f65b7ff132f8027cc794a8ff75bbdc16e10a
3135 F20110113_AACTHY caldwell_e_Page_194thm.jpg
c68ef62b7df0005fd8316f5e2cd1a6b0
0e8229adec25888ca03b54b021f18424ea0f5015
51363 F20110113_AACUER caldwell_e_Page_032.pro
9326545376d05264a3a1ad659f505598
adb8088b66b152c2565d3a65b547b6cf2eebf0da
3978 F20110113_AACVBL caldwell_e_Page_158thm.jpg
17cb40c962c9eeecd93539e34a50e37f
8db6467406f6968b03d9c295ca21dc2f567ee587
14079 F20110113_AACTHZ caldwell_e_Page_212.QC.jpg
360b768c80e7f5ec06720bd9b13e7415
2da6f539262592c71770e65305d8f44ed9610d81
78855 F20110113_AACUES caldwell_e_Page_131.jpg
ebe1c8d6bfeaa641052bc40c100c6ed4
c1fa4273bb64c36a7d238f1745c2dacda064e8db
14701 F20110113_AACVBM caldwell_e_Page_158.QC.jpg
43bc97874afca9d4891801f059bb1cd1
206c6fca942d4ec85377b06e38ac479c1b44ba65
52141 F20110113_AACUET caldwell_e_Page_230.jpg
de9c27f8337ea46cff3648d380541788
ff45d2b55874357b23fba6f957fe7e342a290d48
5329 F20110113_AACVBN caldwell_e_Page_161.QC.jpg
69ad0087af8c537a301aef4f57eaf9cc
e411ebbb60e6bb72d49507c39cd90c6321118292
5440 F20110113_AACSQA caldwell_e_Page_153thm.jpg
0f5fdfe9b869f2a423872ba6cb0d4ca3
5474fcc7f800d3a2701cf8be1952a23566cd854b
5973 F20110113_AACUEU caldwell_e_Page_129thm.jpg
4dbbe57bb5033c0bf7cc573656e20200
bd61cdc09a1319dd8ee77ca5089822be2d6307e8
20595 F20110113_AACVBO caldwell_e_Page_162.QC.jpg
125de7e65264abd475cb5ce09669c4ee
63ba1a093e4c85484240fe4857f2afea9eec8470
7319 F20110113_AACSQB caldwell_e_Page_030thm.jpg
6b7934bf83430a3cb3f73aa8ea457486
cb19798b3b850e3c3140472442cb671f4219b099
40673 F20110113_AACUEV caldwell_e_Page_038.jpg
189d8ed3e97ebddd7805a3ee841b25ca
9bd072302079d1ed1518032a1bb599088d5f26d4
20928 F20110113_AACVBP caldwell_e_Page_163.QC.jpg
cba58c82ba115fec4d0b800c3008cd9d
7f9e2ba48048e1dbd2a492490b4f8c95319f9027
F20110113_AACSQC caldwell_e_Page_139.tif
b8d65729abf9200915f4d5d66ece21a5
42acf6394124decf1243b52b4befb41fbfccd8b0
619 F20110113_AACUEW caldwell_e_Page_078.txt
8b7b19e1823e18106258a098a2354b90
e1c038fe307540670b628c6630c22eadfda5ed0c
5764 F20110113_AACVBQ caldwell_e_Page_164thm.jpg
7a3980b558978cec9eb402486fffede5
f19280ae5e6e58108c7a1f1c11feb863e4606911
305 F20110113_AACUXA caldwell_e_Page_202.txt
19142c6bc358d140ec02cc145a02f4b6
f9a1f53d6c3c8d2d99ccb39eadc16989004a942c
68454 F20110113_AACSQD caldwell_e_Page_234.pro
47dc6dfcb7b91454b68559425eaea758
27e70b6403d4271dc141f0163b6020e3d06525ce
38783 F20110113_AACUEX caldwell_e_Page_227.jpg
5c20b5c8170c19e13bee2299d09e9064
590ea6a5e0bdd1969bad42d3cbfe15405e6dc3ee
19990 F20110113_AACVBR caldwell_e_Page_164.QC.jpg
812f4cc7dcbe5fef4ebe1cad32e72ec2
ca86379539564365e4373e6163ed3c9c1d4392bf
970 F20110113_AACUXB caldwell_e_Page_205.txt
72e8ac713b06786de8740a1ff6b9400e
c36960a775bd2ab2ad79d93c5b5fc4106bcccd2b
5771 F20110113_AACSQE caldwell_e_Page_242.QC.jpg
47be85c9c04e794f73883fe80b2769f1
a8db3f5cc952e12a44ff102cad184b788a543d4d
80700 F20110113_AACUEY caldwell_e_Page_107.jpg
4d4c2d599f6edb9493687e6aeb5bf9e3
169d1ea57f79ada166a51e8b8a4f74f964976baf
5492 F20110113_AACVBS caldwell_e_Page_165thm.jpg
61ded20cc3ad4ae1b947f0ade98e734d
a112c102d492741e7b905d3af0feb467862a3131
3010 F20110113_AACUXC caldwell_e_Page_213.txt
65c70300cc6a5ef8356a2954a4c97123
249b6db135058b29fb259612f16c2f768932c42a
105933 F20110113_AACSQF caldwell_e_Page_122.jp2
2a66900ea39080ac5500641f922feb54
df52bec49d3f6962b47c4bab1d41d37139388dfd
13986 F20110113_AACUEZ caldwell_e_Page_193.QC.jpg
e783496455ea4975843842dd6a8bd02f
69880004ed62b68f09d93a6d9928b5248557a0eb
5264 F20110113_AACVBT caldwell_e_Page_167thm.jpg
d3957966377afc26b4e851fc522dbdb3
f7731ea08f4b35aef291124c29c4bc44dc3c38fa
1336 F20110113_AACUXD caldwell_e_Page_218.txt
14dd35f2d5ed2fc2b8aa0fa849cf7ff8
5c37130089c9b34de79c021b21a2f2c594ae679e
15918 F20110113_AACSQG caldwell_e_Page_200.QC.jpg
b15246cab62777c0b3c3d124269d1f71
91627a742bee032452e3476d7ff9b51c62302573
16764 F20110113_AACVBU caldwell_e_Page_169.QC.jpg
add7e45d9cd1a009055068f45c920335
46106822c06f93a34e86e605190598d9467bb36f
1355 F20110113_AACUXE caldwell_e_Page_219.txt
202193198145d5b92c3e6232ca1bb07e
2836e4a1b1bec02dee6069f6cce9b081e27355be
38865 F20110113_AACSQH caldwell_e_Page_115.jpg
25a3541e251ecb0e09326029a3afd325
30049328d9d210931b5de14b5bc53ea83293d513
20143 F20110113_AACTNA caldwell_e_Page_151.pro
5a552690f17ca759e229d5ab8f82480c
1c8c70c8d8d09a4b25a29647160f5eaf3d0e6cfd
4430 F20110113_AACVBV caldwell_e_Page_170thm.jpg
ba6f76f5c29184862710edc300380087
3f08e82829cfccce401c9c6ff9e4ab622ef9330c
561 F20110113_AACUXF caldwell_e_Page_220.txt
613851d3fa3c345d139292d244e2eb0a
e39453298e83d6c7ae8dc8b7a727d94db3a673e4
F20110113_AACTNB caldwell_e_Page_041.tif
55b9c80e7c5f205ed6bc57a09e39dbcc
cfed96b401d1821799f47fbd3016a53e6f3e19ac
314 F20110113_AACUXG caldwell_e_Page_224.txt
6dd1f366c25893c29913c48040a288ac
454dfac07e45f527c17e2948c2b41105048adf2a
21206 F20110113_AACSQI caldwell_e_Page_064.pro
8066137e1d3ff6963b8dc1a9ebb79798
1ab091956e1b39d13c4dac5d7140f9f1516f8be6
33177 F20110113_AACTNC caldwell_e_Page_243.QC.jpg
ffaa1315a24744de7a51e3006a7111e7
487233e4139b8e3ccf161265e2527cf556013b36
5059 F20110113_AACVBW caldwell_e_Page_176thm.jpg
17e43364f38eda827ce7a4f307f22ac2
4f52a54379628578416074006a0ad1b324bdf25b
840 F20110113_AACUXH caldwell_e_Page_226.txt
3f041dec6f12e1ea6bdb2bb1ea5e61e7
8423bb5073485f58219ecea4e32dd7884c1650e6
24480 F20110113_AACSQJ caldwell_e_Page_046.QC.jpg
25232a47d5e8470069c64bdccbd2f056
e47983da8264a1637cc916e738115893c5240df1
2495 F20110113_AACTND caldwell_e_Page_248.txt
d6012cab7d0fe693abaa72f31f87515a
f10728f4b8268db0d89c176c417dfd9bbae657bb
14381 F20110113_AACVBX caldwell_e_Page_184.QC.jpg
1f857525c6e9ed7a56670f93dbdc0d1f
1e28c031db70388e713e8d6e73e92a8f5de62086
F20110113_AACUXI caldwell_e_Page_230.txt
4e4a1a1c0e57ecbf815852812afc30a4
abd37b5cdbf5a132dfe097f845213fcea036686d
F20110113_AACSQK caldwell_e_Page_148.tif
684de292e0e4d77214643f19d2dcfa08
762885901a6b99cb7cec5c310a9458e1935a0ddc
3036 F20110113_AACVBY caldwell_e_Page_189thm.jpg
1b951f4c9bc1d7736e03a12432711c4d
c8c309fdfeceb81cf720cda6a0fbd008e81c8ad1
4111 F20110113_AACUXJ caldwell_e_Page_234.txt
a5aa6fcadcb693c6e9c00a25983778d8
92aeffea1765bd0d8d2bd6d12273863ca4fe4358
15642 F20110113_AACSQL caldwell_e_Page_157.QC.jpg
f82990937992e8d9a658e475da0e96a8
5683b77d3e043ea3bfeb02a16605d05701288b57
F20110113_AACTNE caldwell_e_Page_197thm.jpg
f6c03a249fe1acacf09b91d17f3c0e20
0269e49e52b0b35765d7de502ffc93a4e656a41f
15458 F20110113_AACVBZ caldwell_e_Page_190.QC.jpg
8694af03eb90e0c03f9abcfbc78e9a70
1fea56cda57282223395b699d664a854b5fcd276
4105 F20110113_AACUXK caldwell_e_Page_235.txt
c10828f845ff6d714062a6ad4661683f
c1bf41cd4b39efa2bc811926ec8ec89aac0a61ef
44262 F20110113_AACSQM caldwell_e_Page_152.jpg
4c7a2d17dcfa606c60fdbfe929d37ce6
18a3ce48af1d61f92e164692bd136822837f448c
5692 F20110113_AACTNF caldwell_e_Page_017thm.jpg
f6cd27a3f9272d1a86d996296f89bb13
915688c3c8556b70f0c7fa93e8753af7322209bf
1186 F20110113_AACUXL caldwell_e_Page_240.txt
4434d7309ac6049896dc9b0b4429eef9
090051c77a41e9928b7c18c2c636fc8eadcc6ac7
13900 F20110113_AACSQN caldwell_e_Page_196.QC.jpg
7ff11b4691310d7b42f9ed89684d1dcc
8380beeb9358ea0d87da20328c6d9c621c3b4f1c
24603 F20110113_AACTNG caldwell_e_Page_084.QC.jpg
16fdc14726cd4f6f8de708452ee59141
fe647290fa017af5d252b77d7b4e97937bb955d7
1174 F20110113_AACUXM caldwell_e_Page_241.txt
5fb345f29c27d17f8dccbb39a0e738e8
5b0a91770abfc1e3a5d62dac1d6dad5ebbd20066
25312 F20110113_AACSQO caldwell_e_Page_024.QC.jpg
944ef3dd95c5ce6bf8ccb04955717bd7
7ff17b9a54f5621b7ba9043f3c5858812c11816f
F20110113_AACTNH caldwell_e_Page_125.tif
0006f5d634a23a5d02e85d8a1cec04ad
772de101126e1aabaeaec89026d58c4814c288ec
65227 F20110113_AACUKA caldwell_e_Page_099.jpg
771dd0fb4955464a6176cd878fbd1bb1
4fc5a7a2acac4ffab2f7f82596a27433866c1ea1
F20110113_AACSQP caldwell_e_Page_178.jp2
f53ec59b7940ad366e972b2c972a0ec8
6697092250aa94fe9e69e91625bb650a220b7a3d
F20110113_AACTNI caldwell_e_Page_211.jp2
ea67fec2d88e61568a8ebe1dc301e07d
cb88557eae9e93eb16234981afd723c367937da7
54462 F20110113_AACUKB caldwell_e_Page_101.jpg
779a1e37f1729f9c2c5f387da5f32d8d
0fe19ff60e0c68ecccbcaa6766fc40a3396c5ba6
490 F20110113_AACUXN caldwell_e_Page_245.txt
1ff29f074674fff12b338d76cf1bfdf8
166e5d4f44a62b9aedba603939ca40e2da9c42d3
51798 F20110113_AACSQQ caldwell_e_Page_154.pro
6072c5428c4cac35155f37c82fb38820
9d44e15b7766e5c41a6e912eab64e11bb3c82ef4
104419 F20110113_AACTNJ caldwell_e_Page_103.jp2
c8cdfb1f476c42fdaadd2984dc5c2be1
550d9a1a21495f2f03e38edae22a7912c1314f13
41633 F20110113_AACUKC caldwell_e_Page_104.jpg
b75bb022a6128bf9c207f3f71d5138da
a5be5bd78b0c861103edd24cd51fa6f365518a4e
491 F20110113_AACUXO caldwell_e_Page_249.txt
f189858797d9fbf2e5e4a37065f9876d
2c2376dffd1d87901bb58455f0fedd643f769885
85052 F20110113_AACSQR caldwell_e_Page_119.jpg
212af3807b3a237d7c23bf7b5b631672
4fe9b9d4873a167362c8f20f34ed65840ccbcb28
1051956 F20110113_AACTNK caldwell_e_Page_163.jp2
ba37e20a8f1120912a419989cb878eef
01d2bf541a29f2b230e99c99ab1b829ea1e8560c
79183 F20110113_AACUKD caldwell_e_Page_105.jpg
e6eca58d5822889b0080ad86a843543e
fe061de569610eaa0505505aaa41f7a697c07be3
546 F20110113_AACUXP caldwell_e_Page_002thm.jpg
94e5062524ecd80be5154a319cef7ffe
6b4a1af41353b3584e7b860df4dfb23a4a5acabf
F20110113_AACSQS caldwell_e_Page_118.tif
e9153da04c1cedd0762dadd76fc5e9f2
f663f4d538eba7556d5aeeda7ab5874cc763a1d5
41509 F20110113_AACTNL caldwell_e_Page_092.pro
9cb095e3888bd2030b7a48cf534b54b0
56b0dec3872407f15c876e48f3ef53aaf34c4713
60448 F20110113_AACUKE caldwell_e_Page_110.jpg
734f0b1538976e05d00c592cec4d99f4
f1d813415ee7003cf6474737b566a888200ff0d8
11020 F20110113_AACTAA caldwell_e_Page_003.jpg
94d8a51bfd4315c0fec6ed6d53f1660c
b09ef176ec92b22f3022688ef77482f8214088ad
1575 F20110113_AACUXQ caldwell_e_Page_002.QC.jpg
d698fceb93250404c1630acf8a4445fd
90317498738cbac93c018072b0e3655af9682ee5
F20110113_AACSQT caldwell_e_Page_005.tif
a1b41cca4245e3b20e80a79429ed9a9f
be7e340579ba2fb46e1c0688bff3a3e5e93540e3
107708 F20110113_AACTNM caldwell_e_Page_043.jp2
336d3fe4c68d6bf4a2d9a9cc43cb33a1
ffdeae6c9c6084ddc9802d360e1b6bbf5dc975b1
67346 F20110113_AACUKF caldwell_e_Page_112.jpg
1cbe26e2ee93f4594976770d37c984f7
6274c06a92a5134c0652da17514acef9de0fbae2
855 F20110113_AACTAB caldwell_e_Page_227.txt
2a64cc3760f472f15eaa5699c8bf2d9c
d3c3b1b021b980bd6a5911203d2579a0cc2fdf74
2988 F20110113_AACUXR caldwell_e_Page_003.QC.jpg
e096bb047ca6e60e455ae67523f3ad17
81b877abbeee6ac164331a887f2bf04e01ed41b7
F20110113_AACSQU caldwell_e_Page_159.tif
36347f22132cc3d0f4d11763cd49ec0f
f3c7b763b5b1ea2c7b676f72496ca20854b82381
76765 F20110113_AACTNN caldwell_e_Page_175.jpg
c71e6e078eb2b9f451ac6ac4b8438e48
91fdd34dba96aed50211795d1d08934ee141229b
66182 F20110113_AACUKG caldwell_e_Page_116.jpg
34809016b85d9fbd68f29a41ba188181
15a0e36fc97cda675506dc881367f0e0b3297b66
3258 F20110113_AACTAC caldwell_e_Page_198thm.jpg
207bb3bdd3f2420c796c45cd5765e1f4
ec2e6e63ff3095ed829f70aa50028fa9e80bdcc8
20555 F20110113_AACUXS caldwell_e_Page_009.QC.jpg
f28d1c2d8cd18fb8db69c8e58e717ea7
e8674ef9015c1c35f2e01b399d958b9fa474b381
82829 F20110113_AACSQV caldwell_e_Page_058.jpg
a7e9f64beb7e8406cf925b184f235a89
6cbfe2b99aa390440145d22de7a3eb2b58344950
544615 F20110113_AACTNO caldwell_e_Page_068.jp2
eb25c027206e81fc3c93755eb2c70278
7744d948ba0561f639c1146265e3c0f39a5979fd
60489 F20110113_AACUKH caldwell_e_Page_123.jpg
c56a5b769b444947d594f247930a92c1
8e628ff0b09bbcd582597cbe9c379f5672cf6c92
13151 F20110113_AACTAD caldwell_e_Page_203.QC.jpg
3f776c20a80dc2cab917c943696feeb6
40064dc085884c04d6c162b6a9e59c266300b90d
3146 F20110113_AACUXT caldwell_e_Page_010thm.jpg
f97ecba07276adab59c617446e045dc7
f90328491c90b367f6b41261fb18beb3655114c2
65485 F20110113_AACSQW caldwell_e_Page_098.jpg
a4ee888220bbd56e2d4f6679b5761271
9e6b160ef1982092d629d7bb13dfbb6bccc01fe5
24213 F20110113_AACTNP caldwell_e_Page_017.QC.jpg
1becc16876a80f2026436766aa2ed45a
316c14451c1013e3647eb2349674e541213c2758
85590 F20110113_AACUKI caldwell_e_Page_128.jpg
7b3ad8f5dcb6145b61c4260dcad5f7c3
2cd7340694fd839305b6be2b06daf07ba2b2dfb0
84524 F20110113_AACTAE caldwell_e_Page_100.jpg
b61fd27f1ad6971a1b54e0b55e7f2418
0eb8db59f5af48b0914b7e0cad0cfa84f7c1f091
7094 F20110113_AACUXU caldwell_e_Page_012thm.jpg
05c940acf9c00fbde55dd45d23ef7778
4ae8da1ded7da23ae1c5dc66decb16e26bfa7d6b
21093 F20110113_AACSQX caldwell_e_Page_083.QC.jpg
8fab5569ae787b90750c4c27443c4ba9
eb20f439ece080044d150961c55ecb4401df37fc
14211 F20110113_AACTNQ caldwell_e_Page_186.QC.jpg
74968de78f03c0045de96e74f5ac2714
8f4cee7cc04794e114bd3e7c39189e4cc3b2a55a
76098 F20110113_AACUKJ caldwell_e_Page_129.jpg
0dad7b3cc1d5f82c86856f07afc44f08
7742f5b3c80992fec053f235dc3322900bbab573
1954 F20110113_AACTAF caldwell_e_Page_022.txt
0515de12a5ae98f042117e47a820ab9a
c014de207b5133044a6e33dcd9fddb78f60a5dd2
3052 F20110113_AACSQY caldwell_e_Page_207thm.jpg
0c19dc3ee7631f675b91f28288174136
35e65cda8a815478a6b625216b73a2d26c48d5f8
25982 F20110113_AACTNR caldwell_e_Page_043.QC.jpg
7cedc39a1aaaab920668724c8e729667
fb33e68517e5a07200d7f9c9081aea04676edb6f
86983 F20110113_AACUKK caldwell_e_Page_130.jpg
713dfffa26cf4716ca2536356557fa45
ce2f70ec714f78ef5746a5c9e9bb53d7f1384e34
F20110113_AACTAG caldwell_e_Page_215.tif
0e55c47ac067c871fc3edf92a0464d90
5eba5edf7a04de309a2eb77dc5c22da5f36da7c0
32561 F20110113_AACUXV caldwell_e_Page_013.QC.jpg
bb5c11a7a1114abf46a0485d3c4858ed
db08ffc50d5c1cb7322ce4152fc991b61c2e8bc3
6268 F20110113_AACSQZ caldwell_e_Page_066thm.jpg
d464da38df3164bd0da186ccc5fdb264
353c46579089c18dfee65b496a47aa32d24f5fb8
4275 F20110113_AACTNS caldwell_e_Page_197.txt
2bfefaeb7dae4c665891af8c66e733c2
7e0745205f42d345e6aa24f60bef689e782b5ec9
85138 F20110113_AACUKL caldwell_e_Page_138.jpg
8debcf263b7c8748fb5801d94c6be95c
be0bc29b2e5ea96805d135b79e5def68ecfa0f71
60265 F20110113_AACTAH caldwell_e_Page_207.jpg
2eb69509111f7513d1d0b1035a5adc46
cd8d1183e1224ebeb54b340c3bb1ed9a5caf0a19
29257 F20110113_AACUXW caldwell_e_Page_014.QC.jpg
8a258e25c1630aa92dcb1d22682b34eb
11698516199ec9cb0e295c01ed6c2aa930792141
6179 F20110113_AACTNT caldwell_e_Page_084thm.jpg
473e0bdbab56ad9b14cdf96d9acfcfee
532f57915e17f26768af539e1100113a5af15be4
80021 F20110113_AACUKM caldwell_e_Page_139.jpg
1bc10079a36f3bc1f6c12e09209ba6d0
dae61b528998f7eba92a52076e72cb65d466930f
1844 F20110113_AACTAI caldwell_e_Page_129.txt
9d41693c1f62082a96ee6d23ec6d663b
84394e6931a6cd0c2b66adc0f7aba2eea0acc751
6705 F20110113_AACUXX caldwell_e_Page_015thm.jpg
5675263c8251ba0cdd04bebfe3b8c344
154c50d80400116284a4990219117fa5922635f8
97385 F20110113_AACTNU caldwell_e_Page_153.jp2
f80e8b1d5c45882a27a30dafb8248b1a
d77658b92c32b1003e51f5839d6ab38493303b58
80358 F20110113_AACUKN caldwell_e_Page_140.jpg
dead1f86e4bfb8a3ff1795945ea9013e
5874fb6c5373566a08df824756bbfc1e6bfdeb39
33006 F20110113_AACTAJ caldwell_e_Page_222.QC.jpg
de97d37be538d17232f3190eaaf5fa96
5d131d302eeb922ed80410a259bbfbb3c5c8d051
5002 F20110113_AACUXY caldwell_e_Page_016thm.jpg
d256c139839c74ee0d8c18b0994ce82b
2ed8236f51850876c5c9052ebdf7ed7949a3317e
1870 F20110113_AACTNV caldwell_e_Page_141.txt
1a949cf0476818cc88b9dd4cfc5ded44
764bb980e18224e99fb6156ac724c598d882fd2d
78550 F20110113_AACUKO caldwell_e_Page_141.jpg
301cd5eba80f3548dc06b26235c2d666
2ed8e76419df433f907d7ab8acdc2a3aa1864494
3046 F20110113_AACTAK caldwell_e_Page_187thm.jpg
88d3a0fd4ef417d7d97e53d24b349881
50966c0a87a249656887d99a19a273c746fe3de2
2346 F20110113_AACUXZ caldwell_e_Page_018thm.jpg
d9289b123dd5b09befa5bb58d7481ac3
b7bb0da49c0d1aead7793de2fd611ca97cfe8cc6
107673 F20110113_AACTNW caldwell_e_Page_066.jp2
0a77431bbe7f9aa16900f2e73c14f388
5353231a1d6b120a1aba928ed76d10f3cce2aac9
76317 F20110113_AACUKP caldwell_e_Page_142.jpg
f673e6bd602cd3592485eb546e220ced
7fecd4c004f40c3873aebbbb1d9b49254de30e13
26894 F20110113_AACTAL caldwell_e_Page_077.QC.jpg
19f4ae47463fc884311f15b623a38c71
7e38803b4bb706825233f680b66efdb0b0ea48e3
45975 F20110113_AACTNX caldwell_e_Page_081.jpg
d4f69323362fd410759ab75eaed7a781
1368574d1b44ef32325a61f3d1d99b31288094ff
82830 F20110113_AACUKQ caldwell_e_Page_144.jpg
ec01a368bf2466daa5ac530b8ea93808
50f68ab2fcf3db1b7a827c73468555cb874bcc70
6350 F20110113_AACTAM caldwell_e_Page_119thm.jpg
ed8f2bec59b014f054df95f0a364b9d4
b90fbeba26a279c7d39399c27e7e1f5e3487b337
12613 F20110113_AACTNY caldwell_e_Page_114.QC.jpg
179fc258665d661f483b4823d292ac6b
7ebfb527f8d17c7c826716cf9a5ff25a2ec56c7c
70874 F20110113_AACUKR caldwell_e_Page_147.jpg
524cc4df47eac2af685617aac1b43201
52373cb3374a53ad4b6fffd7503fda0db8041a41
69926 F20110113_AACTAN caldwell_e_Page_156.jpg
629fdb6be9fb8cac5ae23e51f0cc9a7a
b92aafa54501d1417f7a814fa694372865eec262
16304 F20110113_AACTNZ caldwell_e_Page_095.QC.jpg
9c8aea5bcf9c50bce387748c34fab485
9ee9d1ecf7073da608988f2bd77bf9cbfe678923
19291 F20110113_AACUKS caldwell_e_Page_161.jpg
561b1013269147e8ddd85458cee8fcea
5f344207febd966e494d5b0c2b4e3fb679f0b2a4
F20110113_AACTAO caldwell_e_Page_014.tif
90ff37a553b039a070f6146bb243ed0b
66a7985aaadf39a1c11fef82c0785e5d6480f427
81020 F20110113_AACUKT caldwell_e_Page_170.jpg
95a783c59cc5c7ed375a9143a322b717
b2e59c6ebf6372cbfe20a2e8420f97eef8a763ab
4393 F20110113_AACTAP caldwell_e_Page_231.txt
917c0e28ff0085ea45a5fb20fbc0c6cb
c74004f8e1983d53f26668b8da33ff3e9b89e41e
56419 F20110113_AACUKU caldwell_e_Page_172.jpg
efb4c8b7d7379ce8115c13c9b33ff230
0086377aa65e904a03ef548f5a1897bd6a5d59a6
45255 F20110113_AACSWA caldwell_e_Page_046.pro
19c00f64b99544b591dffc272ecc8802
39a8271126937f4499e8e1b3b5e9fcdba0b86cab
18661 F20110113_AACTAQ caldwell_e_Page_055.QC.jpg
d044ec6b30b4d533fd61e478265f1bde
aea7240537e692f0da281bf02d56fef1caf25672
82895 F20110113_AACUKV caldwell_e_Page_174.jpg
3925dafead51a6f91bb5356ee201e77c
70342c6d2071abb8dfec81643122e370c0af3f66
4833 F20110113_AACSWB caldwell_e_Page_060thm.jpg
ae9b85f28f90db225811a9e948fd4589
a1fc87d12539d83e60913475a472edc4c8a10e44
50667 F20110113_AACTAR caldwell_e_Page_091.pro
ed5c3807693f7d448b54a067a58071c5
6420d49aff6c4abf875a8692bb7a319e6df6624f
14160 F20110113_AACUKW caldwell_e_Page_183.jpg
5d2adbfab76b3e1ccf508da5b6e1be1c
8c9d7097e54cea3b615c75237e4d8e7963147d4a
1051936 F20110113_AACSWC caldwell_e_Page_037.jp2
812791a7ce5749ac136de360e94cf96d
d35b9b46216722192ba15fe2443c62c768048e64
87974 F20110113_AACTAS caldwell_e_Page_040.jpg
dbc261d012790618feaed45864ca3d20
1ba6391419e1d849666962bbac0c95927e6728b9
59875 F20110113_AACUKX caldwell_e_Page_185.jpg
663b50ab15091e95e3fbee2e04076e4d
e4aa2af7746dc0c35b369fa4eb7914a21e75e563
8423998 F20110113_AACSWD caldwell_e_Page_051.tif
714975c01abbfe478e9479dca58d1b5d
e26c1797236893e73176aee75614bd500e5f663d
78054 F20110113_AACTAT caldwell_e_Page_188.pro
a8b8ec907cc63fb75a244ddcdb3b59ec
5e90c4901af293bdb35c6c54e5d16b89c04a8cb4
60099 F20110113_AACUKY caldwell_e_Page_186.jpg
b4e4ca5e6619bee5dfe2c522cf0ffdc4
0e8bc7cb028b6e372e12eca8da91e5b45e197bd4
46624 F20110113_AACSWE caldwell_e_Page_103.pro
779941562bed6849eff2c431e35f126d
5527e0bde3874a58c83f09347300b4befc46e4e4
33623 F20110113_AACTAU caldwell_e_Page_250.pro
bb26dee0fcdd7ca9ebe34c2239c6769f
d21a037f64fe7a7d409b6b481c8db02d00f92f0b
60105 F20110113_AACUKZ caldwell_e_Page_188.jpg
128e30bd54116d04c004546c68acc5b1
20803582fd08908a43ba5898a54b01d5712da5fe
452031 F20110113_AACSWF caldwell_e_Page_226.jp2
abb1c5fdaa799841111fda8467b73c56
2bf6a5cd04749bc8b05bc69e7c603dcf67bb5713
F20110113_AACTAV caldwell_e_Page_117.tif
c76c164d41f60c42eb1d0bcb01c677b3
1ec23e8cca7012691a3be7bcb40585a14dfcf30a
4328 F20110113_AACSWG caldwell_e_Page_201.txt
396194b8ff23050a3922717df263e8d6
a9863a3256c0ca1966dbe0bbcedd4fe9bdfe5a26
119138 F20110113_AACTAW caldwell_e_Page_244.jpg
73a40041981dc17f563e88a2ad1771df
c3f018ec65c9e4c3977c8dfa4eea5227f31c1dee
4038 F20110113_AACTTA caldwell_e_Page_233.txt
d71246e810a0a67cf32e71d2b3cf7db4
6476a77931045bfb9bcff819334ff9bbb20472ff
42726 F20110113_AACSWH caldwell_e_Page_109.jpg
833608378dd531a65f30be6d1ebe9248
c6b2c3b8c0569530ad6eccc723a8a27f29b4710f
81370 F20110113_AACTTB caldwell_e_Page_026.jpg
862b350e49b5f955977d2bc7142f625b
02416ccbf958cba2156acfd4b9a98a10710b0347
22774 F20110113_AACSWI caldwell_e_Page_038.pro
fdb7be67062517fb13edf255c11cc369
0af7495b581cc5e22f24a42ec765dee5e714c8a8
21574 F20110113_AACTAX caldwell_e_Page_086.pro
8da3f7104f5e19758fe0cf1a4e1fe8f1
43065a88839ec3944b329d7793ea5fa43aa8fc49
13330 F20110113_AACTTC caldwell_e_Page_073.QC.jpg
7d85403db8bf92b5aa998b91fe49efed
d8686b89d177669a57f0eea43146b149da962ab7
F20110113_AACSWJ caldwell_e_Page_221.tif
36a2fb5e566a8e9c114b91d29362db1e
034730939f739ca53cd6792fba4c02a4a1c8fef4
9464 F20110113_AACTAY caldwell_e_Page_161.pro
82761de486d8a5755972e857fb45cdd7
59784e0d2427acb45ab0d479e85e2211af58af36
956 F20110113_AACTTD caldwell_e_Page_204.txt
c0ae0adb9b9e68de6de3ffdf01caf0d9
8fe786d0fa9d0d54333fe14ac214444f081b413c
12766 F20110113_AACSWK caldwell_e_Page_115.QC.jpg
abf4fca5f82763788949f792485dad21
18e6ec44fbe1c27d1c2ec56131db2737bce743ef
F20110113_AACTAZ caldwell_e_Page_106.tif
6d864c0826d732359a86746edfbb8283
ed21297067f5021d44e6e3edf9485f3f9d6cfdc6
93390 F20110113_AACTTE caldwell_e_Page_051.jpg
cf32f6c258858e34af3d0941171b6ee3
d40376fd451287deb808d769fa1fadca6c856634
227540 F20110113_AACSWL caldwell_e_Page_206.jp2
3406118ca9d9fed64f2793c28871b6bd
06d1c9e296fb35f8af952fc0ef0d5327773717e6
3320 F20110113_AACTTF caldwell_e_Page_218thm.jpg
c1081ccb5f9f2bf5ccbb42b4554ded45
d615d8be76ca14da0510c1a2184074b73289b5ee
12645 F20110113_AACSWM caldwell_e_Page_238.pro
65ff27a5c2d52e97b0b2d26e9dea083c
dd26b5c92b3280dfe9be8b605fa6dfa269556c1d
5037 F20110113_AACTTG caldwell_e_Page_177thm.jpg
9bdab9c87a6db5de456a14ecb294d6f9
e5b25554d94442723e59cd2c0a9e041f6239aa8d
F20110113_AACSWN caldwell_e_Page_065.tif
ff82571276f4ad6a214ecb43f35ef746
735d02042d13a9fd3cc03f85bdbd310f6cbf7373
99911 F20110113_AACTTH caldwell_e_Page_067.jp2
5fd4a63153e08f2c8dedd1e91963044f
74dbbb5c3d6b3efb7c897259aa50747a49d5cc0a
F20110113_AACUQA caldwell_e_Page_111.tif
d276d00994b871f4b17309cbb530af16
82ce0594b8bb2c7b7503c321fea1bce47981657a
4525 F20110113_AACTTI caldwell_e_Page_224.QC.jpg
74d843e60c9940f027009b0a7dd270ac
debcb3a3118ca8a0460f52d92e6d8e9486b800f1
F20110113_AACUQB caldwell_e_Page_120.tif
0e6689407e52347f07970eed4d87989e
241c0f307e66348d42192a72b0733e03d281b455
49460 F20110113_AACSWO caldwell_e_Page_077.pro
e5a8bc995b7c97d730eae7a16093424f
fcb8e20a73dae5d7fa78cddcda9f4ce60b99d04f
25066 F20110113_AACTTJ caldwell_e_Page_132.QC.jpg
a100671b0fa78c13bebf06d7eb8f23ca
b2cdebd065c1a622a2f0a256d39d7348030d269a
F20110113_AACUQC caldwell_e_Page_122.tif
b739f2952bec4eddee023ba24b438030
5c1061dca743eb470d3bc4c4bfd51eda1deef803
F20110113_AACSWP caldwell_e_Page_025.tif
7c51e40947331a1bdeaa4c7000226939
65f2c66f05b240f80e1b9b9fad8a963aa6605656
F20110113_AACUQD caldwell_e_Page_130.tif
ddee94d20fc3c4c3d9d68f08ee371676
4afec8ef2d49e02d284316cae0f187292f386a4f
F20110113_AACSWQ caldwell_e_Page_178.tif
030b16fdbc8e708cae92286c47012ca1
7d64ce4c698073e7afcac7a1364540004af84e3e
102366 F20110113_AACTTK caldwell_e_Page_121.jp2
9f99af570e913b13a8b897fbdc616839
1aa98f64bdaaf54d4c4cc2b6c5fa2e227b1a3d2d
F20110113_AACUQE caldwell_e_Page_131.tif
9f7a3a0fc0bea35b316eacb29d77354d
bbec5888c373badcb407c5319d7c9241b5a1eb5c
33073 F20110113_AACSWR caldwell_e_Page_150.jpg
c7eae456282628a076a2d409a9b95d87
f6c275354df8ee238eb38853738128c186c8219d
F20110113_AACTTL caldwell_e_Page_160.tif
9bbe5f77cabac748bb9d4801b2d21d1f
a081641f10758e9a599e6292d9bed1f881ac640a
F20110113_AACUQF caldwell_e_Page_137.tif
580349f7d603290799bc2d31c01e0805
44d3b4258f0d84ac5899f1156f5e6445a8965f03
479312 F20110113_AACTGA caldwell_e_Page_076.jp2
3f71623ca8423c12fdb5d750790f1411
25dbdaca2504a3e73ff0556325be9d5ffa6d4268
1848 F20110113_AACSWS caldwell_e_Page_103.txt
942159594e68f5c2051459c014cd9e3b
93a796ab8b8dfd33326803ce29efa54badd29cf4
72792 F20110113_AACTTM caldwell_e_Page_015.pro
bc94b127c52865ab20f99482de90dd7c
54fa0fd5dd0dcd5fe36fccd4cffe46472ab37455
7765 F20110113_AACTGB caldwell_e_Page_236.QC.jpg
f19d06ae2c774472e6e613e218ce8eb4
9ef0ff857b7e9f646493b36bfa8ab594f9e69cc1
F20110113_AACSWT caldwell_e_Page_006.tif
5ae4fa382bb05935a06a0c607ec1d72f
f30592d6f00f56df033e6b6b6156ea2a839e1b7d
1936 F20110113_AACTTN caldwell_e_Page_024.txt
61b4d3c4b6ae6dec5b7b734b6190ec38
4aa6e943050e1facfd04a0af9dd057c588b02988
F20110113_AACUQG caldwell_e_Page_154.tif
db6da4801fa31828e3393df3a32118b0
5b90fc8ad7269476fe17f888edc22836b0f54f6e
12875 F20110113_AACTGC caldwell_e_Page_235.QC.jpg
cc1eed02ed609af4e6abb845511b5b66
6100ed34f8e4d666ab0085520dd6338fd82dde46
59604 F20110113_AACSWU caldwell_e_Page_195.jpg
54c49442baaf9177083391475f2b4c8c
fc0ace458b0a4d0914c2a7cefce13a495cb45ae7
4767 F20110113_AACTTO caldwell_e_Page_002.jpg
6fcff8aeb7720b4ff70b0a79be474131
f22f1d56251d75c6978611798da6a70f752d68f6
F20110113_AACUQH caldwell_e_Page_161.tif
d4858adb9bb14c9451cb79504733aea4
2e787cd32afad17cd00faf5e150e2217bb433c63
70140 F20110113_AACTGD caldwell_e_Page_029.jpg
891b1ba9b2a8e42b3a6ce1a6b1289e1e
52c7e25a368c8e0d927e34e393272e422cbd5cdb
689699 F20110113_AACSWV caldwell_e_Page_095.jp2
d84e33c7411145fe0525b7cc7a1b34a7
6d2b36c21882dfa3ced1b2674f8999576a167d76
49108 F20110113_AACTTP caldwell_e_Page_044.pro
1813820811a7d53554f9417888e98539
97aea65c4f84bb91887768f62c8259f9eb3d1dd2
F20110113_AACUQI caldwell_e_Page_165.tif
24a96c4bd6527cece9f54a26bf01c6dc
f7c68ec11428b05d498ceb666a343d0894649780
F20110113_AACTGE caldwell_e_Page_219.tif
ea070261501060ce353453caf70022d7
452166023c24080f48992f7733647806b3f3d9f2
24214 F20110113_AACSWW caldwell_e_Page_021.pro
0493752403d60fa68d4f60b51e48f526
3dc95b28f14df0d032c541fd2ae6b62a4f45db2f
F20110113_AACTTQ caldwell_e_Page_121.tif
52eea25c3b507b5b2d6d09555b4db30f
e73aa1c0c90865cdcc5acaf7375a50b81d06da5f
F20110113_AACUQJ caldwell_e_Page_167.tif
4b0b9d4051935897b5568a64f044790c
8f9332557de97c3a2124b8687e130fe4c192835a
26103 F20110113_AACTGF caldwell_e_Page_139.QC.jpg
4f14ea168a46f3f8113be860eb09e9ae
1023ed4f50647d6ec39b40a03c7c8d57bd4ab22c
77502 F20110113_AACSWX caldwell_e_Page_165.jpg
f3924616e078dec32d8ebaa5b194b6ae
82589b094bf420dd2f05d1cfee1065ac2798d054
1051986 F20110113_AACTTR caldwell_e_Page_057.jp2
42677e61e1d6eb8f1e1e7c82b136ce26
88b68f59987c25af8ab386dfce922c4c1d8d0a00
F20110113_AACUQK caldwell_e_Page_176.tif
a34e4410d47b8932f498c842bd1f30c2
80caee3bfc1b4814d6e4f601fbfc376ed9b27a4b
14395 F20110113_AACTGG caldwell_e_Page_168.QC.jpg
683ee439652a1b602877a7e85c6709ed
bfa851c92284203901b8e2e276d67ed0cd25c9e1
109914 F20110113_AACSWY caldwell_e_Page_100.jp2
167671594ccfad37e29c62fd275ffe33
dfc64fdbb9abb0003d637a1e0f925799c14b80c1
F20110113_AACTTS caldwell_e_Page_209.tif
4b7e60e07415810d9cac2e077df0a802
9f45ce173e753e1a7225e9dd3bdcb121f945abc9
F20110113_AACUQL caldwell_e_Page_179.tif
56549d8d812eca84c7bf6018904f8f3d
0d8340fe509e603968c15b86cd34a0f2e8fec693
36474 F20110113_AACTGH caldwell_e_Page_019.pro
a835961e45ec87d77fb1f25cb0016054
bb3654ffb893c08a346b54199bd080cc1214166b
225358 F20110113_AACSWZ caldwell_e_Page_228.jp2
99eaaffe23fc9d6040b87a006c500077
8f0c1d7894cde7ee4737acf9afc19aab53d8910e
3975 F20110113_AACUDA caldwell_e_Page_203thm.jpg
ae3c2593f816d2a4968a351aa5e75f28
fa5a6dfaa150193b75681af33002a7dbd95d9771
F20110113_AACTTT caldwell_e_Page_026.jp2
db4856c956c8f7c55446fb461d65a623
add00e639917295388096daf80577e3ecd6e538b
F20110113_AACUQM caldwell_e_Page_184.tif
4b63990c3beca34356b59b4d84d1e09c
5d09bec131d682035cc4c6d2780944e0db30827f
107256 F20110113_AACTGI caldwell_e_Page_033.jpg
9d3662fcbbf74e84c4212554f53d1f8d
37a384d42f6b4365bc5f16e1b0167e58efc0ee38
F20110113_AACUDB caldwell_e_Page_194.tif
c7a02cb2835c76c6625238e71709c61b
25baf779ac449bf7c49b3641826149e8736468b0
F20110113_AACTTU caldwell_e_Page_183.tif
59eca7938e7652e59643b653f0aeee1b
1ea287e4735beebc400a40384750f5a13c0eb2ce
F20110113_AACUQN caldwell_e_Page_186.tif
d863eb5155ece2e91b4bedae57561277
ed0daddd4c501c56d6159cb496c59b4e737a5a01
1051894 F20110113_AACTGJ caldwell_e_Page_209.jp2
f2abecd8630d3276c4852ac77f981859
cbe7866e3dbe1cc87dd5209484ae8dfd2fced677
F20110113_AACUDC caldwell_e_Page_243.tif
fa544afdfde72d93cba0df01cedcbbea
3cdba15df8a83fa19ae67b3b8ecd1a03d32a43c6
25364 F20110113_AACTTV caldwell_e_Page_053.QC.jpg
499d1853a9b85f5c15ed2c2a42fb19e3
01e958bd7bbf593f53a183d184b57ae115abc9d2
F20110113_AACUQO caldwell_e_Page_188.tif
deed86cd48fc1482fd73a017a1d73e02
50192393c02934f037fde6e65421e887ddde1e90
5486 F20110113_AACTGK caldwell_e_Page_179thm.jpg
629a1298f24316bece491a50633482a2
ad3b9c39ae34a532307157794a468465b4e3fdc7
F20110113_AACUDD caldwell_e_Page_112.tif
1c58da650e32b3ac93f99367046cdc2d
0616de851a27915584ec2bc3e8c42f1f6592a453
3849 F20110113_AACTTW caldwell_e_Page_104thm.jpg
2dfc20d1e5083cc8fb5427ac4dcd9d0a
4701a143bb1451aa652585252907d8552492d5bf
F20110113_AACUQP caldwell_e_Page_191.tif
07f40f982f10636d9207b7e9c5582dbb
aef4d5919ddea0797088cf89ff519e7e23adc66c
F20110113_AACTGL caldwell_e_Page_079.tif
1eb24500b11f5e93a2715e1b9f4a844f
3ac234e6c9283af7e1790258e0889d63b14d6807
87467 F20110113_AACUDE caldwell_e_Page_162.jpg
c114b4963d78130cac2a0e93aea7c972
3b701d09773ffa5aa8dc3702697b0679141264a4
F20110113_AACTTX caldwell_e_Page_043.tif
5423270b560134cd23b920da02f9ca02
9ba0abdd179472bb87ab7f662758a4fd0d228347
F20110113_AACUQQ caldwell_e_Page_195.tif
3f9fc82cdf9729f412f91330201a764f
2bf6064d93c93c24b2d148719d1056f37edf9244
6693 F20110113_AACTGM caldwell_e_Page_215.pro
5f79ac5005326497794852aa1eb5e7e6
af8d88b157b2bd2a8420f96a199e0dd8508834b6
12871 F20110113_AACUDF caldwell_e_Page_109.QC.jpg
93c642fb7725d30ad60b983c68194f08
996f41ae66501d9826737947de95f95b9bf80f7b
3941 F20110113_AACTTY caldwell_e_Page_115thm.jpg
928abaa7f9180f6cb9de350529ae9efb
73d8c80cab1b3d9e1267b5d6160d5e7abdaede61
F20110113_AACUQR caldwell_e_Page_196.tif
8c90587b6b1f3ffa00284f57fc880301
8042814953eb8dcc004a28bdd7b7ff0a9b02c835
1823 F20110113_AACTGN caldwell_e_Page_246.txt
8c6522b9dd7bd4070b3ef4f06527a85c
ab92285776e668df934747b765c05c838d2460f7
5725 F20110113_AACUDG caldwell_e_Page_175thm.jpg
2d7b70c16880c0d943c2e4bc6d71aa41
bdfdb4136a3686a36e41c43e9dc118450410a1be
5080 F20110113_AACTTZ caldwell_e_Page_034thm.jpg
cc00df5049944d6b45cb57a3fd9a8e23
75102291c52b10400a53f015da3f74acdea4a47f
4344 F20110113_AACVAA caldwell_e_Page_097thm.jpg
6a4fc13853cc262b31649f110db4d0f0
7ae1ea1cad89309d305dfe864b62f624594886b2
F20110113_AACUQS caldwell_e_Page_197.tif
6ee37055442321504d81b9f6f4ed8aff
48c250909ab65a36f4fe5e31589cad9c78e3bbe0
5819 F20110113_AACTGO caldwell_e_Page_052thm.jpg
e4be051e88e633c8461a3aff9a609145
f1a99854f7340a85a3f0f59b7998dc8ea1302958
F20110113_AACUDH caldwell_e_Page_056.tif
3cdef6980f2329adb5ff7eb998d670c0
7ee069a90b9298e2f3a8abc6cbe49af13938e5f2
17725 F20110113_AACVAB caldwell_e_Page_097.QC.jpg
2dd607e617b5965bfa64a68ccfd49139
3cb757f0636cf9cf0e5378e9b9b9c20efc395e33
F20110113_AACUQT caldwell_e_Page_199.tif
68d494dae431061aaaad9205f0e9e522
8151d1a55a69865c6528f4c1dc55f31da029b412
F20110113_AACTGP caldwell_e_Page_177.tif
80d59063e8d6db43437601b6f78324bb
09df5841f0879f13919a133bbe4e0ea4cf04f010
33361 F20110113_AACUDI caldwell_e_Page_219.jpg
f511f5e796cdfb7c1d931ac0e0dd8c4c
1c4822cc75b20ca7fe67daa4006fabe081d6bbd3
19969 F20110113_AACVAC caldwell_e_Page_099.QC.jpg
e50eb9b53def917babeacffb9f19832d
85030d9e099514390a61e3c166f43dcd755ec7ee
F20110113_AACUQU caldwell_e_Page_203.tif
dcd0797ca426dd311873ded27553d0f0
b149da26f034b2977fe860f8fef0c681a1c3c715
46612 F20110113_AACTGQ caldwell_e_Page_027.pro
6e0c7aa95dfd04d44ae4386f57919c1f
adf5169814f9d34a3dc2234263462b1712f52aca
51854 F20110113_AACUDJ caldwell_e_Page_119.pro
919e3b11ec2db37b18292d7dce4d3dd1
7fa537e33418816f846952bd729233e10e0d625b
6336 F20110113_AACVAD caldwell_e_Page_100thm.jpg
c4ee60ee548c51a36028e0f75707cf15
1b28e963ce46d47418ebf3c8bf8bf155078ef644
F20110113_AACUQV caldwell_e_Page_204.tif
b13674de4e5b4280c420d44d4f537c2b
61b8ec53b7b573cee73da2767796e347887ff482
F20110113_AACTGR caldwell_e_Page_192.tif
2ad83b209290ae50f17aa238411fa743
5ddfeb92244a9e98ecb0f23dbc470ac9a5e439f9
25101 F20110113_AACUDK caldwell_e_Page_129.QC.jpg
cb4ed050d703bd8f277a57c15d9fc834
cc5ae4b89c89c098d45e0a4117d790595d901742
26654 F20110113_AACVAE caldwell_e_Page_100.QC.jpg
424b1847a2e5b872b8899be2db25252e
50657e30a313346bd479d6e802419df5bc846048
F20110113_AACUQW caldwell_e_Page_206.tif
f3b1f0e4a15ca8934c0bcaa3d205a9e8
c4bd56a9fa0dd4beec741e0bb6b109a3d8fa1733
147 F20110113_AACTGS caldwell_e_Page_162.txt
dd6e8098d9a6c4f5c393b951b153a697
14529fe344ba07d79ab2551987af7a9cd8987547
14089 F20110113_AACUDL caldwell_e_Page_224.jpg
49dadc4ddc577510b5e06f01982a9429
d6d7c86463db55e7c80ec81cf6b7597407016f71
17410 F20110113_AACVAF caldwell_e_Page_101.QC.jpg
98973c4982c25108d25047a7bcf516c1
f77a7b94d04a6810e6ab2ee2f9f7dab0b47a76a6
F20110113_AACUQX caldwell_e_Page_207.tif
321378691cfe9ee3e9aab2fe7ef09900
8d9058bf98936122ba6ab123eecad1d724c4b23e
26800 F20110113_AACTGT caldwell_e_Page_007.QC.jpg
77da2d79d42edcd124f359e093a91f33
615f9e651bb589b64f2dab1194252d200486f8de
81241 F20110113_AACUDM caldwell_e_Page_084.jpg
7976c32010accb57e1dcc22e3e66a6c0
3f8309920f581cb09a0c65319f28efc463401959
4034 F20110113_AACVAG caldwell_e_Page_102thm.jpg
d1e7a2db777b1bb0705eab3f676a963c
3cfffed5aca72379735261e12270e967907a32d6
F20110113_AACUQY caldwell_e_Page_211.tif
6f1f74e33bab13caf3203208611e9876
b847d6f1769bd5a2c5b8a19f518fcab0d489c2bb
84254 F20110113_AACTGU caldwell_e_Page_032.jpg
93cda16c6f790f69af4aa6a5f4dfd410
f4f5b0829d29578c235e2ff021a3efc6e7a73ca3
155 F20110113_AACUDN caldwell_e_Page_178.txt
6b836afe465b1f1af8405e452bfa91ca
929bb0e290ff195e79a355ec76a47d382888ddc1
24518 F20110113_AACVAH caldwell_e_Page_103.QC.jpg
4277df83b3620094497450f63bf27a90
fd20b5e62a78f1395283d5e719742d52ea584428
F20110113_AACUQZ caldwell_e_Page_214.tif
978148466fa818397e3b503f934d6600
8ee1036533a38489505ce1c766aacd1dccec6a8a
119 F20110113_AACTGV caldwell_e_Page_004.txt
9322bfb80331c45071f6f605ec45b8c9
5003b3f2a9163c9eefa33c6f0acf315bf6e3a58b
73991 F20110113_AACUDO caldwell_e_Page_088.jpg
c805d64aa18245265e48c51d67ae84fe
0b3498f7ee6480a2d7c4a5dd8dc0c47a35a31d69
25507 F20110113_AACVAI caldwell_e_Page_105.QC.jpg
3aa97eb1bb9eafad6ad729fe322d9610
2385f1e7ab45c1779c461f05a9176914ad41a54e
2056 F20110113_AACTGW caldwell_e_Page_056.txt
cbcff1bd4b8b2ac1d92eb59f8b366851
d1072ae1e407c4a669fbebb4dd1bae069462bbdd
F20110113_AACUDP caldwell_e_Page_050.tif
e8ab86a4c6b6deafc107c191dee1fb11
345300c73f2fbc05344ac52bce8a567ede42025d
5817 F20110113_AACVAJ caldwell_e_Page_108thm.jpg
d31dd054380847e80eae246c5fa8404e
71a76c7b1693cb735e73017dfc600b766a2b1b96
F20110113_AACTGX caldwell_e_Page_102.tif
4fb397f3d941c3f6a8500f5f3b867bf1
6b5d10ec59350dae618b388bf146459204670c72
59740 F20110113_AACTZA caldwell_e_Page_193.jpg
2210753f5a98a71ab046b5772df2e58e
67c0ad0f4ce02d4aa0b1d40e1f5f0a4b7d54f265
1024942 F20110113_AACUDQ caldwell_e_Page_232.jp2
fe279604505bb559519ae6ae306dacd0
8d6fc9b71532446e5f01c918a75f4f10e19e0e38
23755 F20110113_AACVAK caldwell_e_Page_108.QC.jpg
5bfce37e6aff96ecbcd5737da50959d5
feedefe9de8e74d414d16923b659443f1ea16b6b
18599 F20110113_AACTGY caldwell_e_Page_005.pro
2a62cdc2f6169957c7101a613f8b286c
3e26160beb3a35f47004d375c0978c37aa9b77ba
108614 F20110113_AACTZB caldwell_e_Page_032.jp2
e7498744cae54b4561151c0b26799dff
f810761e0760bfdbae2d0b65aa1a90414ca93fb3
1804 F20110113_AACUDR caldwell_e_Page_046.txt
0487e4d6024d8321ca4086f3ae9a72bb
69ddd474625233eb6cb050e010436e63d836369d
18971 F20110113_AACVAL caldwell_e_Page_110.QC.jpg
4087174557466f4f8b95799619859dc1
5454fc27275b9d148149f808b15cbee33bf53853
6006 F20110113_AACTGZ caldwell_e_Page_131thm.jpg
5d549af0fb98ba34e1d3680a7e32bfff
db58f969fc1a80c0b8bc3111058947f2f131e2de
2418 F20110113_AACTZC caldwell_e_Page_228thm.jpg
bb4e09da86e3f6cfb34da2c804d5add8
4f922691079155c2a20d0752f08a42d3e3e27935
1910 F20110113_AACUDS caldwell_e_Page_136.txt
eadf49102c9a18ce34c5ee467aa75db0
19e3a7bae24bdcad16b31caaa4324875a7f2aeb9
5387 F20110113_AACVAM caldwell_e_Page_112thm.jpg
495cee352c8f09079f6a51a4f753004b
9d0c10a6be7d0d47b7c71c4b9a14d477ca9a1d56
5782 F20110113_AACTZD caldwell_e_Page_027thm.jpg
9603eb05e7734b8c7841734918ca80ee
ba9bc3b6edfb9f9da79aa9f1f145eedc1a48b66e
21724 F20110113_AACUDT caldwell_e_Page_096.QC.jpg
782a1ce01891d78d4350fe3d4be2d855
33b15abf5cae4ad3402c01e1eaf447abd6e09c33
5600 F20110113_AACVAN caldwell_e_Page_118thm.jpg
81c3897e08bb3dc3b64cc9165885e8fb
ae9b50b5c131bb6f148e223f41dd73447b6a0869
23067 F20110113_AACSPA caldwell_e_Page_249.jpg
11775cf0cfe10057150cc61ddd444916
d56e8f2c620f11c25f6f9cc44f68dfe2099af2e1
36462 F20110113_AACTZE caldwell_e_Page_226.jpg
1c5fc99486c0085df0c3f72fa11e1ff2
4aaecc17ac173572a4c7a94a28e7e4d16f593b34
F20110113_AACUDU caldwell_e_Page_129.tif
1bf8abf506e506acb04821db30a966bd
7ffcc638dcf81ea637c8859050008dc90df1de91
27270 F20110113_AACVAO caldwell_e_Page_119.QC.jpg
e737337d102f116804023b1c8d256c26
a393f7732cc9b309a6aa7aa651c5580412956adf
2585 F20110113_AACSPB caldwell_e_Page_166.pro
3f18a04ca5cc4bf884be1689210e6f66
6dc3f538fc9add7e0567ad847e3621585dd3cbb9
4878 F20110113_AACTZF caldwell_e_Page_171thm.jpg
6226ee2335220e65d10426bf8149eed3
1bf24be43b237c2b7af79115036cc3d976c4baa4
25904 F20110113_AACUDV caldwell_e_Page_144.QC.jpg
839c3013c290aecb4032efcb7e7ee448
5efa2b9d4e60fcaa69be8dade4c5e6274b58103e
6139 F20110113_AACVAP caldwell_e_Page_120thm.jpg
a925d1312ec942d9d5ae1031ecff72ce
15bdc81393a15d20e455102608b882adcec1e689
F20110113_AACSPC caldwell_e_Page_080.tif
8ddead96cfb62f7344b29a190cee26d3
42601ebacede42e26cd366283b900ef7ab7e19fb
16815 F20110113_AACTZG caldwell_e_Page_176.QC.jpg
cad5760505649f8c87a4ab4f1f1c7038
12334a2b57bb2ac6c01e77b40c1fecaf0b81175c
15267 F20110113_AACUDW caldwell_e_Page_213.QC.jpg
9fa6380d84402520bd46ab37a8d21107
586f51797ebc74b56727e3267417722095ce01cc
1905 F20110113_AACUWA caldwell_e_Page_139.txt
8f27bc6920afbe254d6fced83c557c49
d3e7cd15b9741a1bb947823eb6efcf11b70c9707
6124 F20110113_AACVAQ caldwell_e_Page_121thm.jpg
ec244b5269fbc2c1856e172d5a676540
04633a7cfe824bc88536f266cc01c913b901150b
9323 F20110113_AACSPD caldwell_e_Page_001.pro
9883020eb7f32e94a14b346990bd7532
55ccecd4a35e65cf4344e37963c2edfe57723c08
1280 F20110113_AACTZH caldwell_e_Page_097.txt
a8fb9986b028f491aff633c94c8f7a6c
7f7250db311f7d4a88a2459163706de3ae7c9151
5312 F20110113_AACUDX caldwell_e_Page_172thm.jpg
316be07f0814d880cc826c54b2afa7ff
8de306e2e1090bc3b338fffc54e524389bddb195
1762 F20110113_AACUWB caldwell_e_Page_143.txt
10d48df283c4634e6cb1429d1676be1b
558d036f66f7927f3dc3056ee7830db6a21c878f
6199 F20110113_AACVAR caldwell_e_Page_122thm.jpg
89b4d1c178e16bff633b055c195daff9
a6dfb70575694dc706d55e0afb1f72b97adb86ad
43021 F20110113_AACSPE caldwell_e_Page_246.pro
64f4763ad57b212c2897d6e037ee8f19
4884cb6eafc258f38e2d650a6332b8fc688f62f9
88252 F20110113_AACTZI caldwell_e_Page_201.pro
09cc8d28c796e73a15f956a2d48bec4f
588668ca2de5041c11bc85c32b25a8053fe741ec
26238 F20110113_AACUDY caldwell_e_Page_037.QC.jpg
bb42b5d20fd522671dfeddff3953ec04
efe6e7a608138232bac01df327414ce9ab900165
2007 F20110113_AACUWC caldwell_e_Page_145.txt
1238363e9f935ea41d75020f232ba03a
ab96792d4e7e21fca3af3447f5b42d726199351f
25641 F20110113_AACVAS caldwell_e_Page_122.QC.jpg
d61684a9032ca5c30c85884768013a7d
fe7d55c84bffc4b92705e2859aa91dc2f1192503
2130 F20110113_AACSPF caldwell_e_Page_117thm.jpg
4be9781db8fc29e87a2512d0f17e057f
3d43127dfa292521135dd70ad188c2dea72c0c43
17523 F20110113_AACTZJ caldwell_e_Page_179.QC.jpg
5af32e060e45b3c55e4de5b3e223e583
80afaded24ded96aa48053a1811ed38302a4ff92
1871 F20110113_AACUWD caldwell_e_Page_148.txt
967128dfe85b43dc548c63a9ce74ce47
3d0feb8dfc58148a51c06a644899c6325315f23e
6597 F20110113_AACVAT caldwell_e_Page_126thm.jpg
eb7c4a1112ab46084d1098cdb4dec450
95414d9b7c7c411dd97c2cd625f3114f59ad12fa
4374 F20110113_AACSPG caldwell_e_Page_198.txt
080942908d970fb5450f432025b6229a
c9eac789c570e29299672217d5401795ac942379
4881 F20110113_AACTZK caldwell_e_Page_019thm.jpg
564a5ba09a404411a588c560d2137bd7
6cdb910976cafc8eacd2f1534cf202bb884f146e
3301 F20110113_AACUDZ caldwell_e_Page_200thm.jpg
707ce026f550e61cdafe25739b6df0ee
0ed4eafc946c30e24af2cbac9e94f114cb37a485
1378 F20110113_AACUWE caldwell_e_Page_151.txt
ae3be8fffd256b6847dd5f084dd899fa
54dad30434d068d4af47edb30ebbbca85fe1db90
27265 F20110113_AACVAU caldwell_e_Page_126.QC.jpg
6e20ba6c5b32123d99c335de0a763dd9
654c55312ffe93afaf046134d19638205340be89
71731 F20110113_AACTMA caldwell_e_Page_021.jpg
4e137f2030a2283dbccbb23fd13a0674
1b3b735ecc4b940a063785cd094d324565751e15
F20110113_AACTZL caldwell_e_Page_211.QC.jpg
ec4b93a075c72cf163ba9d23ea39a242
0c536a94dcaeba1b6af07b46c98b0432883c597e
951 F20110113_AACUWF caldwell_e_Page_152.txt
0383b4c2cedbc45b2fdde58fbd46010b
99269aad87e4d9eb02008393cab713f48f2fcae2
64384 F20110113_AACSPH caldwell_e_Page_207.pro
b161c1c8ca618021b96eec23342c0d62
596f67ce20c9e700ed117c447d8f2d81a006c326
F20110113_AACTMB caldwell_e_Page_024.tif
1217e35fca775bc4a2613ab060601d1a
e44bcc71394261e900f3789bdf8e9310a01b9aee
6484 F20110113_AACTZM caldwell_e_Page_244thm.jpg
6f58ab824b11e51a57b3592a9d7e8f09
1241e213a4ce49f585384abb7f083c4b532222ff
1985 F20110113_AACUWG caldwell_e_Page_155.txt
7e200a3645a4f5c936a8250348c5f617
d5e6d6e92bf917b76203ab8971c0710d80f9e685
26626 F20110113_AACVAV caldwell_e_Page_128.QC.jpg
5fa57bb9485703b0c0a9ff042cfaf392
736800161efdc9a68de3b315270133fe6a08a773
5419 F20110113_AACSPI caldwell_e_Page_116thm.jpg
80f7c6c8f102acde5bf63826a690eea0
466521b4b28ba75459c62137d44203dd2dd048c7
51369 F20110113_AACTMC caldwell_e_Page_157.jpg
71190e3b467edc253429bdd6e1ef0e58
1c26c0339cc27d7a2bc27cdabd3c803773bf5953
79010 F20110113_AACTZN caldwell_e_Page_193.pro
85d42ff1bd028b1fb1d241c17b465fb6
34f8a8b1d791df4d2ae164c05e92d796718748fc
1554 F20110113_AACUWH caldwell_e_Page_156.txt
ddcf59d53e63a1b28a8af0280818cff0
dc3dbbcdb5760da1cbd457586a9f52cae9932fc4
25220 F20110113_AACVAW caldwell_e_Page_133.QC.jpg
72a94572d973df4ab11ad18a68c1da02
9b55023065a475fa39017e342ba78acfba69b21e
26098 F20110113_AACSPJ caldwell_e_Page_121.QC.jpg
90024cc5febac939bb4c7a13d7b03af5
1e7d5f62c8c5f530da2518e9bf5906fcfaece024
1027822 F20110113_AACTZO caldwell_e_Page_229.jp2
6375b8efa968befc687df98466614e2e
f14b9666697e49f033b58cd72473cec660a58fe9
833 F20110113_AACUWI caldwell_e_Page_160.txt
1aa6b92910beffb37a2f040da7787003
b18d3aa9037a2db1f2601b0c5724a6d6e97d8191
F20110113_AACVAX caldwell_e_Page_134thm.jpg
40412f769fe37eb1d14e72ac64f11ffa
adf0de486589391b3e83ca672cfb3f6b2250cef0
35048 F20110113_AACSPK caldwell_e_Page_214.jpg
decce721f069d134e4e3081ca2cd6d8c
9a9211641c7f6aa538f305ebb7c64ef3e453b870
106731 F20110113_AACTMD caldwell_e_Page_022.jp2
81b98951a0dee1f6ec6515af0858c28e
51d028df131222339364ce3497be636ad4bca1cf
F20110113_AACTZP caldwell_e_Page_098.tif
2dd244d12c7544f0701af8276efa09cf
c2ecc49bb3e40473d59afd31afd2c8a7993ce8f6
457 F20110113_AACUWJ caldwell_e_Page_161.txt
d2d32a259712f0f6eb37717e25b1b779
27d82ccc6cb82a4e195e8fabafe155bb3a9b1204
6195 F20110113_AACVAY caldwell_e_Page_135thm.jpg
06680bd56d40a0fb85de4c756fd7bb09
c33b7f2b08434892af94c039b53ca48fec560492
6074 F20110113_AACSPL caldwell_e_Page_024thm.jpg
504a868b6e0295ec4b6391449f9ff148
aed5fc416ae35b2496157a5af4b17005543bc9d9
5927 F20110113_AACTME caldwell_e_Page_154thm.jpg
566e9354e4215f98b0aef739516b7694
0953b00721cdd3f7b94ecbfb3a3186f1a6ead70e
149 F20110113_AACUWK caldwell_e_Page_163.txt
ba4ccaa5e4192fdb64bae6d4b26fd6e4
9dc87222e8c5316c3d498fc389538ac14d11bf90
6408 F20110113_AACVAZ caldwell_e_Page_136thm.jpg
6f81aa6623b32737bbd0bbb9aa2658b3
366a0b6c13bcd82e1f809cda2923952197e2cf5c
84284 F20110113_AACSPM caldwell_e_Page_146.jpg
13567dd01389ba57a059dff0ff9615a9
42cfd5c74871b9770a4b5337392c99a1821d5af9
1001 F20110113_AACTMF caldwell_e_Page_157.txt
0ba94acb3005128fd8b494b16edd3c22
7ae8ac88eaa31d1102c46709a475bf34e772d807
F20110113_AACTZQ caldwell_e_Page_184.txt
90bfe1eda65be952629443063ed436ff
c5f0ea1ecc9555a53859891d28be87f59c784ea4
150 F20110113_AACUWL caldwell_e_Page_166.txt
4073269d70c55530824b39aeab76eacf
722bccea915edbadcbd092200b8bfc6ffc3d1274
59628 F20110113_AACSPN caldwell_e_Page_189.jpg
ba1f6019a4ad4d51ad2eb9a970d0dc3b
41fdb0d90062138c9574143428e0c1e7b3d7c054
1903 F20110113_AACTMG caldwell_e_Page_107.txt
1219d5916a60b91c1dd3ea31a35f41a6
650ec0510942b17b577fbf3f704131ebabb9e3dd
1736 F20110113_AACTZR caldwell_e_Page_039.txt
236f582c93e759fb5a906927b8a55b26
94cbe074023952ff71bd818aab88f8d2e571d9cb
F20110113_AACSPO caldwell_e_Page_010.jp2
5229323e254f1eeb8d381960df80e588
5b120a49c68103c76a381b32a161eda8d2558320
43211 F20110113_AACTMH caldwell_e_Page_035.pro
dd1c6878dcb226d9a0d63052886a830b
fd1f22c2866541b3e9a7f37a678d7a30d05ef88b
113926 F20110113_AACUJA caldwell_e_Page_012.jpg
2536c385952402840f669027c7f07913
fbc052d54757a699abbace8905304fc73f1192e8
F20110113_AACTZS caldwell_e_Page_124.pro
f2149746c8ecb79027b560bd903b1199
fc685d3fdddc3e5912263ddc14363dce43b0fb65
151 F20110113_AACUWM caldwell_e_Page_167.txt
8f89a0bf37c171f74b56fe971e1f7696
8e141af3d3619b3071a9a52b06c5ea5d1912e1f8
878407 F20110113_AACSPP caldwell_e_Page_098.jp2
b0e7357f3fe224b2f2f6c0638825d3d1
038967e41518ae82fba13171535572d35bae34e3
3059 F20110113_AACTMI caldwell_e_Page_188thm.jpg
854c729978c5847b129781e0582cf68f
29a7f21a7c78d354251e394e01d10bc6552a8a2b
88782 F20110113_AACUJB caldwell_e_Page_017.jpg
9fc2135fa7946c39f7b7125ff0e2cc36
2bb91e014820cc1e867c8796da22d4f652272b39
65083 F20110113_AACTZT caldwell_e_Page_181.jp2
1d9aa06fed9f903b4feb6107d0170177
c1707992e9a109613f84f1333bff9ab0cfc2d9c1
F20110113_AACUWN caldwell_e_Page_168.txt
c6998d7a8b0fd8a240d83d8b00ca5f8c
b473e158b595f3b47e88c77ef5c55f05853b9c01
49248 F20110113_AACSPQ caldwell_e_Page_160.jpg
01b52838ee4088301d69491d4ec92827
287b113854fbd6bd77041e03d04093ee40e4d86b
506782 F20110113_AACTMJ caldwell_e_Page_074.jp2
dddb2373b1c586ddc3ecf33533c780ee
799f220d2452664fedd5b1df4c4d0ca7e7be8675
33607 F20110113_AACUJC caldwell_e_Page_018.jpg
0d11abbece8a67ba4a00ffdedd2cad11
0db6d28b8d2e3a81ecf5244f1990d3c2fa793332
829367 F20110113_AACTZU caldwell_e_Page_099.jp2
98744bdffd5da06bc7a6ab01d3ba0d81
7dc1035e598c17a48c54f9beb6fdb0acc461effd
191 F20110113_AACUWO caldwell_e_Page_170.txt
88c500f1280b2904e328649e4c578049
5c30b542e2f010223914cf825a0e9b0d7608342d
1051984 F20110113_AACSPR caldwell_e_Page_207.jp2
5da7de2a6bcd3ec9ce652bed5572569d
3643fe31c2e37a95f680eea725342103be3f46bb
6641 F20110113_AACTMK caldwell_e_Page_228.QC.jpg
c6936706711ea8436abfc43dba9989ca
c4cd09ad3a1c8c402694eceedd9a8e447f88e0a2
37378 F20110113_AACUJD caldwell_e_Page_020.jpg
7de2113a18be4581ebe02b126c852bf3
f0ed8d93b8a5de4759eda2fab4f6491ffc4fc630
1430 F20110113_AACTZV caldwell_e_Page_065.txt
54697758f08cc05cccacc1c9f98d2ca8
2bfea265d0c6ecafe1fb5cd779e1fc8d5c0fc062
440 F20110113_AACUWP caldwell_e_Page_171.txt
ec0b2b3bfb5fab134b3fd0252106292e
36082dd596e45c61a9ff45a8af394ef1b25aa457
2855 F20110113_AACSPS caldwell_e_Page_229thm.jpg
46b72aa2c95c4ee827dd2cbf8c9bf39c
f78179f47e42c545b2d7e54822f53286bd29d3f0
68262 F20110113_AACTML caldwell_e_Page_169.jpg
d21df4a20d939cde155166526394e233
5403cd8fce47e5957fd270c1e8ac7a2703431f6e
75146 F20110113_AACUJE caldwell_e_Page_027.jpg
8bbd38283af110b2b619db3f43efdde5
664f332557f26321d10cdd6a8827cadf5d1c3846
100107 F20110113_AACTZW caldwell_e_Page_137.jp2
b27210174bc624c7b7f698b01aa223a8
67a58296c7b07f245469acdbd86c43737e2d0aed
F20110113_AACUWQ caldwell_e_Page_172.txt
2ae5ead76778bf2d2ea94243553702cc
69fda586d1808890dc5bf014410e47a9e81a0061
73736 F20110113_AACSPT caldwell_e_Page_143.jpg
7420953a57bd14a8c6d824d0202d4b74
e5ef7ad4ac48b984a28370d50cb078b0f62900dd
104832 F20110113_AACTMM caldwell_e_Page_136.jp2
c7e8aa1c4af139a7fe7692d6c856cc7d
da9e6c03c63ee8206e09ade9b75926a38f97d7f3
11282 F20110113_AACUJF caldwell_e_Page_028.jpg
ac5b4eb6f46812101910cf13e1756301
a58d282f314286ee5388f7657bc7d2eb2605e8bc
18758 F20110113_AACTZX caldwell_e_Page_019.QC.jpg
e0891010adcaa3458cef10f64e461304
2f54667a8f6bcfb4cdca88868afc17146687f103
154 F20110113_AACUWR caldwell_e_Page_173.txt
b34b2828210b51d4d9482c43e796f156
91f0203e4a8741ea65c5fa9a56aea655e11e80a0
5568 F20110113_AACSPU caldwell_e_Page_039thm.jpg
6eb752148d418ca6447c2c9f512cf80a
6a7b3e86b278d90d03627f46e01fc951999dba68
1987 F20110113_AACTMN caldwell_e_Page_242thm.jpg
ce06928339696afc9bf00b3913f53636
f3233816e5e490a690078fa6a1a9ee4317c895a9
63674 F20110113_AACUJG caldwell_e_Page_031.jpg
1a227c0531ce45aea472733f37a3e9f8
e565c51122595626a22b2cda921b1cc9a28cab54
355129 F20110113_AACTZY caldwell_e_Page_241.jp2
06940a1f5aef71ccf5d71e25d4ebeb7f
6a3b44948611995c9fffd24710749e7a2c4ce30e
F20110113_AACUWS caldwell_e_Page_176.txt
080773bdc180e69fc0c76a3455b4ebbf
71eeb1485c658fe073253764daa1d929d84a0b9a
24494 F20110113_AACSPV caldwell_e_Page_120.QC.jpg
2948a5b900690b33c5f5b55d62daf9f1
abb1f521ed26a43beca96e389d5a2c54cb0d82c2
F20110113_AACTMO caldwell_e_Page_134.tif
1b6ec3d54e5177a877eba4ff3ec9f6e4
8c21e9e86b5928bbe719b5e694a41cb16550fa34
74168 F20110113_AACUJH caldwell_e_Page_036.jpg
80b6108cbc6de70cee7f9e22ac993d02
f160313499c92cfe9a6c5a056db38227a9b4d471
1627 F20110113_AACTZZ caldwell_e_Page_245thm.jpg
c252186bf5027554dacb56bdb4d0d218
8350a0bca7ff86a18ddb711de289cf70fd383b77
4586 F20110113_AACUWT caldwell_e_Page_186.txt
25613d5c5306d4da9214c7311d1ded5d
4376c210c2193278b6724b72b556871ce92e77b1
79059 F20110113_AACSPW caldwell_e_Page_163.jpg
f3e5297af861e945d7a56343f54a45c9
39ddacbb5572f31b8665eec7bed130f1e5a589bf
2126 F20110113_AACTMP caldwell_e_Page_055.txt
d6cf9dabdbf659985036bde39c4a7a76
b273bcaad931cef725dfe02fb91e5a7a9f8beda8
73366 F20110113_AACUJI caldwell_e_Page_039.jpg
d4b060a60afce4434b978507380c7833
a2e93269730081ff20f452a70a25563bd53390c4
F20110113_AACUWU caldwell_e_Page_190.txt
59249459403843c424f49f5e7b991452
ce1f684d8123e47ff2d48a92e3fe3f74891e07b9
F20110113_AACSPX caldwell_e_Page_142.tif
283fd15919cfb9cc6317664cab5b6fb7
fb93defba103e7c156984f736442be65632b7707
F20110113_AACTMQ caldwell_e_Page_073thm.jpg
c204ad3f4ff9880edd68a1d88a5f6b46
3e2cbf170ef966e6d5f3d95d169e45442b3a31f1
83623 F20110113_AACUJJ caldwell_e_Page_043.jpg
3a70275ac957366f0d111684cbf6929b
3273384fd0bd296560ddf7fefcc9b28c5ba936ac
3906 F20110113_AACUWV caldwell_e_Page_193.txt
fb8248c9e58c261ed5096c8a0523c256
9a8dc45929eec531710c77393d835c309cdded69
54490 F20110113_AACSPY caldwell_e_Page_166.jpg
f67012949c9ba528499a437a4ed96495
2b390495a51cebf60799c226db3f95223d17cd42
16188 F20110113_AACTMR caldwell_e_Page_150.pro
4cb0790a7d0cbf7697e665004a68980b
fa8439dbf2261ad9b33f5e911a67d645f1a47469
81701 F20110113_AACUJK caldwell_e_Page_044.jpg
7f044233a2028958511c23a97a17fe91
ed1486e7dce9e4d6df630bf354c934e4b0b4aa46
F20110113_AACUWW caldwell_e_Page_194.txt
5e3ee820f44e529acfeaef10da74f835
ef34254e87db08bd06c16bc1e7e6eaf354a21d79
F20110113_AACSPZ caldwell_e_Page_049.tif
26b3874ea505ebb441acb0efe9fbe688
06e1b32ab4c479597e20e5557d559e43af523702
F20110113_AACTMS caldwell_e_Page_149.tif
1a6911ca6d998fbf6293207c14e39cc5
6d20631be41609e557ea362b5136b826bbbc965c
75407 F20110113_AACUJL caldwell_e_Page_045.jpg
53af274fe43dee6bca9f47a9d70de536
36f29cfb99b11b92915bca6af2c4fb31ec54f139
3973 F20110113_AACUWX caldwell_e_Page_195.txt
b0394370f29f65e998f443bb97f0497a
0d7993c435087504ee5e3144a3329ba0337c1422
F20110113_AACTMT caldwell_e_Page_116.tif
55def969c1655297c7863408dab63558
ffcc5da57455a82ad628348ac98d775b93739921
69204 F20110113_AACUJM caldwell_e_Page_050.jpg
812f805d0d7ea592755a330cd264b3d0
69b1c9111dba1da47c02ac47e2e58546d0e68287
3974 F20110113_AACUWY caldwell_e_Page_196.txt
20f592123486554cf9566179df7b7ed5
b81b59929f4162195cb6c3d54e611422e4c09cbc
2001 F20110113_AACTMU caldwell_e_Page_001thm.jpg
c6ee9f7497c8b2031d54328d0316b3d6
c2d34bd9ea9c360092281a819577b178fce1473e
70733 F20110113_AACUJN caldwell_e_Page_052.jpg
ef5865660ec74e75af108677c718eeae
d1c8416591140ef1a8b755fdf43848d6f1bbd29b
4359 F20110113_AACUWZ caldwell_e_Page_200.txt
bbc2c902f81c5428f6c9a22007170e62
30a73cb598cb0d33bb6abc15ddf52a8cdd378622
23669 F20110113_AACTMV caldwell_e_Page_223.jp2
bb3b4f6d32b2a235a9d146c52ae64ac1
fb62e1896163d013038c2517233431c6cd8aa896
45597 F20110113_AACUJO caldwell_e_Page_054.jpg
5a74c7922f98653c7f9e297b2f6feeb9
8c5a62fbda38e2201158ae27654c93bba3d8a5f6
1263 F20110113_AACTMW caldwell_e_Page_237thm.jpg
d61efd8b4cd00350139801beb12fd261
9abdede293359c087677ce9cd3e6a822323c1195
39794 F20110113_AACUJP caldwell_e_Page_060.jpg
9bc660fe5a11f7660254c1cc3a57b20a
26e65ff0b2174ce3c486249481b0edc2fe94cd20
F20110113_AACTMX caldwell_e_Page_138.tif
f95f364b49ce0e826206df20c719d925
703892a5386e25708bc6e0dc6237fdeb627062d6
75797 F20110113_AACUJQ caldwell_e_Page_067.jpg
8f34d879206f1009f250a97b5b8c8d5b
84a094895a4ae13b0e95635821aca6bf3d31a684
F20110113_AACTMY caldwell_e_Page_174.pro
81a01d5a6ad94d25a9f31242435cd4fa
bd172edd5e18e54fc6844cdc23ae4c0d7c84c2ef
41610 F20110113_AACUJR caldwell_e_Page_069.jpg
3094387c0fabfd490d9135f0d95a22b5
2631f3fa35b492efda7e414d0961e0da7660f723
2948 F20110113_AACTMZ caldwell_e_Page_175.pro
0df12b20fade2d25b31f283f8c1211fa
72e4a36fe58dc0921224f9eae16058abfcef0154
82556 F20110113_AACUJS caldwell_e_Page_071.jpg
82668a1d901ebcbe22dc7c6c1b9518ff
130512bab7e511e87d51e6fee4f99c1988f4b8c9
43564 F20110113_AACUJT caldwell_e_Page_073.jpg
320d51c93c7af7549c583175f299fff9
4b64b5de2fe601c51b64283e5b62a8d191802d77
42671 F20110113_AACUJU caldwell_e_Page_076.jpg
b354cfc451742878beb1845381de1bd6
a364c5b5226e0048803b96d1cc7118c392cd5004
14039 F20110113_AACSVA caldwell_e_Page_068.QC.jpg
98caebc6e6c9e5ba7317a7ebd6054dfa
81c37b65f0f0211d18b019f5f91e0e4ed6dde5ed
83967 F20110113_AACUJV caldwell_e_Page_079.jpg
3731fa785f27621da66137cd0a418cc8
295e6d0bf8058b27c5bf6bbadd9074c34057cf86
1224 F20110113_AACSVB caldwell_e_Page_030.txt
419643743fa91834fdda540cff7f85c9
da0ca88e067bf65dd25ac2138a0dc6953f32b30a
42917 F20110113_AACUJW caldwell_e_Page_082.jpg
1499355e69728770510836213a32b7fa
35d7109cd0cc15021297cdc2b369c3efed4da36a
5207 F20110113_AACSVC caldwell_e_Page_110thm.jpg
7bf7b2dee9017bd2c8eeaf044dc78c54
8674342034dae02abaddd2a8350102f7773e1c2a
46563 F20110113_AACUJX caldwell_e_Page_086.jpg
ecde915edb5b525c2822a697fd577780
08965b03d9a9764d660ad1f9305d684583e636e7
F20110113_AACSVD caldwell_e_Page_202.tif
ef1f7b21eeba5971cf8b5d524b6e6c77
ccfd9ec27817191cf6ae770bfab6c686f1f64e3e
70579 F20110113_AACUJY caldwell_e_Page_092.jpg
1a65340a7d3e3b639d7e9ff250c2ba29
0b9f3322d051aaaa24f887749f18b6e7a7573493
85686 F20110113_AACSVE caldwell_e_Page_126.jpg
00cd1169f7e2beaa7a3e77df9e077682
72cdce639a274c84dd33663f0aa2e5477e745f93
71571 F20110113_AACUJZ caldwell_e_Page_096.jpg
0d615a8abfe8b6405f789a3a3d3b6b5e
692596365ede67523ebc3e1f70f59d04b0e8ef27
47069 F20110113_AACSVF caldwell_e_Page_121.pro
db98fd09ea58e616b9d88253f4ad659f
ce751e29805980e10abe951620bb19a287524cb4
69812 F20110113_AACSVG caldwell_e_Page_017.pro
59a3c9635afbb226c0f3b0265c01e505
7794e46dddbd61346447d8af905ee358564edee8
3769 F20110113_AACTSA caldwell_e_Page_113thm.jpg
1b394cc7d176284d4f4515afe8370b76
55533d6f4c8a3d58ac8a335011ce24a06c45231b
F20110113_AACSVH caldwell_e_Page_048.tif
5d28a2082923da42a6fea3d7b62694c9
6718827f8f77bfcf00078a66437fb149ed25a1b5
F20110113_AACTSB caldwell_e_Page_061.tif
5ed7b4f4e19a68f626e5cc89a11b2cf9
68a7e3f9c6a1cc4d8d050c9b23336389ae464120
F20110113_AACSVI caldwell_e_Page_238thm.jpg
9a33439d40a1e039b469ecaea3485251
582b2d5f4c0595cf7bf7b7fb96b7d9465a717ff0
84939 F20110113_AACTSC caldwell_e_Page_030.jpg
415aa92ae16a4d67764db3114a800f11
e9cccbfa5caac6cf95ed6232ae314b89ce916e7e
12230 F20110113_AACSVJ caldwell_e_Page_104.QC.jpg
87fbf7b428de9d842eb9458080f51f75
03a9e8620dfb7014c5984205c6743bbab7df04ca
88704 F20110113_AACTSD caldwell_e_Page_200.pro
2f3623522fda6261254d7b0be2a0ce10
7f3ec2126812e9ab9b3ad6b638f14e1b088f3285
20771 F20110113_AACSVK caldwell_e_Page_116.QC.jpg
1ba3ab4f3fcef01a53bf2fcba04dfded
ff11c297653a8a1135015342aed3ab5e2c38d6d8
13970 F20110113_AACTSE caldwell_e_Page_202.jpg
769908b66ef237ac48810240a8f18d9d
934a8509401e0840b180e45a4a8869aaba8aee46
F20110113_AACSVL caldwell_e_Page_146.tif
56eda10b73c6f6f673524a5641fb0182
422555c4f6f73903d3dc222dc5ea50786ce9924b
331 F20110113_AACTSF caldwell_e_Page_215.txt
9abaa8ad75747b89fa4503c855d51158
ef1993b57078a13b38b28f9d7a37fcab230379a9
3439 F20110113_AACSVM caldwell_e_Page_219thm.jpg
c93480e7fdacdf9df62668a74d9f851b
ed009db5c6977fbdcc4c790f2980ef546dd998db
F20110113_AACTSG caldwell_e_Page_081thm.jpg
0354887a4fabcf46115bd394a9d63437
a441cd4c20d63f99af2af9fa97ecdcf6da17842c
1577 F20110113_AACTSH caldwell_e_Page_026.txt
b3abf16331e1ae84a6f48a26fac7e797
3d66b724ae718abd16d13881f483df1bd313a65b
F20110113_AACUPA caldwell_e_Page_029.tif
8fbec6b8c2c2074f18509fc9aff375a4
fae13d9aacc7226c775301c43c9eaef3ba36e7b6
62633 F20110113_AACSVN caldwell_e_Page_213.jpg
9b548b6188dfbd1c5d0b15bf788cc983
ce5ce2c05c469f3132562421eb4fca1c527276ab
348256 F20110113_AACTSI caldwell_e_Page_238.jp2
7b8ba461a0291bd9eb72867946905fee
07a7bb7a7ba7dc53758c7e955a4209a62e3fc5e0
F20110113_AACUPB caldwell_e_Page_030.tif
da6aa73be16ef3379d3c36fc449184dd
833716af9977d6f48ff21e2d2796beaa977b1840
2088 F20110113_AACSVO caldwell_e_Page_154.txt
f46c7fe865b8744d7fc7312d96420c99
ffe9869e567468d72bd971a8d051626d1dfc4f05
F20110113_AACUPC caldwell_e_Page_031.tif
aa1ceb56aba4baf9d27428b3e06e48df
810d6efd9c2d0c46f2fb12e687c12dd9460adc9e
1227 F20110113_AACSVP caldwell_e_Page_202thm.jpg
5644a9b9fbe18fefb100562866b219d2
541b03c9ef9b82017f6ceec471396e831eab3743
6372 F20110113_AACTSJ caldwell_e_Page_032thm.jpg
d3916b2d57d30437fffdd449a576e82c
cc28ef3a8e2ff27bde9fd90626d2485cb90ebe5f
F20110113_AACUPD caldwell_e_Page_033.tif
7c7e74a8a7a1c7018a5d6f3d32032362
090bb7e32fe21ed9f159f75f7c99af6c73df0015
1610 F20110113_AACSVQ caldwell_e_Page_116.txt
5d0206761f738c65251366d13210f0d3
7e7b31046b938d698d5161a3215e86d0c13e509d
11199 F20110113_AACTSK caldwell_e_Page_217.pro
9b62b38cb7c030f1c704c3eb77b98641
cf9528a3a9bd51c83e62d84609794f116c2002e4
F20110113_AACUPE caldwell_e_Page_035.tif
e5ec52d87d0ab6e9dd392a378074d18a
c4c2a18318f4c6e6985eed2dd780125582b68e11
79482 F20110113_AACSVR caldwell_e_Page_187.pro
5e5c30d48b4c5d5c79dcef69a4889f05
ea73a760c1632f82d0ba7ebf3fb4d27d93fa18a7
62524 F20110113_AACTSL caldwell_e_Page_179.jpg
2f281594c266307bb695d1f14cb0976b
fc194fad41b278a97882dbca4a7bbda2673800c1
989447 F20110113_AACTFA caldwell_e_Page_035.jp2
4dc918310f37b70f8405bcd5837e3394
b29848bbbf6b8f71631049d3e994ca5178c3ee65
47137 F20110113_AACSVS caldwell_e_Page_141.pro
7237fc9d45f1e18e0f6b32a37180198f
c0a92d95ec2770997fd6648a5ebc53c79c5854a4
4041 F20110113_AACTSM caldwell_e_Page_114thm.jpg
7caeca67ae969c05b7faca302d7ba0da
cf4c032a0d581a4b355966f8b96c8448ea3f7387
F20110113_AACUPF caldwell_e_Page_039.tif
39732047775b63d6f2eb2b355f05da0b
e1dc099cfc156567c0329c928af27f63e659fd9f
67242 F20110113_AACTFB caldwell_e_Page_200.jpg
10fca408bf5db8e0a741781a5d68c8e7
97af6c0560fd3369d15af10d2f3e8b58afc04295
79369 F20110113_AACSVT caldwell_e_Page_135.jpg
6f706d86fae1799a906446365243ccc3
a121a2333985dada52f4b7c69c47ca2507284772
1208 F20110113_AACTSN caldwell_e_Page_183thm.jpg
eb063917396caa1df235cf6ba27bbdd3
f89c72c4b37d6713a7900efea98562118c257b49
F20110113_AACUPG caldwell_e_Page_044.tif
3f595dff04a85d819e6a5e9a164c53e8
205de6d37c651283f24f2269b4ad01f85a1ff5c9
35558 F20110113_AACTFC caldwell_e_Page_096.pro
97b737df74414f0b655ed0c8614e1e70
0959b3ebcb5c954cd73dd3359f175747cca2afed
F20110113_AACSVU caldwell_e_Page_241.tif
c6f5a6d6f977d6bac8db3e39832add15
3e2c40d4c2ffe20ccdbabd8f1b0be8caf03dc73d
49445 F20110113_AACTSO caldwell_e_Page_022.pro
349712b777e572f260986a5dc00493f7
18474c72f311bc8ffdd7b653f06fa3111b1f9eea
F20110113_AACUPH caldwell_e_Page_046.tif
2476b8d5b9796cce4eac8acfc594510d
8cde83d7a702cd58a88cab743d0b3dca25e1766c
F20110113_AACTFD caldwell_e_Page_198.jp2
899e290d28661928eccbb708dec40845
313454e5dbaa54df5292b99e9077eec64ad84a5e
918 F20110113_AACSVV caldwell_e_Page_038.txt
c0e94525fc0ea9b410a7caa4719b9b99
01be75c83627890f68889f39be6c45d5fd354aef
6565 F20110113_AACTSP caldwell_e_Page_145thm.jpg
03f4f39e420b3fd69c799530610eedb2
25a78d08d00be1cde8e8877cb6464be921195edb
F20110113_AACUPI caldwell_e_Page_057.tif
512e25f0e915deac7049db2b8a67bdc9
e88a9d550afcf343e7fbfef92ee486e68f88da21
46772 F20110113_AACTFE caldwell_e_Page_158.jpg
733d69267abdbe3312c2fab7e1185726
3f85ba2cfbbd75bc7fd9f7f3312b614038810d2d
15184 F20110113_AACSVW caldwell_e_Page_093.QC.jpg
8a354884111c681cea1d2abda70f6028
75e270237c7dd8ef3d3348c3349439ad7417b05f
31049 F20110113_AACTSQ caldwell_e_Page_101.pro
a3e0fc5e68444a4eae02e79514977316
c72a4138a646695228520d4609ebd4856a5ec243
F20110113_AACUPJ caldwell_e_Page_062.tif
22037a759c94460f7e251e04649e86c0
2eef995b73d13ac0c3890e99f446596b194e7204
F20110113_AACTFF caldwell_e_Page_123.tif
41666e692bee77c08855a614722abc77
aebcfd58dd17bf70658a73a762626b61c52b680b
F20110113_AACSVX caldwell_e_Page_199.txt
0a9d90f2459a821f0aeb0cc2706f6254
8e823ad2120a5c6a46654bbfaaf9f2ef4f898de6
19233 F20110113_AACTSR caldwell_e_Page_057.QC.jpg
607d57df9fe3ca5f1446cd90a10b9c0b
2404fc9370291acd349df43229d31dffc7a3e8d1
F20110113_AACUPK caldwell_e_Page_066.tif
fb414c8606f4067bc70e78f0a0b58544
7b9f5952724df58e5836dc5b0689ea8d3decb0e3
100407 F20110113_AACTFG caldwell_e_Page_142.jp2
8346f4c3919be64c0be50a3ee5f47fbc
4666df9a5cfe027c4b66c366b3accbb44f09c810
2995 F20110113_AACSVY caldwell_e_Page_211thm.jpg
0ad3d58e7d1a07be625ee101a3898268
98dce675aa6690c7e6483a998a2cf76db3ef6dab
19603 F20110113_AACTSS caldwell_e_Page_175.QC.jpg
bd7de99ec0c554994247e9a32ae360ae
b868e2ecd95f8c37f18d0aaad15ca090df7fe051
F20110113_AACUPL caldwell_e_Page_068.tif
437c43ec9d443b8b831962ffb134a44e
3ac2e3fd3cbd9216ac4e666750e3ee6b146eb7dc
103821 F20110113_AACTFH caldwell_e_Page_063.jp2
6827333fa254afb4bf7489e3f3021698
1125296adbf0664d103c8e6f6694a616d9e63932
48153 F20110113_AACSVZ caldwell_e_Page_107.pro
a74a1adac09e7f7a75d34bfdbaa0c91b
057ef07cca3bbf48ab66abebe23baa02beb6c342
15472 F20110113_AACUCA caldwell_e_Page_191.QC.jpg
d0389bb9453fd990de04c4eb1437789e
f12ecc6068e065751db36c4e3b467defd19df3cf
1607 F20110113_AACTST caldwell_e_Page_223thm.jpg
35598d6a25f722167fd31295a515612c
c53fad1d9c63d99d15a1615d0f0c3bd82ef86a7c
F20110113_AACUPM caldwell_e_Page_071.tif
0d6d2384e82e3d4197118c2d98e548ad
57cb19b7933cfb1500f44f40a28c76d1aac680b5
54976 F20110113_AACTFI caldwell_e_Page_097.jpg
8ce27dc9b584a1d942b755f253fbee2e
110c2c8df6d6ec3f1dc5bb2c557fe097f1e07bc4
85048 F20110113_AACUCB caldwell_e_Page_091.jpg
5971e16a8879a6115b1134f507ba5f4a
a5967b95fc03cfdf482bd2ff65b615b803f2e037
96409 F20110113_AACTSU caldwell_e_Page_108.jp2
9794a26eeff5ab438796dc478582d2d8
88374dd9636b844212b8f2eee09f1408f0616049
F20110113_AACUPN caldwell_e_Page_074.tif
d703ebdc75b5ede46572ee0a54c8031e
49d869d8d13e0d24a799483f6a3a255456a54411
28180 F20110113_AACTFJ caldwell_e_Page_040.QC.jpg
4e3150f61f5929327122ef31571adee4
8838e6ee4ce76a263356ef2093b1d609960a3d97
31140 F20110113_AACUCC caldwell_e_Page_239.jpg
b3bcc04f080eb0f1290e9d29c7deb920
f954f045296c82a237863c7a0120fe20f5cd9fd7
6785 F20110113_AACTSV caldwell_e_Page_245.QC.jpg
02e5db24dd1d7969a724436726505724
aaf461b37ea45574cce2b9aaac25e3db02d5535e
F20110113_AACUPO caldwell_e_Page_077.tif
3d7df94debdc262db3804ce04113f57b
a800db981180ec8f121a91dca9d2e372823810a0
F20110113_AACTFK caldwell_e_Page_147.tif
bb4f92d2c14b37b0726f2420d5564d72
2489a534a899e1f2adc33d7ee045a6de34ba0bcd
107380 F20110113_AACUCD caldwell_e_Page_072.jp2
90fa9d700704629b057a210614e10459
3b84dc151320391a4e6dbc1f5bf9f7dbec2c0667
F20110113_AACTSW caldwell_e_Page_181.tif
8f5fb3ec8739f3a6be33a180788e3f0e
b33a276c1fbe4f404ad7a09b3f47e7d409159631
F20110113_AACUPP caldwell_e_Page_078.tif
b9531638439b9fbd17b1b889d8ba5d08
bd91c9b23692dcbca2583f7ff90bfeaf08e0101a
44739 F20110113_AACTFL caldwell_e_Page_065.jpg
90192a782dc9d7d0631a456bee427fb4
68e95b495feb765a41c3fd338d55e74d4a631bd4
788 F20110113_AACUCE caldwell_e_Page_005.txt
bea5ad6f543a652bdc4bf805768d70d0
722c2a16e907812e6c65072457743d7d4283739f
F20110113_AACTSX caldwell_e_Page_237.txt
5c536ce2ec0db780d0da83c73c4f3ffc
deafa88a707017678aae70d040383805569a35a3
F20110113_AACUPQ caldwell_e_Page_083.tif
3c22105e78632e57f006dc8db485dd3e
a3750cea53c59db174f55098a25202018bcd0d85
F20110113_AACTFM caldwell_e_Page_099.tif
f5041f0defbc6a8a6dff39b46e2168af
ef06a271211f031a33837362ccee8f30a4a0dbd4
109154 F20110113_AACUCF caldwell_e_Page_058.jp2
3dc9fb37dfde33fb08452ae0f6fd3036
80d3d0a8f6c14d358d57373841a5b8e748c214a7
F20110113_AACTSY caldwell_e_Page_054.tif
966e526fd0084fbedef8f395bfe5ba24
ed8097fc08e86fd00ea4a4cad85110ddc955c3ef
F20110113_AACUPR caldwell_e_Page_086.tif
5023e0df854dd8ae3feded8dbe0608bc
415c457decef179cdb881dd0254663dfb05cb2fb
6157 F20110113_AACTFN caldwell_e_Page_141thm.jpg
d6dba083f2e765c6e61b3ce50ae731ce
cf532aa8c04aeb9a89a272acb5107f7dbd750f73
72453 F20110113_AACUCG caldwell_e_Page_178.jpg
8a79e11301a9b1ae20dfc37d59a202cd
48b08b9ad275e4d85e0e887e01f90b2c377bcf05
F20110113_AACTSZ caldwell_e_Page_246.jp2
63d41edfae5eaca532b955df5fc9cadd
3acd06369182b30fdd6ae44188b3a7b0e4ad1ce7
F20110113_AACUPS caldwell_e_Page_087.tif
1e82f20f939418108640809c480158fe
49a1cbbfa8e8f0d496c59b84c59aafade3a4759b
69025 F20110113_AACTFO caldwell_e_Page_042.jpg
4fc3146dbbaa67f8c39b45d661662f66
f2c788de38adfc43c49768e1fb82d755ea8a4d91
25025 F20110113_AACUCH caldwell_e_Page_011.QC.jpg
ebebe2c941ab808f19795718d4120cf1
55ea5a1fe15a562fe3cea7901807f49cefbc7915
F20110113_AACUPT caldwell_e_Page_088.tif
a68347b1026ab5c392ad9257832cc4f9
2dcc01640f96301d573e14a129a11a416dd5ed05
119106 F20110113_AACTFP caldwell_e_Page_222.jpg
0977cfcde0c800825f137165c3f7f971
0c65081d68f0a3113c9cbcc6ae85b3617dfec5cd
18417 F20110113_AACUCI caldwell_e_Page_059.QC.jpg
17faf6304d68879e76b7777f998fe1db
e6c6abaf9f9d7902a256406fb161c23e48095b56
F20110113_AACUPU caldwell_e_Page_089.tif
e6d52e9442636588b09a4d06b4d6a1d5
05026b1354a88b7f092a3d4863143e6d97ed357d
F20110113_AACTFQ caldwell_e_Page_233.tif
ea8af7be4c0422c9ab678506890e0b4b
80d016549664edb7ede4323f6250c91d196fa0ff
2721 F20110113_AACUCJ caldwell_e_Page_233thm.jpg
0ba5253b2fe8988b1796315258216cd0
156d079622d9858b732bd2846c02c6509c290962
F20110113_AACUPV caldwell_e_Page_091.tif
9d1e5f83bab7a36ab156c3c1a143d2d8
aa5a5e57bfae6a90e2627df64777484f1be8f1d9
44373 F20110113_AACTFR caldwell_e_Page_005.jp2
4600ace29b65160337d0b6adc0ed93f0
1acdc158decd9e5433d3546ebe8531091e0f5803
F20110113_AACUCK caldwell_e_Page_142.txt
fa736f4f4a7dfa8aab9d18973c64cafb
582bbfc92c28c4ac583fd52528442f50ae5df96a
F20110113_AACUPW caldwell_e_Page_092.tif
4119fb7311c43cc6a6b492cf008f040b
2624dcaa723744dd033c6add51e20351679bfc79
2798 F20110113_AACTFS caldwell_e_Page_016.txt
f1e5f68c7c18ec95557f1d0170114c37
105cbf002b6f88b7bef231050159f9bb862fcb58
873 F20110113_AACUCL caldwell_e_Page_114.txt
943a3817e0a71a8ec220dfcb3fa46247
7ddc3335a13f41e74d50a0483f313a8dd914bc3c
F20110113_AACUPX caldwell_e_Page_094.tif
38bd0a0bed3ed0743d3bc47342932020
ef902882fa76a45b5e138890fe5b66b4fafb6361
336418 F20110113_AACTFT caldwell_e_Page_239.jp2
9b3d374e58be43ce49834c066c97a98d
f0045e6f808fcd5a0801ccbc6d7b513a942a707e
67639 F20110113_AACUCM caldwell_e_Page_210.pro
3c9e34c3b8c7fb8981e51ebea6e77606
d6da632f4b7d8a2d3504b7155ff4a57748f91983
F20110113_AACUPY caldwell_e_Page_104.tif
c6fffa26551948befaf9dfde14078cc2
015ee57a9350202a5dd41d99589aa328364e9c80
60135 F20110113_AACTFU caldwell_e_Page_211.pro
092ef62ccf6adbb948e18b5d7850c107
3b423ed5bdb117f577de58adc1b3cc30c894f911
F20110113_AACUCN caldwell_e_Page_052.tif
3a05c9037b18eac42d9826776f81d4fd
960bf5a7107f79ebdb9755c94b6e546585e8af14
F20110113_AACUPZ caldwell_e_Page_105.tif
347ebc6f543e7c6b64171750e999ee8d
83d98b8f900620725fddcd69510330576dcb29a3
8037 F20110113_AACTFV caldwell_e_Page_004.jp2
09fe3ca428b6e5398edeb6a66e852873
5227cf3dd3918a00458869f9bb6d5c97a3481a95
26217 F20110113_AACUCO caldwell_e_Page_072.QC.jpg
10feb18030a07c38d9dbfa936ce4b89f
a4769e129e6f9641c97e76fa9064910a5b099645
21676 F20110113_AACTFW caldwell_e_Page_070.pro
467ca5e4b05d950d0c9c73338daad9e4
7c3753c06a270f2e645a8740a4eaed1ae48b12c1
F20110113_AACUCP caldwell_e_Page_174.txt
4227eae19cb41cb39912033cfe99823d
5c49f6d88e437c6d8032d1a58b43a9520408ebdf
F20110113_AACTFX caldwell_e_Page_222.tif
1f40cdf24ee8af6e90f26e9270c66ee8
a3f1bf73aa6150a5432b00d2b9f5149ca57ab86b
F20110113_AACTYA caldwell_e_Page_187.tif
7b34ac3d1bdbc99b712d7efa2d7cd9e6
f386a862e877cdc69d242694bc169b67420f2016
111809 F20110113_AACUCQ caldwell_e_Page_128.jp2
19e96beda3eed529ac027bf60f76592f
c6c44bbe78bf1031c5d3e8400bcfcb16257bb617
118247 F20110113_AACTFY caldwell_e_Page_221.jpg
1021f7c1754596bcb958f3431ba3e69d
be2c5af4d3795bd370c539ec5b5d98aa8fdcf19a
F20110113_AACTYB caldwell_e_Page_177.txt
1c91b598a5cf0aec10b094a2f2cad31a
252a55bc84c46f26fa999a13f5b4e2d49c384e37
71509 F20110113_AACUCR caldwell_e_Page_159.jpg
a25ec46cda8489cae83e662e19137131
54e7426ec3d85f0fcb01c08e61fd5120127d02d9
13676 F20110113_AACTFZ caldwell_e_Page_231.QC.jpg
e73e73af4af41d1fad248e3dc618b487
135381de0623e53c6a58bd43af454a9b509ee935
35114 F20110113_AACTYC caldwell_e_Page_034.pro
6499ba3e4b6f749f9e8e7b20899ab941
4e2f0f52331faa45e4925ed783d9e1e0a7e19cdb
91708 F20110113_AACUCS caldwell_e_Page_052.jp2
f513195a92f50395763d2ae086c48d9b
9b0c30e046bfa3b15c650e01b0f7b6c749716932
1051985 F20110113_AACTYD caldwell_e_Page_009.jp2
1af01d153591f231e24d73fc5a768576
7c8c3586f6c9390d9d8f0316fe715dad40e173d8
72470 F20110113_AACUCT caldwell_e_Page_097.jp2
378ca9c750642e61158f3ed95418c7f5
c826a0ba3372663bc1d6ce59682f266052aa1fc4
82008 F20110113_AACSOA caldwell_e_Page_122.jpg
bb0450f75ceeb4cc1e33ec1aa59a6d32
536bf39be85e0fe472e8dce037b40c5027a70af3
4368 F20110113_AACTYE caldwell_e_Page_168thm.jpg
e87078bdd4f9cc60d46194cfd8cefc55
db0c3a63d848a7367e4a02be3fd5d874b091d474
782 F20110113_AACUCU caldwell_e_Page_104.txt
2ce9e919ae9e78d5d66af1b72a3e47be
2e160ec7922f04c1ee736ca0d11b87def317e21b
48666 F20110113_AACSOB caldwell_e_Page_133.pro
651488042101e3e0405dcc82a4c0c0cc
d55342232ef4a51665814d401ce979e830d33f0f
F20110113_AACTYF caldwell_e_Page_152.tif
40f4f4124036e52291113937f080cc51
cc4eb28aa1603940d6295149d3a7afce4f2444eb
57411 F20110113_AACUCV caldwell_e_Page_009.pro
973fb5dd6b03633251fb2507a61b1378
532d11b4dfe0f171fbef286fa5ef98997e1d1492
22807 F20110113_AACSOC caldwell_e_Page_134.QC.jpg
3ef9564131407d03fafcf09eac753134
a9680d20c172b6b269606ff780db01314b98a9c0
2247 F20110113_AACTYG caldwell_e_Page_051.txt
3221c228a4539aa2636e1b6fe8c2c827
f53df1f24c4a4c4e188cdd2f6f18270878b5cfb4
83987 F20110113_AACUCW caldwell_e_Page_077.jpg
67743eb4caacf75fba8a8adb2b83411a
d5889eaac0e22c71ceb17a5476f203ad44c62e5a
2719 F20110113_AACUVA caldwell_e_Page_037.txt
acf2cacfa31e6a4f1f3635e1460d7e21
bd89c207e5692c6f81a2b0704e9ef8b0ad631d1d
4388 F20110113_AACSOD caldwell_e_Page_078thm.jpg
80c88c7f8de142ee49b720e5018d8937
898963a5adaf3c952fdf9d1a7a272f1beb89b76f
344474 F20110113_AACTYH caldwell_e_Page_218.jp2
06e7778eb6ba2dab4197a630bc9a821f
f2f83b90459d069bd1502669556781a11ba7ca0a
849649 F20110113_AACUCX caldwell_e_Page_124.jp2
081a110c3717e4f14453af6f4a988609
189f1a9c56701354c92137af8817409e7fa4707a
1024 F20110113_AACUVB caldwell_e_Page_054.txt
5208f11b93dc95438f1f65f291e43011
f1f7d10e1ad9ee4ccb7d992e3c1c1eaeb5667628
6398 F20110113_AACSOE caldwell_e_Page_149.QC.jpg
e5b97e87482363ff36dc6a46b896787d
5e563ef8d73e49043dcae2ae953141607a2335fd
1535 F20110113_AACTYI caldwell_e_Page_124.txt
638140adf4f443e6ae79bec3f1d6ad37
2ce319c99ec54704f63e4a9c00caf70cbeed3036
F20110113_AACUVC caldwell_e_Page_058.txt
59933b9f66bbff653ad9307f973b864f
6fc2434c34bc64e0a76db76289e172a716516033
100979 F20110113_AACSOF caldwell_e_Page_141.jp2
7a3a8dc4238b56331dcc389e490e2a6e
343b174592fc7d06e5059d34012d0e03b50c946e
1457 F20110113_AACTYJ caldwell_e_Page_068.txt
0b774ff350416867c576f8d25e046839
b269e5e4e709ac656f2f0daa6dc96de1bd2ca58f
46117 F20110113_AACUCY caldwell_e_Page_118.pro
42b54f1fcb5d96baaf8ca057a3e9161c
655f74e8784e40a0a3ff4920e8eafb4bc7666156
1551 F20110113_AACUVD caldwell_e_Page_064.txt
24a1779a1eb25dde0ce8d9e904a1ebca
f26d5153803da834d409f7092cf9329e61c5b0ab
81825 F20110113_AACTYK caldwell_e_Page_019.jp2
bfaabc9911e845b6b78501aa218ddf62
303d52183c901af9032d112f048d132760f9594b
F20110113_AACUCZ caldwell_e_Page_119.tif
3b7921cc66048aa9c36016d822ce693a
536adb01d64bfe2f27cb763131628bd0349dc526
1937 F20110113_AACUVE caldwell_e_Page_066.txt
8e76d358594a14d9e4d5c09bc1f2cb8c
cc1ec5fb279e0933449516b617080499e6ece553
103777 F20110113_AACSOG caldwell_e_Page_080.jp2
8b447ed8de516a66ed8c625ba93c14d3
93d8b6d348a9f9c79c13cdb8853db546d24c6d72
13814 F20110113_AACTLA caldwell_e_Page_241.pro
42c8a0219569638b93a64aa591d90583
5c12826cbbc9f2f2a6d8b346ced7207afb6fced0
F20110113_AACTYL caldwell_e_Page_027.tif
030684728155dc17865b43091f4f841f
5eea12742aa1dfea41118b3f323ecde6e5be3e12
1319 F20110113_AACUVF caldwell_e_Page_070.txt
3c1ee04635a2164dd12e4e677744e2cc
1167c5fbb58ad2893b632a34b8e526ad2f75b5a3
80515 F20110113_AACSOH caldwell_e_Page_121.jpg
2b5e5e0d06a452ee347e6dc4ce539bb4
132456175b4596349e74b61d278f838cb4d5a51b
F20110113_AACTLB caldwell_e_Page_115.tif
3bb5be886c19357e91688679116f8872
165eb97e1eb595988e18a376bb928e21978b6e35
F20110113_AACTYM caldwell_e_Page_082.txt
14c9ef0b61a66fe9590cb28b85d1a8ce
25c51212ffe930166e46eebad5251df4b01892df
1952 F20110113_AACUVG caldwell_e_Page_072.txt
313911d7cd343734be659c79c34593d1
dcfa5dade49e32a6dd79fa72c797e2b0d94306a5
F20110113_AACSOI caldwell_e_Page_082.tif
58ef01e0d5c507f99985f61cf79e097a
3c5a9cd4e2fdee1aee487e1bbb4dc25b3442e50d
509993 F20110113_AACTYN caldwell_e_Page_113.jp2
ec1c94a6839fa6a0e24001d12f9af387
2c66b0007e5b04568387c313226360ed196610c2
1948 F20110113_AACUVH caldwell_e_Page_077.txt
fb4d9155abdc954ac6d101460a5d70fd
db94bd4b7c70130cacf1d51e8c5abb0f42055efd
497550 F20110113_AACSOJ caldwell_e_Page_094.jp2
a2caccf0d3802390cb11bcc754629972
a7e430855f47565f320bcaf4f2f00045f785c5d1
1491 F20110113_AACTLC caldwell_e_Page_249thm.jpg
d76f9a85eb04fcc0f30571fce64e59d1
296a2dc9fcbc1e28b0b3b6d55436a115685dc726
492548 F20110113_AACTYO caldwell_e_Page_073.jp2
a21fb7e4bd62b829132a211c6f1f5e40
fad08c2a53cfb6950638ac152d53a392796a923e
2004 F20110113_AACUVI caldwell_e_Page_079.txt
5b4c25951ef6436354d5fef360a0a574
cc1ade16489c434e110e7979f7a4634ec3719c78
49160 F20110113_AACSOK caldwell_e_Page_066.pro
966087ff0c53c64412aded02abf2a1b1
02de2e8f0f3cbf8d3bdd6e2acd59f29c2e3b1fde
F20110113_AACTLD caldwell_e_Page_012.jp2
a951568084c9a90b260a33be12b2a8b1
67ec00d1204c9c209fa916340f36beb041c10257
1931 F20110113_AACUVJ caldwell_e_Page_084.txt
04a70cdc07a33bc71f26b0220ece6e9b
1f392a085a39d67912b4a1abdcec11b57c93a60f
34195 F20110113_AACSOL caldwell_e_Page_182.jpg
fb5a8fde8fcbae521cf5104917b7bcbf
a05203a117c35423665438937f0f2d57aaae95a7
62718 F20110113_AACTLE caldwell_e_Page_034.jpg
104a70a29f8d20e61fff5599422ccd14
3df7a58aa11063d100aedf79b4c197934c87602c
653 F20110113_AACTYP caldwell_e_Page_106.txt
fb7e7b43a0f2174999d96826d4a8d29e
8a8499cd15c5ed5468acdd271f544035666da32c
1527 F20110113_AACUVK caldwell_e_Page_086.txt
610bb14b7b08e4eb477cdf4e38fa6ece
734564e019c299429015f13b127aab02e92fa1ae
75767 F20110113_AACSOM caldwell_e_Page_118.jpg
3681ef2d54671bf5528ee6b71f34706a
fae873294897f8fa7f4ed30f88e3bac606b3e96f
1309 F20110113_AACTLF caldwell_e_Page_050.txt
f70c50db45aa617492c5b276ef4499bb
57972b8f945f9823643c94889e8aa907cf6540c8
F20110113_AACTYQ caldwell_e_Page_208.tif
e0ccf45bf6af7df3cad079ae9187bb6f
849133781df8128a3760c5b7dbab3d78c1ff3387
F20110113_AACSON caldwell_e_Page_095.tif
3dcbbb78dca1977488410c5eb939cd23
503c5f37ec92b05390dd460976e44cdca2050a95
6602 F20110113_AACTLG caldwell_e_Page_037thm.jpg
642d474e0696767e113fdf3c4ec66c7e
b511c5695d5b78c9fc40fe70394a357bb0b97a2c
1332 F20110113_AACTYR caldwell_e_Page_123.txt
ae55ebbf54d45333f1f0b91683f0d036
36ce0f33d2d0d73bff5a2fd47b793bb18ee5d480
1646 F20110113_AACUVL caldwell_e_Page_092.txt
05af6ef76d88cc93e773cee3e0aa785a
bb0c8d2beea38ee24b9047caa367bcbc40e0f772
538887 F20110113_AACSOO caldwell_e_Page_114.jp2
2add4e501e882803b6eb87a0d9992241
a2d00b36bdcc6d18d762786d748b86c088b7ede4
63757 F20110113_AACTLH caldwell_e_Page_177.jpg
64b96991d2304a475a46466025b21583
c14f544c10796990e5de7b04660392b93f05d248
67928 F20110113_AACUIA caldwell_e_Page_229.pro
2c440edac25f8250a7c83d7c88f36323
522681ad8f045ddbcb83117bb6c1e2aada067180
105845 F20110113_AACTYS caldwell_e_Page_139.jp2
5c48de0f58d28ce357bd94826dd4a225
caa847b4717f3c531c43792764d88ddf472c78a7
2207 F20110113_AACUVM caldwell_e_Page_093.txt
21be8ac8f3816515a3cb087a0fc12274
ecc42236a712e3fe711224b9ac23069922fa5727
F20110113_AACSOP caldwell_e_Page_097.tif
df69913bdcf367e18c60176793030dbc
4a828d7cb89e41a5b5e582dff4b0d8d31fc3691b
47772 F20110113_AACTLI caldwell_e_Page_135.pro
f7bd90646e587b28417e53f1459074c3
575db56b0c02ac044add5674e06bbb08d818bd76
14636 F20110113_AACUIB caldwell_e_Page_054.QC.jpg
3e2bd6067c1425469504a44217877f99
3274be9526a29f9ad9d7db979fd2f4316ca81717
F20110113_AACTYT caldwell_e_Page_226thm.jpg
26e109c48b05b8ed2b2137473a82fbf4
5208bc29d2fb11f17eefd54636f88ed2c9df5cfe
1751 F20110113_AACUVN caldwell_e_Page_098.txt
87c158499d6b7e998116bcf63955217c
edb526ce03c001ba1dbe315a526db10e36f32634
992 F20110113_AACSOQ caldwell_e_Page_102.txt
adb819e0fa7acd610c34701c48e2e13e
3b285449d55a690151acd20d7a2c16b3ff00ed4e
1598 F20110113_AACTLJ caldwell_e_Page_096.txt
7ff6b08f4d5a31dfb5598808817187e9
14e55f1ec5c722573889922b1edf09423405d4e3
29465 F20110113_AACUIC caldwell_e_Page_248.QC.jpg
d99b142b2795d2123c13f70651a74d37
799905524e0f83c7cb824010ed109a9b807d097d
2842 F20110113_AACTYU caldwell_e_Page_212.txt
c8a623c993335b6d38fae9369e2d5b2b
c7b46b5fdaac8e9ca506f4397e8df8551e010215
1731 F20110113_AACUVO caldwell_e_Page_108.txt
b1fbdc3425da3ca8d650cf1fb8de7a87
02e848a3c7892d5d961fe813bd2c9cf3312d1984
36236 F20110113_AACSOR caldwell_e_Page_055.pro
c253b4c04fe880a98534d1757168600a
63e5c8dea576d1830bc8ae469d7c6eea59a4c616
1409 F20110113_AACTLK caldwell_e_Page_085.txt
21f1ef5bd4120df159b5b7e2d97df551
e51660abd0e4bbbca109667ac9d440b68f58497b
4016 F20110113_AACUID caldwell_e_Page_151thm.jpg
3f7180fdf3d851caa6f07e8a72c91d89
f9426729aff7845dbd15dfd295b8bd9c0ceda3bf
F20110113_AACTYV caldwell_e_Page_002.tif
7b74bf4c8a2c40c0ea8ad15cecd73dc3
7da2e1a9d7264d7d4dff76c387d42aeda90d2684
418 F20110113_AACUVP caldwell_e_Page_117.txt
18487ce758035c2a4b9e64d32a6e57b6
07b3129a6db715b1093bd411a82adcfb85bd5990
F20110113_AACSOS caldwell_e_Page_173.tif
569b567c67cfae87586f8e609887b27e
d427204fbc874a3f165a3a4d7df8703d2e7e25fe
50573 F20110113_AACTLL caldwell_e_Page_053.pro
34c3520a7fe74a5062cfe211d73ee3b2
3e58f6d6c8560d32e7ecc2495c4d25226e867093
37182 F20110113_AACUIE caldwell_e_Page_204.jpg
04802ac928b6f18bca413721e8f2be41
3f82fb61f342badfbe3146559b69ef6f168a4c57
76758 F20110113_AACTYW caldwell_e_Page_006.jpg
040f9485d2c6576f301b380629a844ee
e2df5a5c65a31e20deb2e24b68408cf58dc5e661
2039 F20110113_AACUVQ caldwell_e_Page_119.txt
b6e64d5aad48c6fec8da26880c621302
09542a6499d8046fc0a45bafe4fbc86f6d0d1ee1
3913 F20110113_AACSOT caldwell_e_Page_152thm.jpg
52a5e3b09295519353f277a0daa4b45a
e39c823b67c44b99a076cdae77406fd4a0982557
F20110113_AACTLM caldwell_e_Page_008.pro
590861a44f72aa9944b9cfb7470cb2d8
a58add7534107317663d051a95fc3d0a4d3350a2
997 F20110113_AACUIF caldwell_e_Page_217.txt
6c0dbf57d0511e9d0abf1a78f1891d7b
670276fb659a95cbb935c7ff4b21daf22708c438
81055 F20110113_AACTYX caldwell_e_Page_053.jpg
5ff70199deca08fdb54a081a77fb3bec
4f9cace82c523f3011aea83d37ee071df75185ef
F20110113_AACUVR caldwell_e_Page_121.txt
74b13830f89e1f79f422f5f4d9dfc111
3cc562f2733dae449565dac29d8c220c88b8bdd5
1183 F20110113_AACSOU caldwell_e_Page_109.txt
23df7518878907a50eb661e2a5aae0fc
3e3d5fe20109dbc354d931cc3dffec3a124592ea
43276 F20110113_AACTLN caldwell_e_Page_108.pro
be208784d566577bff15d637d8f9c494
fe4b1446f8fe2013ae785136ecf4b8c357208b23
2792 F20110113_AACUIG caldwell_e_Page_005thm.jpg
9f5859e3ae1e532f3df64d04cdc54af9
ce8e57729d5da3872135e1599ab03f71e40d6d1d
1239 F20110113_AACTYY caldwell_e_Page_101.txt
826eed16dd662fe12c5e6ca242ea0541
bd7461fbb2566f8278399a55470b0405b228fe42
1951 F20110113_AACUVS caldwell_e_Page_122.txt
f103beb39dd0c47fac6e88902d233f96
e8ca743c85144acaf5454683609638d97ea78c07
4434 F20110113_AACSOV caldwell_e_Page_007.txt
ee021adf26416764832df0ef75949d94
a07fbdbd1ea02c7323ac5026ae332784358c8f49
F20110113_AACTLO caldwell_e_Page_171.tif
69262f9434cb9f7e711b68e17fd24679
4061a81124995b71a077bebee0d399c5969269f5
F20110113_AACUIH caldwell_e_Page_018.tif
b7edbd340b2dc6241e20cdebb361ec63
fe0e62e812420de9a36074a854fd080155836b56
6013 F20110113_AACTYZ caldwell_e_Page_011thm.jpg
6d81ee9dd8f4e30e1d19d1d13fc28d0d
e76582e584a362da0acd92e571db73e9e062bef4
1909 F20110113_AACUVT caldwell_e_Page_125.txt
778ac00ca7a38bf1b62c40eaa0fa66f2
387389f7023c43a2075dfea3d58243ba1c439923
F20110113_AACSOW caldwell_e_Page_037.tif
6a8b74fbc978429c27b7e51c496106f7
95f51b543c6bb3252ab2e624231de67058d0cacd
43396 F20110113_AACTLP caldwell_e_Page_070.jpg
4d88c198c64e196a7a780670b2fdd80c
9bce8732258f1d7f0beba0daba4c5f3a28b07ade
16923 F20110113_AACUII caldwell_e_Page_183.jp2
46588be2157e54504e55908f796b7203
7fbedb70bd04a7c778a538633cac91077c9b1040
2057 F20110113_AACUVU caldwell_e_Page_126.txt
0093ffc73177c635758f71f88eb5c3e6
d0540e8adbe9d726ab99c6226ada1091f73b10e7
13197 F20110113_AACSOX caldwell_e_Page_225.pro
642ff4456062c5c6a9e65d29873cb93b
ac89869d33c134a6b40f39af1068ca0d7e5fc646
6165 F20110113_AACTLQ caldwell_e_Page_026thm.jpg
6fa27618e43ef62fe1923f85f3d25a48
f2af922f70e5eb8f88b5f24ff3d56b5398d4add1
304 F20110113_AACUIJ caldwell_e_Page_164.txt
7fcea0256b1b913bd8c190fecceedccd
7c70d08c8b560b3ba22699edfd78a64558b0aea3
1862 F20110113_AACUVV caldwell_e_Page_127.txt
81713fb3d345da27a41ca309b902231f
60e61de9ca04fc6f543dfb7e4a94479883be9de3
2097 F20110113_AACSOY caldwell_e_Page_130.txt
a2c3b875f7c77c10deb41507126203a1
26584823a4b36d534e40e9229b711f8e76fa4a87
F20110113_AACTLR caldwell_e_Page_176.pro
a3fa5f29717ca9a89b82061e4d4239dc
bf52d8f87a9db9c14bc04398982ea9896ec2815c
F20110113_AACUIK caldwell_e_Page_214.txt
fb89e812b385d5ca4df85ac424243424
fd242854766839cbfaa2bb87d88307de0cb896b0
1887 F20110113_AACUVW caldwell_e_Page_131.txt
52f31819c81dbaabdf46adcb0bd585aa
7cd331a665be153dbb594620ccdbfce62a90a600
1814 F20110113_AACSOZ caldwell_e_Page_052.txt
97d18dc5af40a3f4a80b1db526eab296
598f14f6fa3a4b0fa04e3e6fc722e861c2024465
6232 F20110113_AACTLS caldwell_e_Page_053thm.jpg
7d76a4b9401e2fd55c279b595132f1b5
231152e07e31fcc604c856d190c1fa9d306e5ddd
F20110113_AACUIL caldwell_e_Page_157.tif
e6d87306360908928d6ce7abd2354080
77cd10e17c617bff60053539e603b6729ef0ec8b
1929 F20110113_AACUVX caldwell_e_Page_133.txt
4e2db46c38e6d8cb0e066c7cfb4a6dcc
19d90238696a6cf4c8927ba892bb489a5432923f
F20110113_AACTLT caldwell_e_Page_135.tif
afe61581e505a6f301b3a78b838c6632
af2fb22457a8862e2395dfe955b43751e65cd7a5
3895 F20110113_AACUIM caldwell_e_Page_106thm.jpg
f0aba1ac2690658abe90f796a7d9d1fd
020c8534c223734c5eb2e81388d70bed5603d17b
1707 F20110113_AACUVY caldwell_e_Page_134.txt
727a8af32a3cf4b555d2a2e8fc18a504
b5707a077d15e2e115257d08546c861695ea16be
24935 F20110113_AACTLU caldwell_e_Page_142.QC.jpg
c43f66425276775829aa01e2a89c38a3
a0704c094b690b4b9b7e164eb4b8125521d8987c
F20110113_AACUIN caldwell_e_Page_170.tif
5622eb448b8ed7c5325c97dcde8499b8
1e7b0e0b7844c197b6e4a650a129ae4fdd2946ef
1897 F20110113_AACUVZ caldwell_e_Page_135.txt
251d3d4bc365489d5e1d053915134fe3
609377e98d8e0b350cd3359d654d5dcb39f2e64e
70953 F20110113_AACTLV caldwell_e_Page_047.jpg
9107510cb014700cbe9c53562fa3ff9f
00e52485d2b18cbfb4457e12282c4cee82854474
77230 F20110113_AACUIO caldwell_e_Page_120.jpg
c0b9f6bbe013e60388a83080c4c78a32
6e8489863afd7e9ecfc6d0a99cceba6090519741
1381 F20110113_AACTLW caldwell_e_Page_250.txt
7b083a939c8fe6d054dae54f7c92cb8d
6fec97a7fa3c31efcd2ad1a419da138f293bd4a2
15127 F20110113_AACUIP caldwell_e_Page_062.QC.jpg
63b73448645a7bf5ac963e09462ae17e
707b89b69249281fe58437dd251812c20b906efa
F20110113_AACTLX caldwell_e_Page_237.pro
4ace76c2aade7d7b380906dbad60eb73
a502a6f88eb2e10ab55124aacfd8f6ef18161cc0
17947 F20110113_AACUIQ caldwell_e_Page_242.jpg
8a84d4c937a93ff7f78e032e4cca5aff
cc267f552c0b8c19fb32a8fd147a2f3b3c002731
25842 F20110113_AACTLY caldwell_e_Page_066.QC.jpg
dfd232d4ec6212e6f141a2dbef0c8f97
a7ea444cc4e6ef6359650d4b3164bdb0b67c875a
F20110113_AACUIR caldwell_e_Page_056.jp2
4b08e5433710a4b10705d41e966059be
9df3d2fe077c095de096315467eb076d3175aa69
F20110113_AACTLZ caldwell_e_Page_113.tif
201c41a78dbcc1d96e61d453adb12fbb
a81c1e70a9700d75280a057546c46e15b9ecae3b
1621 F20110113_AACUIS caldwell_e_Page_112.txt
6f4e15b11eafa10cf83b2e91cc3b4151
941b2c3e4cceaf31cc5acbb15ebd11eddd0997a2
1996 F20110113_AACUIT caldwell_e_Page_091.txt
c6d286eb571a817fd5fe757ff7ad9642
5a31f02f737e15d51979eca1eaf80f9c77fc6209
374841 F20110113_AACUIU UFE0006302_00001.xml
11c619b94d6db14f02b52c10cfd2bf14
437017cb952647ca7d3af4c0b2fa896ab1daef47
F20110113_AACSUA caldwell_e_Page_062.jpg
1c9b869224f16c1a4c5efb2cc9c516fd
c51e6922f6cc257fa2909676aaf17829664ba632
436145 F20110113_AACSUB caldwell_e_Page_150.jp2
8e23ecd82d45d840c033f610cf1a11d6
77b166c7180c367719d3abc39ef883d255e118f1
1028144 F20110113_AACSUC caldwell_e_Page_235.jp2
190107283ac8305ad3c3a259f324e161
bc7cfc0ea7747cfcffadfe38732d6ba183dd7bc3
25864 F20110113_AACUIX caldwell_e_Page_001.jpg
f5452832bbc4aa23a79033bfe4ae5e3a
0802ecf25e08c7d1277adf12ebdf9301d20ea15d
39275 F20110113_AACSUD caldwell_e_Page_049.pro
3bb7484c2861fa9c5a79839739776ed5
0bd9a3d57f96ad5cfdb2f2060375895b406da782
5910 F20110113_AACUIY caldwell_e_Page_004.jpg
47ced492d889318fa4a17cb9850d30fb
53a3f6eea2e4145509481511fad143e44eb73cdf
F20110113_AACSUE caldwell_e_Page_084.tif
5a2f7ccc4e4e9edacdfed6aacbba8649
951994d1cb3dd77a5853ec71f26cf95b5220d925
34710 F20110113_AACUIZ caldwell_e_Page_005.jpg
ceabc289b00fc713420fbacd84bf1587
aad91039250d12dcabdd3e773f8efdc1923a6952
509 F20110113_AACSUF caldwell_e_Page_001.txt
7bd8495361564b237b98f1e806a39da7
98d305c5ac8802a6e212d0516d3e9d48e52f2e29
1051951 F20110113_AACSUG caldwell_e_Page_166.jp2
fcf5780caa84cf32ccde98fdd491d4b2
83e0ef9de31e37f006fcc227cab131ceabd12bba
45183 F20110113_AACTRA caldwell_e_Page_151.jpg
0f10b20047358121b51aa8abea909f04
93679fb81144d8787044f48a59893bacea77569c
F20110113_AACSUH caldwell_e_Page_101.tif
f5c3ad4b336fef55aae54acceb7d5ff7
39ed21c6ef8999c06364474afcdc2f343b99b90a
6345 F20110113_AACTRB caldwell_e_Page_144thm.jpg
9334e390d294dab8aa46d788a1a512c4
2e3b34da838400b7311a56c4309354620e2a38b0
1207 F20110113_AACSUI caldwell_e_Page_115.txt
0bd07e59a426e21fd5bb4a782d89dadc
2fad31dd79941b22087f928d7053cc8f8bd058c3
14328 F20110113_AACTRC caldwell_e_Page_074.pro
3c8caf7fb611305d58f8cdf3403a597e
67ac18dcfd42099949c055513370af6669d834fe
F20110113_AACSUJ caldwell_e_Page_196thm.jpg
5e177344bdcf55f6afd0dd9caff48d0d
69be5130cc537c864778c5de0e4ade284ee978de
F20110113_AACTRD caldwell_e_Page_179.txt
afd40c5c866dc6e1cefe181b78c1e418
0df7c058ba61c48fc64142a9eb2d63b90c7d167a
F20110113_AACSUK caldwell_e_Page_047.txt
5eb02b052e2589ebcf8da5d6ed206468
db266af0dcfe0581fedb4fc53270d93c13957733
85411 F20110113_AACTRE caldwell_e_Page_037.jpg
d91c695af54fd36b3cae4ec8f2b06658
ba1473ac6d715a9e32267fbb08b6891c1385e9ba
73389 F20110113_AACSUL caldwell_e_Page_167.jpg
5421aac00a675398ebb91506dc837c9d
20ea73665dfdba6072520e35656eb53c4a6db8db
47658 F20110113_AACTRF caldwell_e_Page_131.pro
df496322a5efdf909c8de487d569548d
3b1048aab781549b5cf1e55ca2f56e0723bd1af0
5415 F20110113_AACTRG caldwell_e_Page_206.pro
3220064c0804ddad6080f23236f82483
12ec2e5d6990384754457d1417f225024298d5ba
77978 F20110113_AACSUM caldwell_e_Page_148.jpg
92b014bea83985bc8e71d9858110852d
cd55fc5559fd5f479715f35af051af91b322a580
42351 F20110113_AACTRH caldwell_e_Page_087.jpg
075dc51bccf46de9b9918d96288fa4e3
25b8ecd667a0339db2a1d8bc0f7698ddb6ef2027
1051961 F20110113_AACUOA caldwell_e_Page_199.jp2
42491aae5edfd8fdfaa8ea463120f5aa
74a85522cabe69a89c58795f916ee2c3fbb01cd8
32088 F20110113_AACSUN caldwell_e_Page_097.pro
18edfc3f4cab4ba8c5e595aa0277ca0c
4a0a55f6dda7c4b92b2f81d46573418fd5485a97
1051945 F20110113_AACUOB caldwell_e_Page_200.jp2
99bb44531447defcaa7c714e80cd3095
cd06d0c72a2719d45d9208eeb581f655cfa57151
98051 F20110113_AACSUO caldwell_e_Page_046.jp2
44c7de8bb278c4059661adf9592588d3
032d1957db4d127d74327e945bbe95d0ad0a2d56
5399 F20110113_AACTRI caldwell_e_Page_089thm.jpg
498b1a582df4ce5c2d75644a1867e46e
68c52346d70ce9958579c5b0f302f1f0f2cbf160
451102 F20110113_AACUOC caldwell_e_Page_203.jp2
1782eb43cf5d2d03b6cfb5030b7e85e0
2225a86540b42d98ee95351f192741bea71c8d4b
68148 F20110113_AACSUP caldwell_e_Page_232.pro
c9800fcfe38c280934f9aba55e3f40ca
cdb63865c99cd367f354c8de342bfb63f5f9d74f
21825 F20110113_AACTRJ caldwell_e_Page_031.QC.jpg
90315f6bb00d5951c3530b341dd71ee9
4ae1717f9ffca1acdfc5d7d9b8eda32243d693ab
452157 F20110113_AACUOD caldwell_e_Page_204.jp2
713a399e8e30f83c5bd20c5166db2d3e
83efefc953f554f2d810b6d2812bac8e587a201f
4165 F20110113_AACSUQ caldwell_e_Page_070thm.jpg
c66a75fb970ddd5280858bc983f60fb3
cdaec7ccb0949de1450af2af368623dfa5e29202
3856 F20110113_AACTRK caldwell_e_Page_109thm.jpg
fa3e5102604ca0a651aa91a6e4f5708a
7832bd402d52edea7490915a860a83dc3af7ac79
2771 F20110113_AACSUR caldwell_e_Page_235thm.jpg
8e20106fbbc31afe2324d6e9640f908d
f3a786db668a0a02bab823e5b528712a99108609
F20110113_AACTRL caldwell_e_Page_060.tif
42838fd769499915871ecd727402cb25
e4be27cb82fb2892fac3641470675c9e6856a558
1051952 F20110113_AACUOE caldwell_e_Page_212.jp2
d1a9d9bd72302b69269f7c7f92e4f94c
a22f06714f293cc4361b2c7722ef54df8d5155ef
49650 F20110113_AACTEA caldwell_e_Page_025.pro
dd29f79fc433270d2d2827d326aa18bf
ec1532a2b1deea0bb3c55aeb06a14ea0750f823c
23101 F20110113_AACSUS caldwell_e_Page_073.pro
f9d2fdc43af393608ebecb5a0f3dd191
de356edec5124b0b1aeed84559c1e00e7325aa42
26279 F20110113_AACTRM caldwell_e_Page_136.QC.jpg
1ceb7440362c740a6203de9817887ec5
99961693aa5fc846002e8d4560e69e046871642f
F20110113_AACUOF caldwell_e_Page_213.jp2
a820c429525dc25ce519988dc4203617
3a8ad46f80afd0853db2fcd63416a3607b654975
43772 F20110113_AACTEB caldwell_e_Page_036.pro
8a9d80aaa3179381bbb1e3c8a34434f7
de04c34e4b8128f57a0b6595290b5623e94c2665
333 F20110113_AACSUT caldwell_e_Page_180.txt
52c1472a4e320a5f5191cd25c9579677
bab996ec02a176e1ded0d36132bcffec9579c063
5336 F20110113_AACTRN caldwell_e_Page_098thm.jpg
a6ed0e69cc76bb7f1268daff2f2dbe38
e259481faa03445af6e48a88f36d2e2b59042122
674447 F20110113_AACUOG caldwell_e_Page_214.jp2
181595b7e95455c35363ecfeefec43b4
bd47af7720ab234317b297e6a575735afd292eff
F20110113_AACTEC caldwell_e_Page_109.tif
b43e65742a41f08dddcf99fb93472134
2250f8c20373eb8a1188e06d09632034ca6496b6
33141 F20110113_AACSUU caldwell_e_Page_221.QC.jpg
5774f4a90acb5ae6aa8594ebe929d876
ac7a0d511aaed1ba4fe40768873b629bb066930d
F20110113_AACTRO caldwell_e_Page_229.tif
c8582446e722a237d37c579e55ffcf84
d5b4d5ccac17f0d53b116e4a4219f6ab21904e57
347336 F20110113_AACUOH caldwell_e_Page_216.jp2
b4cbe943c03cc0a7e7ca9feea16aa317
7340f8b55ce7e369bb15d465b52f6a6e80d0c071
106740 F20110113_AACTED caldwell_e_Page_132.jp2
47f249bb18c90258219d7336542b2362
b645a35310aa7848d93fd13f0e18ab8357d1b328
5459 F20110113_AACSUV caldwell_e_Page_155thm.jpg
09ce7099d78355f5a1ef8ee99b42e737
8c5b9d02b23089d9da97a8f19d9bb3f3ed239994
21792 F20110113_AACTRP caldwell_e_Page_159.QC.jpg
51a44b58c53fcea9f446f16c6b127732
565f0fb3382fcd876096f6f713f313ade8bd44b0
16865 F20110113_AACUOI caldwell_e_Page_224.jp2
62e013ac2b69536f6343e967248e6599
a115c11e0488f48498c44b16091c2c840cb0a0dc
14630 F20110113_AACTEE caldwell_e_Page_061.QC.jpg
d039b47f1356be04072ee14df0430003
7508e60de297efb9c3a4988befa9d86de00a939c
F20110113_AACSUW caldwell_e_Page_043.txt
c78bb3badd75c5724326a7e1192b0c17
9dcc667b61287225f56f54786df6babfd82a945e
129593 F20110113_AACTRQ caldwell_e_Page_222.jp2
a781b95c840e52ba5eab70505d649034
9fe6d5316981638774e1fc5d30f187c511a2841a
451111 F20110113_AACUOJ caldwell_e_Page_225.jp2
a9d6b0f1d272cb4a71508053cc329c22
25329089508fbd9894f931fabc36beb5b9de5b54
6242 F20110113_AACTEF caldwell_e_Page_111thm.jpg
a1ab69ae0bc80ac739021c339e55f178
afc4bbb173867dc69805bde88f8443d3c71a71bd
6025 F20110113_AACSUX caldwell_e_Page_142thm.jpg
2c79445a87f61376a7727ecf02b180cc
0c49b314a05f23002ffe967d08101abc1886b9a9
F20110113_AACTRR caldwell_e_Page_220thm.jpg
850d4e6d687c8b17b1dd56546c756101
401827728a19a0d68b97ab00f511e5aec94745ad
1027851 F20110113_AACUOK caldwell_e_Page_230.jp2
dcc326b7ac2d754ac6a8ed830f6b44a5
6d3d9cf89eb26a45cb7f533d2a9d53153e3911a8
785 F20110113_AACTEG caldwell_e_Page_061.txt
6fdfe1b2a72f71fb8beb81a838846f98
aa199ff5a893f23e398176f1370d6df2a1c851f2
76876 F20110113_AACSUY caldwell_e_Page_127.jpg
2c503f2a5ad183ee4146927b19647c24
b23ab2d3a22bbbb413ddeb614e81271245d42005
875 F20110113_AACUBA caldwell_e_Page_087.txt
46dc2c0b6df2bd1792413333ffbf7b6b
15eb2bc0fb8524d089fa4423916c7c79db319fae
F20110113_AACTRS caldwell_e_Page_231.tif
7f0b2a4427bb6e81b1721d842ba5cb01
9f5de212a8674ac396cf5bdb4099f28735478ff8
1030097 F20110113_AACUOL caldwell_e_Page_234.jp2
223382708450efc263c6c5fc53676d14
6f20f0312e346284374148a91f948756e647480c
112747 F20110113_AACTEH caldwell_e_Page_014.jpg
c83e6d88c6c833c21767f0ba391333da
2365680d99f2e7ef3cef9fddb63c047df9721a4b
36187 F20110113_AACSUZ caldwell_e_Page_225.jpg
4f26a1cadfd57efdd2fd29b1aecc4b9e
cea384857eeb82ebf1ede92f894166ac8dc1fccc
F20110113_AACUBB caldwell_e_Page_069.tif
9222259874d8c91db8a6c3817a4fe769
f10db751b18ebaa076d8594064f6bf1b18b7d530
1051782 F20110113_AACTRT caldwell_e_Page_175.jp2
00d43f174bbd48edbb1ed732bff752e2
05f7eaa83d38027e681553b48778cae33fa95ed8
19148 F20110113_AACUOM caldwell_e_Page_237.jp2
4f246d4f4fceb88e8016d2011f15db98
3170bbed5a3b58197de855dcfaedbbea454b0dba
6111 F20110113_AACTEI caldwell_e_Page_249.QC.jpg
defc3c7561518abcdc5765ffa1c9093b
bc3c1b009a866f23652f76320d2ca0c8e0d73a10
1051855 F20110113_AACTRU caldwell_e_Page_165.jp2
ed0d03315244f0fc2fee9c5dea68d41d
35ce14ceb72eb2a941ee3f9a7dcb9047843c7c51
1051915 F20110113_AACUON caldwell_e_Page_248.jp2
484310a4f258b63b8a0caa19eca9cb31
64d82b9ff370873e844ac6010b102fb6a1125ec5
12846 F20110113_AACTEJ caldwell_e_Page_076.QC.jpg
2c4a2fa37149d7b0ea15f813d55e0b05
f3bbdba86ba81a9f2119ef596cfeb16aee23a553
F20110113_AACUBC caldwell_e_Page_034.tif
b4e18b68c4efd4f8a5393ac6b99bff75
cb460499acd18216283a7a38b5b61912175cc01e
F20110113_AACTRV caldwell_e_Page_222.txt
9aa9c93cfbdf5c5a98c9a1885020ad79
07c73e3c36f6fd26fa94ed44ee08bac5b2a0b6bf
F20110113_AACUOO caldwell_e_Page_001.tif
0fbd71a3718f76db5e8f789f18ac47ef
6ad2889c5cfde246e2ec81458ba1dfeac03f35aa
76422 F20110113_AACTEK caldwell_e_Page_137.jpg
1effc8287f6bbf9d4d59bdc832dfc61e
8a2f75648413926ed487b22ca828df27420df30b
77176 F20110113_AACUBD caldwell_e_Page_023.jpg
f44e5301dc8008e7d585c4790c2e91c5
6cff5306a4be94bc36d9aa78fecdc40deecb9466
79293 F20110113_AACTRW caldwell_e_Page_103.jpg
81ae8f16eb88aa1b8a6822ef67603618
4f676627f6377b61d3c2d7b71784caec3572df51
F20110113_AACUOP caldwell_e_Page_003.tif
05c5532c57cb59894e713415982830da
ec47b27fb6e545c2942740dfa940930892385529
26732 F20110113_AACTEL caldwell_e_Page_032.QC.jpg
4a23451c27946271c4210817fd701372
7d221dd2fff09650eaa7ff25a2602eb3a80d9f15
F20110113_AACUBE caldwell_e_Page_238.tif
a45d1054762df82078988aba86f4f35b
eb53fd97e6cc7faf6ab248aea31238314e2423eb
17698 F20110113_AACTRX caldwell_e_Page_171.QC.jpg
4451eda072780a0ba45bc36e3f902390
4121af3ab0dd6cefa51e230bcb1946d3a985cf43
F20110113_AACUOQ caldwell_e_Page_008.tif
4edd33346422b688e45fa5f754bfcf88
aa386fa9443385ba7307995eef4d1a7002f3a52a
82125 F20110113_AACTEM caldwell_e_Page_072.jpg
8fc7380d41f95926269bbdefcbec4565
1e21eba58c8d96f7770fc748e76d885dd728f9d9
13250 F20110113_AACUBF caldwell_e_Page_102.QC.jpg
647dc15eaec6b144b0947168229c9df3
cfa21eeb54765ec28186f45b40a43422bea1fed4
21675 F20110113_AACTRY caldwell_e_Page_174.QC.jpg
a70f1bd8ebc58245dd856d822dd36269
11652d98d1ce21758d0d0d0dc41060a4b942a204
F20110113_AACUOR caldwell_e_Page_009.tif
871bddc48ef3abc3e716a9c6392c667a
60a94114898df2bf148de0cd05d54960b9523cd8
23539 F20110113_AACTEN caldwell_e_Page_067.QC.jpg
ee73af4af5dac179666db013b46230ec
1daf4d72ce5f2e6e91fc2e1ef5797b75c81914bf
105355 F20110113_AACUBG caldwell_e_Page_024.jp2
399e9015faa2e229c95f5a81d64c119f
095a29fdfe3b7a8229340f22c8813a2640c96480
2377 F20110113_AACTRZ caldwell_e_Page_057.txt
89772d27331aacad7d14da0bc9010e2a
ec9456de156c3fe827012bcf3d292509223712b8
F20110113_AACUOS caldwell_e_Page_010.tif
a7fd62dbede527238d099bd7b933d854
c6dab8a0a12d845892583ba059e892e66cd59920
22160 F20110113_AACTEO caldwell_e_Page_223.jpg
1db845b1f0f58ce153ba26bd0f17d9e3
18d0791e46e180d168c5c1faa42e737c499954d9
593485 F20110113_AACUBH caldwell_e_Page_078.jp2
71577c73764f81a60b3d44c7ab450f09
2c48d946c9879d149296e3391e6e32c2916404bb
F20110113_AACUOT caldwell_e_Page_011.tif
c0dead52f8a6f8c0ffe972f1a3969439
290a17c6af546d5fcd413247056c62f93c46f8f1
F20110113_AACTEP caldwell_e_Page_140.tif
9fbd452fece0ac555247208a6e5c55ff
91fe2483ebe630721a2fa75b5accc72dc33449c3
288 F20110113_AACUBI caldwell_e_Page_169.txt
ff208a624faca1413001157ee365ee06
b665698060fa1fde0de79a0cd7eef4d586e3282e
F20110113_AACUOU caldwell_e_Page_015.tif
e9613aa6d70950c829dcebb1e47bd618
bb4c1f37903156e54ad30cc41b01b3f4ca12d406
18895 F20110113_AACTEQ caldwell_e_Page_056.QC.jpg
f2a172cd4dd2d8eb54f975e22334fdce
1945dc1260e3b519597ca4d2a3ae5bdf81b5b3b5
64004 F20110113_AACUBJ caldwell_e_Page_176.jpg
4aa8dce74623317ccdab051c6c014677
1830aa69cf3e0be1d476c5e47726b029153dfc5e
F20110113_AACUOV caldwell_e_Page_016.tif
39ee4b91724d1b373dfd28fdfe545772
3fa94abae4df16cea96708845baa85d9e5601113
1890 F20110113_AACTER caldwell_e_Page_080.txt
b2f3dbc84038eeee9a1d58c1b113b852
441d7c848f7de074ce9b0669f8011c059143c8bf
13309 F20110113_AACUBK caldwell_e_Page_064.QC.jpg
2b73b16a7d8c3b2b1b102da780126b58
6df78aa3733d10323ea6c1c6631d2f8b2bd4545e
F20110113_AACUOW caldwell_e_Page_017.tif
8601d70f5aa9785e9a54c300315ba5f2
65399cdf3deb6f2275aa9a3580d19d28523f8c14
F20110113_AACTES caldwell_e_Page_044.txt
80bd7800711434aaeee9cf98afbf8c66
a4ce0c9f1f0b65772261d1ed5bd6c2dbb17d5424
19847 F20110113_AACUBL caldwell_e_Page_160.pro
38a2651359a6fef218c0db6e81eceff6
70e9395c1593e326eb3fa5badd407adbc6a84862
F20110113_AACUOX caldwell_e_Page_019.tif
3110a3a44039bf4f2214710d3b430b86
78307187d54e052f2f61f869e4bc80a4473ce6ec
F20110113_AACTET caldwell_e_Page_155.tif
cb9a6bb2603a6c8fdb564c1dd0d8e669
36df9bf2612f03d05402d8b89b7af90113d57b7b
F20110113_AACUBM caldwell_e_Page_192.txt
8b455995133f9a0b395a293c8cfb176f
2e5a8983ab3be39cd333a141fd19d30b6936872e
F20110113_AACUOY caldwell_e_Page_021.tif
c20b80ad69ff66fcfad98f062f630ecd
5987cb15213f1e839f7a1eefea3b0213a2d01a76
F20110113_AACTEU caldwell_e_Page_008.jp2
d33ff688dd3043372625779c80592ccb
64217edd0fa39f332ec9c6b501252326a0448774
345197 F20110113_AACUBN caldwell_e_Page_240.jp2
418b972dfa457bb63ae9d83501401f78
7b806c83a47051a444711e7b235019591d1c96f1
F20110113_AACUOZ caldwell_e_Page_026.tif
4028669197602e069409bb34f1a52c27
4ba0dec93f4a86a382f789c4b687cf07786d3c94
2023 F20110113_AACTEV caldwell_e_Page_128.txt
b8cba3e16e746c43563364d0a882187b
efafef0ab537ad7295990556762bce2e5c174921
18005 F20110113_AACUBO caldwell_e_Page_102.pro
6e28727972799ae41d5fd512ecc20e4f
13cc4b02054b8d970c2085c703d38eb12698105c
F20110113_AACTEW caldwell_e_Page_193.tif
ba771b5f3dcb46bfcf9a5ce35ffd043d
85919801c9b80b3f7b7fd7996c1eea4bce3df153
F20110113_AACUBP caldwell_e_Page_055.jp2
9a26b08315d2e97c2418ab23d333ba5e
bd84cda521fc04934d021d95b041e7a58203d230
4700 F20110113_AACTEX caldwell_e_Page_057thm.jpg
f42d21fd45601aaaeffb2d96f4288e56
881209d50b147e02a26e60dd152b27bce82ad466
45727 F20110113_AACTXA caldwell_e_Page_137.pro
1cf7b0e60b884c5af11dec8fffc6c902
673ec056807caba3f2eeadd6f644ea80d3a3f3d4
28434 F20110113_AACUBQ caldwell_e_Page_030.QC.jpg
1cdc23ea6e95298423da6a6798c6ffd1
8ddef482d91eb80dff04a35d4c5af4c5ee101810
93167 F20110113_AACTEY caldwell_e_Page_039.jp2
8a7acdf998eba032fcb8808be3937880
5768f20fac5337fb88cde81c0d640b2e7ea3bbec
6478 F20110113_AACTXB caldwell_e_Page_222thm.jpg
7a3683d8c4cefc96c41715721a4b4417
e0061c635e6852884fd554d746e64c329a1be854
13809 F20110113_AACUBR caldwell_e_Page_081.QC.jpg
2f230801b065c91d47bef03bf6cfda7b
7411e9fb35d4f3588659ccd16e01709c1ac162b3
F20110113_AACTEZ caldwell_e_Page_163.pro
5fd740d00121c116f71421c7a66963ca
74dea2adaf9d3ff8fa17d283267efc92ef417fca
526 F20110113_AACTXC caldwell_e_Page_223.txt
8b9b41b5a36fcab72024563150e7b617
00810afc327a4c978f5b14a2bbe6d2814f58bf38
F20110113_AACUBS caldwell_e_Page_136.tif
eab959074648d4979e466a463f9d1713
4a48f3b272138fbe0f3fdd4ab723bae1d9ac8e42
1747 F20110113_AACTXD caldwell_e_Page_099.txt
e635e915d0cc9ab06777e671347d9c07
ac2e29f686b424c4d575adc3aac3f9a1e279276a
66332 F20110113_AACUBT caldwell_e_Page_019.jpg
394ba21ed9662cc3ac5428d59a2163ba
c79fc3da852a4122748e272a5b038f5714f1a599
50903 F20110113_AACTXE caldwell_e_Page_079.pro
108702f3e7ae9a4cebd0ff0028101343
dfc5c80cad6cb77317021cada658d0a6ce292b29
75322 F20110113_AACUBU caldwell_e_Page_108.jpg
57ef3c041b4106d4f1bd15a7e26011a5
f6b0b41c2c110519c4d08db9b2912f7e4ab8993b
10876 F20110113_AACTXF caldwell_e_Page_239.pro
b7064564096f0d230370615e4fee50fb
5dc3813f2654fef59a67792c586045b0db420957
F20110113_AACUBV caldwell_e_Page_059.tif
7dceeee43ca5f019e31cc5dad988625c
7c77ce4acc63324b9d76f886143d38ded2e12584
60815 F20110113_AACTXG caldwell_e_Page_248.pro
b71e3d5596d3b13b968859407f1f8002
3f9a87534debf5c1c5141cb643a1832178622cf8
1241 F20110113_AACUBW caldwell_e_Page_048.txt
3d6a00a5526200901e3af93b14ab4677
0214099680be728c99dbe24f4997cb94fbf6d40d
35404 F20110113_AACUUA caldwell_e_Page_214.pro
caa90131e7005bd708ef1b07052dd5a6
78f1aade98bbc0d5ba8d7ffb66f9bacb2ac4a559
81006 F20110113_AACTXH caldwell_e_Page_173.jpg
8fe18595376aea9e59dcd29cb09cd24a
3fa081a2d4c14687dab06c15e5084d21c7723aa0
18105 F20110113_AACUUB caldwell_e_Page_219.pro
0fb2bdd903dd1e6c78c6410946282355
537309039f03f0fe06f5faf96a8a987f9a86a738
903 F20110113_AACTXI caldwell_e_Page_182.txt
dae598b201885e1b920177a2e7ed3a03
2d3519012ee56056900e01ab37c6e2bcc2f0197a
F20110113_AACUBX caldwell_e_Page_223.tif
3e66d968fb60cff1c52c0f1bcb4c7e81
f456ec296a82480b7ad922d68896ded20ef7be7e
6123 F20110113_AACUUC caldwell_e_Page_220.pro
08524922be955c09ba69747bcf46622a
5fea5185fec1b2a37bc7474193cafb52cb0c517c
60133 F20110113_AACTXJ caldwell_e_Page_212.jpg
2e99f4a55b2fcd6db22d4ec93c3fc18f
3827937efec6e095e63b856908b479460339d336
95117 F20110113_AACUBY caldwell_e_Page_088.jp2
cc41252f8d96fc763aa54da8da6b5d80
216886a7a41ac7ce0c140ad0cd758903eda1e42f
11228 F20110113_AACUUD caldwell_e_Page_227.pro
5eee0d83112d2fb5838fd312d745d101
cb60b2a956fa9e70550d429fad4b8a0cbaea5850
60358 F20110113_AACTXK caldwell_e_Page_158.jp2
1cbdf95be48c7a0e965f1f13cad62395
31b8401458e63b88dbe531461d8936e6b1b41898
43060 F20110113_AACUBZ caldwell_e_Page_159.pro
a5fce3a7e7751fe63fdc1e746e9b165d
fdbf8d4e0dcf1543d7db1955f5c852115b86ab32
6586 F20110113_AACUUE caldwell_e_Page_228.pro
07fe045baff76af30f2654ea1e328fe8
85b6e3210efda683546ff284dd80412500a7598d
1051897 F20110113_AACTKA caldwell_e_Page_196.jp2
b3bb0f94836b751f283efd2ef826163e
3f72a9654d2668951dafc36a4998abee06476bf0
25158 F20110113_AACTXL caldwell_e_Page_022.QC.jpg
b4a42520ebb019cdfbd5e817e12011d0
50b6b703fbbe25deaff1916cb86638a9620b1dee
72295 F20110113_AACUUF caldwell_e_Page_231.pro
6609a4b2cb9b1eff2262e6a6f9c85422
2513f8811d8fe579f74a44e4e4028038283a8ffe
5501 F20110113_AACTXM caldwell_e_Page_124thm.jpg
afc20b35fa57011b35afecf497ffefae
92a5c59de7d899bf144a4daa179450208fae5649
73267 F20110113_AACUUG caldwell_e_Page_233.pro
234897e466af16ff988940d2c652e39c
8b13a38fb40b40b07fc10e334c45fc1b392f76e1
1176 F20110113_AACTKB caldwell_e_Page_076.txt
d9c060347d39cee1074b991c8b9a66ba
1d0aa77160356c27490f08b3822dcdae8a1efde1
F20110113_AACTXN caldwell_e_Page_133.tif
6a4dd2d1296175adb69120365bbbc927
fc106350159d51ff5b16a353c4397a868d4a4a67
67882 F20110113_AACUUH caldwell_e_Page_235.pro
cdd27258db2d11e441e1f47f87ccadc2
99d3d0ee177f0330e5c47b4304145c3fc882800b
31091 F20110113_AACTKC caldwell_e_Page_217.jpg
38560dbddbc82529947919a133fb60f5
d419cc069194e81b85293421ca64b121bdb5aaa7
14546 F20110113_AACUUI caldwell_e_Page_240.pro
e5822b25593241b3b194becfe226743b
27d74b9e9eddc5fef2ae3a3d9ce80ce9a40b6b48
532565 F20110113_AACTKD caldwell_e_Page_085.jp2
34f4174133a29527b43542700afb676d
04bb483a876becc23b3e84702d74d35e173f2cb6
3294 F20110113_AACTXO caldwell_e_Page_181thm.jpg
5f405e2d87ce1f5c9e99c30f86d69b56
e14c3103b1c4f9cdd8edbdc729ff24fc178ca0ed
6134 F20110113_AACUUJ caldwell_e_Page_242.pro
63a12682236a522718092c1ef6f59423
4c8ecec3e8f7308d0c62e2c0f123b4efc2819e35
F20110113_AACTKE caldwell_e_Page_243thm.jpg
834bbcd01c8494dcfe43f9da2d5c7881
59660031534a859ad02d957cf47885b92d315827
15510 F20110113_AACTXP caldwell_e_Page_201.QC.jpg
615fd323bb2a19331dfbee869ee5b20f
74a53e37b781a78f98595cd775147d2e1622c03d
5815 F20110113_AACTKF caldwell_e_Page_178thm.jpg
fcb444573b7ffc4c45bcb590901fcc82
9494ceb7853b89319567f52abe009e86f73a17d5
110198 F20110113_AACTXQ caldwell_e_Page_154.jp2
845eb18fb67aedb568d549f498ba51de
cc1ee36c39f5b37cbfaebb94e1378e4eeb1ca544
65184 F20110113_AACUUK caldwell_e_Page_244.pro
8d6c1f54c0561a54bd8d07453004ff4e
c01ceccc8ae7c06239af98bc1ca4c988c5d8e087
78986 F20110113_AACTKG caldwell_e_Page_195.pro
17bb587225ff7f19fb4e66a7b5bcef78
347d5062debd2e3467aecb2afe2dd2854d5f8a46
52750 F20110113_AACTXR caldwell_e_Page_229.jpg
d5ea416f84392afc01daf1c75f1c832a
e552d264a80d1a4944b17548273f974b032a596f
10177 F20110113_AACUUL caldwell_e_Page_245.pro
1b4b42233ed2db805e7970675199148f
ed180dc97b92d3d80a91960d9667cccaacd9fad6
1612 F20110113_AACTKH caldwell_e_Page_069.txt
012026b34a7cd5b10cd0f18e0ee5789e
0d82de1bec0be0daf25f9c36dddf0f2247b592a2
23275 F20110113_AACUHA caldwell_e_Page_143.QC.jpg
609764f3bf1e5770bcfc744d22c8d940
3f0f7d76a5a211383750c74e582d6a1fcaffd1d0
42745 F20110113_AACTXS caldwell_e_Page_113.jpg
72b87cd60b328cbe178b949c7c971bcd
03190aea08218ecf3269b220555ace481b56ccf4
58293 F20110113_AACUUM caldwell_e_Page_247.pro
9cefbcd5ab9df91da4446a977aa4d91f
24c53ed9da07c9844ade529e1d97ccecedf3f975
1810 F20110113_AACTKI caldwell_e_Page_090.txt
2e5a65c74322de1a3683d9305ae7b7ec
29261a49cd2e1f7d71b3e144e60d53e1ced5b2a1
95253 F20110113_AACUHB caldwell_e_Page_134.jp2
0e567a63783a86cc82bf992dbcea5cd7
b96117a11dc0e2b54d1120b14df4e1e23ab77c04
1741 F20110113_AACTXT caldwell_e_Page_036.txt
6abb7654daaafa96e700f2cb1d15df48
dbacd20559471caf3cba687dbb8af49179c8dbc5
10884 F20110113_AACUUN caldwell_e_Page_249.pro
5aadece3b90952ac009e76822f20fcc7
c856711befcf2187c8226200c4f1800d6ad2e9f1
F20110113_AACTKJ caldwell_e_Page_036.tif
2019efafde73cc0a2635ee6ce906b1e6
4195dc1ba9039732726238556089bb9e3fa85729
28633 F20110113_AACUHC caldwell_e_Page_015.QC.jpg
b36d459ef0f7918e29fff8c8d6e2d7bd
4e53b38b19b95674d0593c9e58a3c07638f23140
66231 F20110113_AACTXU caldwell_e_Page_221.pro
aa1351d44c271cf40b3132a93b1cc513
1a0b4f9419eb16f223382f8cf02f04daf00e4ebc
278 F20110113_AACUUO caldwell_e_Page_003.txt
6a298dfe0de86c0bb53da1836284ed2b
d2c58147d4f137979d70b18cae7085e93692caa3
68445 F20110113_AACTKK caldwell_e_Page_057.jpg
7934e51e3731f820f2e7d6f00c42158e
061ca5f28151211202b26eef5a79e14cf261ceb2
4365 F20110113_AACUHD caldwell_e_Page_101thm.jpg
e76498123875ab25fc299105c5fe85c7
9ef02dfed8c41f255dc8193c003647ccc1158560
6287 F20110113_AACTXV caldwell_e_Page_133thm.jpg
52e8dd22cc49df2b509d3bac1cc51e42
25f4dc7411ab89e41a1840ee2a6c4ca24592039b
2290 F20110113_AACUUP caldwell_e_Page_009.txt
e06bdc96ba7ac305bc20ff50f512ec9e
a3f33efe5c5beaeaeb0cfa9dc6aac5abd062cf41
2594 F20110113_AACSNS caldwell_e_Page_011.txt
f7b9e1b0a01ab947ed3a126d6264cc59
9ffceb8f2cc2fc4ea424d53c15128573c348ba06
7393 F20110113_AACTKL caldwell_e_Page_117.QC.jpg
3ded35176f75a030e548e262bb483a71
a8b7137233f0c3b6bb0db2fc17ca89bea924433b
4538 F20110113_AACUHE caldwell_e_Page_042thm.jpg
800a4e385153ae5a1e15b5375d7b2c72
51d55acfcdb41a725579b168bb59b13d229e80bd
6145 F20110113_AACTXW caldwell_e_Page_163thm.jpg
48ab34ed1d70dfea3d7168ffa7202253
1435eb0f24b8efd4d26a4ca8ef1e8785674123c5
3211 F20110113_AACUUQ caldwell_e_Page_012.txt
bd120ae969757fa4233e104b520df74e
42d47f3ff03f617bbe34cbd195b1c59de0ac4bdd
14076 F20110113_AACSNT caldwell_e_Page_188.QC.jpg
3766e14e6b114b9789d9de06ec89a979
76ffcaa6161b1051cbdc1af9fcfd983c2026063d
2871 F20110113_AACTKM caldwell_e_Page_232thm.jpg
058a59026a9f925fac87f78db10ce5f6
bffef26ce01c48259400696c198f1ce0420d0264
4655 F20110113_AACUHF caldwell_e_Page_169thm.jpg
3de8033de924d18c39a360d84b72d9f8
9773dc18f424b3dad656ccd760f2cd1b277c01d5
50193 F20110113_AACTXX caldwell_e_Page_008.jpg
244a57baca776e19a19af09503d13dd0
4310f68f27a6b70bc7ce811f6847837598951522
3196 F20110113_AACUUR caldwell_e_Page_014.txt
f1c6d3086ac1f10cc3fc2af83cb56104
f672024d7b7e8739e638d40388837dee07d1c51d
F20110113_AACSNU caldwell_e_Page_174.tif
3c0e6df3f93f4bbd8fd5713130e04bc8
6deb0b953996f63d3d1ba8f327a618749e1a75a4
6116 F20110113_AACTKN caldwell_e_Page_224.pro
65b93857a9f9a7b297dc8a3c8ca2a7e1
fd5fdbaede518b1fe1d60d39cf56aeee1ac9ee42
12944 F20110113_AACUHG caldwell_e_Page_229.QC.jpg
362814f1e631f1d56f8c8ff468f22bcd
9f7666cbc066f1d2ce555d222f1ea8d0073b1e7c
13403 F20110113_AACTXY caldwell_e_Page_074.QC.jpg
353ba13237e1d12a0e28c824ceeb1d30
33e7e52202a9ccf06b842285bff55498674de651
2872 F20110113_AACUUS caldwell_e_Page_015.txt
e0ac31cbc294a54cd3d8639bd2b57d8d
3230e79051b8b78c0e25e1f540a2089ab9ee3861
6442 F20110113_AACSNV caldwell_e_Page_247thm.jpg
3d37621560a6d5525429ae8ce09609cd
43c1fda3c45e63780ebe5951e55d79ac4f3b4693
F20110113_AACTKO caldwell_e_Page_180.tif
91df5bddd5178e666452da57fa316c3d
820b236332efe4e3231bfe00177a40d0c309544d
1898 F20110113_AACUHH caldwell_e_Page_063.txt
cb170ba48753c0d5d614cb9ccb975db3
73813c71ecd78f5f41d145b64e48f93f09a9c4d0
F20110113_AACTXZ caldwell_e_Page_124.tif
2fee5781228b1ae27337758597e09aea
eedca785dc3bfdee23e2a5fcc29d6914e57189af
2695 F20110113_AACUUT caldwell_e_Page_017.txt
7cc61d9acde4490e135a96bc0d54fcf6
fb6f7ba9e733e023e05b9ef79fbb7e0696e53e87
24299 F20110113_AACSNW caldwell_e_Page_154.QC.jpg
342e6f5f3d2ce2f6c797de15a59449d6
bf055e02db5890a00c29792efe9f1e4c8054ef06
5630 F20110113_AACTKP caldwell_e_Page_088thm.jpg
8721e2c1ea3c1ffd6add67819dc257d2
cca5ec24c223efc65d8caa3aa85700147f183e99
10437 F20110113_AACUHI caldwell_e_Page_216.QC.jpg
d916d978e79cb1d1abf4e0b8a345a0db
e67ea9244d54cd66e9a4dda4799ab0357d2b001d
1639 F20110113_AACUUU caldwell_e_Page_019.txt
6c8c8d7553b3722f93e931dc8758d33e
817d7f046a6bcab1eca9285feaa2c21724a10cc6
22422 F20110113_AACSNX caldwell_e_Page_123.pro
4bf90b5bfd2e0257fef485418a5379fb
3c208408a5c0c583c7c8f8f62394beb55ade048b
80809 F20110113_AACTKQ caldwell_e_Page_132.jpg
aa1f60bcb25ea2cb3b509fb7e2f5cd58
afdc8232f31105358bfd582944f1811010fc5021
F20110113_AACUHJ caldwell_e_Page_247.tif
b72523634c2f6e944541f03945bd813b
3cc9367b7f42671fcb84923257e435e46890f68c
1970 F20110113_AACUUV caldwell_e_Page_025.txt
7c03771a9f660ac9d5a95e20dd393bda
7417ebc5a36c55ca81839a3c94c75bc693b43b89
11818 F20110113_AACSNY caldwell_e_Page_060.pro
74937e20221f2da44569191f5f703aa5
b1ed2d9effb3794afa2657e54989518397e206f9
19119 F20110113_AACTKR caldwell_e_Page_215.jp2
5acdd750a7a79bf8fb3da69d7e465d5d
973161fbfbbe92e76727f5d404894b46ac0a7947
127900 F20110113_AACUHK caldwell_e_Page_013.jpg
4bcda6ab1a39c35bba7e34f85c87bad7
1abd12e0a21cfc9b52d800c180ea1375c7107afa
F20110113_AACUUW caldwell_e_Page_027.txt
cf300c4214905847a976d37bfa585de9
0984558feff5558f73067fff94df0d9fac042072
13907 F20110113_AACSNZ caldwell_e_Page_192.QC.jpg
3c0428f4bd87cc506c6bd9a2a0cb4e2a
bfd1c363ee54b8610fa851c10d237c408314a71a
F20110113_AACTKS caldwell_e_Page_022.tif
a5a52ed45ff735c4e5456c3c25f85cb4
9b6220c7de72838a62b41f33eac1a654f919ffa6
41118 F20110113_AACUHL caldwell_e_Page_057.pro
a4d100277a448da4379efc1e0717a275
e7f082acace105352d2639d598afb92eff99a890
254 F20110113_AACUUX caldwell_e_Page_028.txt
45802ccbcff66bf48fa241e273c455fa
65c0943c2b9a4621b6c48c0e45738325700b7429
2978 F20110113_AACTKT caldwell_e_Page_186thm.jpg
5d2ed31c6c7ca543fa304957557029ca
29520be469063bd87d4df2e5586b70c10a792e87
42899 F20110113_AACUHM caldwell_e_Page_182.jp2
c9abd6129d236945557fd98c3313a30e
1cd786ff0686a6938c197b6f7ac3d896ce01e0e6
1291 F20110113_AACUUY caldwell_e_Page_031.txt
9ec81434c78b9c10254d18d7f6859e05
c27c564a5223f44e204868a0e84586bccc2bfcf3
15953 F20110113_AACTKU caldwell_e_Page_076.pro
efb6227694e7dcc6ca2d00c3c0cf82d6
9a8da92a3b3db6c7fa3434942f902cdc48ea3033
46791 F20110113_AACUHN caldwell_e_Page_127.pro
cf8f548d45504957c4af7e9a24d40be4
5a34b875bfcc5eab0dc9ab5d7f5d874ae62721f0
2826 F20110113_AACUUZ caldwell_e_Page_033.txt
66c8680351a8c00c9c6dbb6effa663b6
0d95c78f7be136e434c3511d4082960e8663e962
F20110113_AACTKV caldwell_e_Page_212.tif
2626c306ee3d4604f0d9b45cdf8b57ef
5d661a8fb19897bc686c7091e4a1a4ae2da38769
1051963 F20110113_AACUHO caldwell_e_Page_016.jp2
a034f9da3ee614ce655ee714410e1a5d
6d163832b4adfb5388120ed4d9760976b923f62a
10203 F20110113_AACTKW caldwell_e_Page_218.QC.jpg
f084d7657ca3e93b0e3e5a8498195fd1
05c9126618354808b86fb062f46825c733f9b621
F20110113_AACUHP caldwell_e_Page_141.tif
5b1fe2a289b424de153a64e90dd13714
67601c7f6cc7741f3ff22c10a52360c257390123
5522 F20110113_AACTKX caldwell_e_Page_125thm.jpg
41153e4e19d247f227e08a4beb610551
3d94ec1c500fad0cd73a11670f0b066fcd6543ba
129 F20110113_AACUHQ caldwell_e_Page_002.txt
a94c287121b50a73ee07f2e62555d213
6de8a81e9336ea0546f5a9704cd2ea18f4dc716a
1003 F20110113_AACTKY caldwell_e_Page_203.txt
f351209a1bfc534cc82af4d4e2244537
a74fbaff710f996e76720277b5c64ca2bb5ffa07
20302 F20110113_AACUHR caldwell_e_Page_098.QC.jpg
428e5a79c759cca642162ef8d764a739
6347640caa117d5ce5e3c8cfa1ca6784761b8707
F20110113_AACTKZ caldwell_e_Page_096.tif
bd6a909b6d349e3f56ca728918a52628
076bd0093500ce05d21e6f186d2b2ff782781c1b
28834 F20110113_AACUHS caldwell_e_Page_181.pro
f45d10b3a1f05c719c21f89408d20968
6d63ed30907600d76398a7f9353b03ef8a324816
1973 F20110113_AACUHT caldwell_e_Page_100.txt
4cda319b507c99f4a4cacb8280c26686
150350c38d520bf0a30de685a9f83f5fb341e23e
25451 F20110113_AACUHU caldwell_e_Page_111.QC.jpg
2c3ba11bc53ed22c945a9119e9ead965
0d287b523073e3605530b6535d207cc7c1ac14ff
68915 F20110113_AACSTA caldwell_e_Page_033.pro
ac46d521e628268cae4cc7824af97e14
a09ff5753983a5e985ff15cccbbc00b6bed9895a
41617 F20110113_AACUHV caldwell_e_Page_039.pro
eedaf422a6f4bbc4d8343efafde1434c
fe880fa322fa52c5b448616422c38e6205f3df43
63136 F20110113_AACSTB caldwell_e_Page_209.jpg
65df0ec887421d76e1c762780f6afd87
a2279d2bc8aaf597bff8e8e78f5a2fa6113fd8f4
49308 F20110113_AACUHW caldwell_e_Page_041.pro
bc462b0202ddc9c9c10ce4057f18f997
9660464e0968de4f6ee173271e89b210e00d9328
22028 F20110113_AACSTC caldwell_e_Page_147.QC.jpg
bce9c4d41046fba0315e7990df15d59d
d6b6d95bca30d91de387bab8631c84ba96968af2
47983 F20110113_AACUHX caldwell_e_Page_139.pro
6ab3166db7101cb7251cc5d89f285e10
57d5a7ed1bf75dc0922b5af69b5a057f0c8d0737
F20110113_AACSTD caldwell_e_Page_007.tif
f05466cc78570a8649f710dddf92745a
ba070d2dd63034143fb70eb19ffcf74db9ad8bf0
F20110113_AACUHY caldwell_e_Page_208.txt
255942e55972e80f77f7da396a68f4c1
8d73adeb1a86873a18954c6ad1b0f5f153472b2c
20553 F20110113_AACSTE caldwell_e_Page_049.QC.jpg
cecb2f1d17461a93719ccc5de1c25a86
a16fd73eab4699e14de0de04fb2a1d0fd9250306
23546 F20110113_AACUHZ caldwell_e_Page_245.jp2
e07180ea4c06121045e9e7c4af899d4c
963962108c557bf624ae6835d8b7ca2d5b19aa38
26799 F20110113_AACSTF caldwell_e_Page_249.jp2
c497477dd1f707390d4a1b5bc816f73c
7f0ad3e20fcf68199e5898ef423a2b86786198f7
4117 F20110113_AACSTG caldwell_e_Page_229.txt
294a0bd469bfdb3709c27d04e94c36ae
64fb3cc1ad930c594faa2a5ee6f6f66e0bbeb507
F20110113_AACTQA caldwell_e_Page_227.tif
953013142d57c3548f9c4c770b74f0d5
222de96350b47afba39716ebd17601230cf8002a
664 F20110113_AACSTH caldwell_e_Page_216.txt
89f0c3c0cbd3126ae755778faea20c93
bb47f8ff5578b79738de350734147c652c26150a
5266 F20110113_AACTQB caldwell_e_Page_029thm.jpg
fb1a3c2729eb62779300930031c44daf
55b01a65f0b31c2e9c5fe5b8048a220eeb362d42
480506 F20110113_AACSTI caldwell_e_Page_070.jp2
71ea69563deafee257f7bbf635b9ee8b
c4d13661caaab800537eb4dbfc0d277ed9aaba62


Permanent Link: http://ufdc.ufl.edu/UFE0006302/00001

Material Information

Title: A New Method for the Modeling of Elemental Segregation Behavior and Partitioning in Single Crystal Nickel Base Superalloys
Physical Description: Mixed Material
Copyright Date: 2008

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
System ID: UFE0006302:00001

Permanent Link: http://ufdc.ufl.edu/UFE0006302/00001

Material Information

Title: A New Method for the Modeling of Elemental Segregation Behavior and Partitioning in Single Crystal Nickel Base Superalloys
Physical Description: Mixed Material
Copyright Date: 2008

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
System ID: UFE0006302:00001


This item has the following downloads:


Full Text












A NEW METHOD FOR THE MODELING OF ELEMENTAL SEGREGATION
BEHAVIOR AND PARTITIONING IN SINGLE CRYSTAL NICKEL BASE
SUPERALLOYS















By

ERIC CHRISTOPHER CALDWELL


A THESIS PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE

UNIVERSITY OF FLORIDA


2004

































Copyright 2004

by

Eric Christopher Caldwell





























This work is dedicated to my family and friends who have been with me through good
times and bad. And for those who travel in harms way, there is a light at the end of the
tunnel. Godspeed!






















"Nothing of value is free"

- from Starship Troopers by Robert A. Heinlein















ACKNOWLEDGMENTS

The author would like to thank and to acknowledge the support of Dr. Gerhard

Fuchs for providing the way and the means, Dr. Reza Abbaschian and Dr. Robert DeHoff

for support and consultation, and my family and friends for their support and

understanding, especially Dr Daniel Villanueva for making me realize that I was in the

wrong career. Additional thanks go to Wayne Acree and the staff of the Major Analytical

Instrument Center (MAIC) at the University of Florida, and oddly enough, the United

States Navy for giving me the backbone, courage and dedication to see the job done.

This material is based on work supported by the National Science Foundation under

Grant No. 0072671.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ........................................................................ .....................v

LIST OF TABLES ......................................... ............ ..... ix

LIST OF FIGURES ......... ......................... ...... ........ ............ xi

ABSTRACT ........ .............. ............. ...... ...................... xix

CHAPTER

1 INTRODUCTION ............... ................. ........... ................. ... ..... 1

2 LITER A TU RE SEAR CH .................................................. ............................... 9

2.1. Evolution of Nickel Based Superalloys..... .......... ......................................9
2.1.1. The y-y' M atrix ................ .......... ............. ............ ................ .. 10
2.1.2. Casting and Specialized Processing Techniques.................. ............14

3 MATERIALS AND EXPERIMENTAL PROCEDURE ...........................................19

3 .1 M a te ria ls ........................................................................................................ 1 9
3.2. M etallography .................. .. .. ..... ............. ................................ .... .. 21
3.3. Scanning Electron Microscopy/Backscatter Electron Microscopy ...................24
3.3.1. Electron M icroprobe A nalysis........................................ ............... 26
3.3.2. Verification of Applicability of Analysis........ ........... .. ................. 28

4 EXPERIMENTAL RESULTS ............................................................................29

4.1. Prim ary D endrite A rm Spacing ........................................ ....................... 29
4.2. Electron M icroprobe A nalysis.................................... .......................... ......... 30
4.3. Elem ental Segregation and Partitioning ................................... .................32
4.3.1. C obalt P artitioning.......................................................... ............... 38
4.3.2. Chrom ium Partitioning ..................................................... ............. 39
4.3.3. R henium Partitioning........................................... .......................... 43
4.3.4. Tungsten partitioning ........................................................ 46
4.3.5. Tungsten Partitioning with an Addition of Molybdenum ....................47
4.3.6. M olybdenum Partitioning...................................... ........................ 51
4.3.7. R uthenium Partitioning ........................................ ......... ............... 51









4.3.8. Palladium Partitioning ......................................................... .... ........... 52
4.3.9. Tungsten and Molybdenum Partitioning Interactions ............................55
4.3.10. Tantalum and Aluminum Partitioning Interactions.................................57
4.3.11. Tantalum and Aluminum Partitioning Interactions with an Addition of
T titanium ..................................................................................................60
4.4. Segregation B ehavior................................................. .............................. 64
4.4.1. Cobalt Segregation B ehavior................................ ....................... 70
4.4.2. Chromium Segregation Behavior............... ............................................71
4.4.3. Rhenium Segregation Behavior...................................... ............... 75
4.4.4. Tungsten Segregation Behavior ...................................................78
4.4.5. Tungsten Segregation Behavior with an Addition of Molybdenum .........79
4.4.6. M olybdenum Segregation Behavior.............................................. 80
4.4.7. Ruthenium Segregation Behavior............................... ................80
4.4.8. Palladium Segregation Behavior............................................................ 83
4.4.9. Tungsten and Molybdenum Segregation Behavior Interactions ..............83
4.4.10. Tantalum and Aluminum Segregation Behavior Interactions.................87
4.4.11. Tantalum and Aluminum Segregation Behavior with an Addition of
T ita n iu m ...................................... ............................................. 8 8
4.5. Scheil A analysis and Com parison.................................. ...................... ........... 92
4.6. Verification of Applicability of Analysis ............................ ................96

5 DISCUSSION .............................................. ............... 98

5.1. Primary Dendrite Arm Spacing ............................ ....... .................. 100
5.2. Partitioning Coefficient and Segregation...................................... ................ 101
5.2.1. Comparison of k' and K Techniques for Examining Segregation...........101
5.2 .2 C obalt E effects ......... ................................ .................. 105
5.2.3. Chrom ium Effects ............................................................................107
5.2.4. Rhenium Effects ............ ............. .................... 109
5.2.5. Tungsten Effects .................................................... .. ........... ............... 111
5.2.6. Tungsten Effects with an Addition of Molybdenum.............................1113
5.2.7. M olybdenum E effects ............................ ................... .............. ......114
5.2.8. Ruthenium Effects .......................................................................115
5.2.9. Palladium E effects ...................... .............................. ............. .. 117
5.2.10. Tungsten and M olybdenum Effects.................... .................. ................118
5.2.11. Tantalum and Aluminum Effects ..................................... ..................120
5.2.11.1 Effect of increased tantalum with decreased aluminum..............120
5.2.11.2. Effect of decreased tantalum and increased aluminum.............121
5.2.12. Tantalum and Aluminum Effects with an Addition of Titanium ..........123
5.2.12.1. Effect of decreased tantalum with titanium..............................123
5.2.12.2. Effect of decreased aluminum with titanium ...........................125
5.3. Scheil Analysis ........................ .................. ...... ....... 127
5.3.1. Analysis of LMSX-3 ................................................................................... 128
5.3.2. A analysis of C M SX -4 ................................................................... ..... 128

6 CONCLUSIONS ................................. ............... .. ............133









7 F U T U R E W O R K ........................................................................... ..................... 13 8

7.1. Solidification Front Curves from EMPA ......... ........................................ 138
7.2. O their Elem ental Interaction......................................... .......................... 139

APPENDIX

A SAMPLE BACKSCATTERED ELECTRON IMAGES .......................................141

B ELECTRON MICROPROBE ANALYSIS SCHEDULES AND SUMMARY OF
P R O C E D U R E U SE D ....................................................................... ..................160

C AVERAGE ELECTRON MICROPROBE ANALYSES RESULTS ..................163

D SCHEIL ANALYSIS GRAPHS FOR LMSX-3 .............................................1..82

E SCHEIL ANALYSIS DATA AND GRAPHS FOR CMSX-4...............................195

F SCHEIL ANALYSIS GRAPHS FOR LMSX-3 ................................................204

G SCHEIL ANALYSIS DATA AND GRAPHS FOR CMSX-4..............................217

L IST O F R E F E R E N C E S ............. ...... .......... ................ ..............................................226

B IO G R A PH IC A L SK E T C H ........................................ ............................................230
















LIST OF TABLES


Table p

3-1 Compositions of the 18 model alloys in weight percent (wt%) ............................22

3-2 Com position of CM SX -4 in w t% .4,6 ............................................. .....................28

4-1 PDAS measurements from EMPA and from hand calculations. ..........................31

4-2 Showing weight percentages of each respective element in each alloy from the
dendrite core and the interdendritic region, and the calculated k' value for both
techniques A (in orange), and B (in blue). .................................... .................35

4-3 Comparison of values calculated by k'B and K ....................................................73

4-4 Comparison of k'B and K for CMSX-4...............................................................97

5-1 Ki | for the eighteen model alloys and CMSX-4 listed in order from lowest to
highest. ............................................................................ 105

6-1 Elemental segregation effects for each combination of alloy compared.............. 136

7-1 Recommended alloying variations to investigate in wt%. ..................................139

7-2 Recommended alloying variations based on at% ......................................... ......140

C- Average EM PA data for LM SX-1 .............................. ................................. 164

C-2 Average EM PA data for LM SX-2 .............................................. ............... 165

C-3 Average EM PA data for LM SX-3 ........... ................................... .................. 166

C-4 Average EM PA data for LM SX-4. ............................................. ............... 167

C-5 Average EMPA data for LMSX-5 .................................................................168

C-6 Average EM PA data for LM SX-6. ............................................. ............... 169

C-7 Average EM PA data for LM SX-7. ............................................. ............... 170

C-8 Average EM PA data for LM SX-8. ............................................. ............... 171









C-9 Average EM PA data for LM SX-9. ............................................. ............... 172

C-10 Average EMPA data for LMSX-10 ......................................................................173

C-11 Average EMPA data for LMSX-11. ........................................................... 174

C-12 Average EMPA data for LMSX-12 ......................................................................175

C-13 Average EM PA data for LM SX-13 ................................................................... 176

C-14 Average EMPA data for LMSX-14 ......................................................................177

C-15 Average EMPA data for LMSX-15 ......................................................... 178

C-16 Average EM PA data for LM SX-16 ......................................................................179

C-17 Average EM PA data for LM SX-17 ......................................................................180

C-18 Average EM PA data for LM SX-18. ...................................... ....................181

E -l Scheil curve data for CM SX -4 .........................................................................201

F-l EMPA data for LMSX-3 Scheil analysis. ............. ........................................209

G-l Scheil curve data for CM SX-4. ........................................................................223
















LIST OF FIGURES


Figure pge

2-1 The y-y' matrix from model alloy LMSX-15. Image taken at 10kx. y matrix and y'
precipitates are labeled. ............................................... .................. ............. 10

2-2 Al-Ni phase diagram. The A1Ni3 field is visible at 85 87 wt% Ni....................11

2-3 FCC matrix shown above left and Li2 ordered phase ofNi3Al (Ni shown in black)
above right.6 .................................. ............................. .......... .............11

2-4 Ni-Al-X ternary phase diagram. The Ni3Al phase fields are shown in the phase
diagram with the various other additions, indicating large regions of solubility.....14

2-5 The improvements in alloy elongation and rupture strength for the same alloys (M-
252 and Waspalloy) for vacuum melt and air melt. ............................................15

2-6 DS casting operation is shown on the left and SX casting operations are shown on
the right. The primary difference is the use of a constrictor or single crystal
selector. ............................................................................. 17

3-1 BSE image of LMSX-1 taken at 100x equivalent.................................................25

3-2 BSE image of LMSX-13 taken at 100x equivalent............................. ...............25

3-3 BSE photo of LMSX-1 taken at 100x equivalent. Yellow line indicates location of
the line scan reform ed. ................................................ ............................... 27

4-1 BSE image of LMSX-13. Black lines added to image were where PDAS
measurements were taken ................. ......... ..... ............... 30

4-2 k' values for LMSX-1 for techniques A (orange) and B (blue). The green line is at
k' = 1 ..................... ....................................... 40

4-3 k' values for LMSX-13 for techniques A (orange) and B (blue). The green line is
at k = 1 ............................................................................. 4 0

4-4 k' values for LMSX-18 for techniques A (orange) and B (blue). The green line is
at k = 1. .......................................................................... 4 1

4-5 k' values for LMSX-8 for techniques A (orange) and B (blue). The green line is at
k' = 1. The difference is noted by a circle.......................................................41









4-6 Mo segregation plot for LMSX-7 and -8. White points were used in k'B analysis.
Second order trendlines are also shown for both alloys...................................42

4-7 Al segregation plot for LMSX-1 and -18 shown for comparison. White points were
used in k'B analysis. Second order trendlines are also shown for all alloys............42

4-8 Partitioning effects due to increasing Co concentration for elements showing a
preference to segregate to the dendritic region ....................................................... 44

4-9 Partitioning effects due to increasing Co concentration for elements showing a
preference to segregate to the interdendritic region. .........................................44

4-10 Partitioning effects due to increasing Cr concentration for elements showing a
preference to segregate to the dendritic region ....................................................... 45

4-11 Partitioning effects due to increasing Cr concentration for elements showing a
preference to segregate to the interdendritic region. .........................................45

4-12 Partitioning effects due to increasing Re concentration for elements showing a
preference to segregate to the dendritic region ....................................................... 48

4-13 Partitioning effects due to increasing Re concentration for elements showing a
preference to segregate to the interdendritic region. .........................................48

4-14 Partitioning effects due to increasing W concentration for element segregating to
th e d en dritic reg ion ............ ... ............................................................ ....... ............... 4 9

4-15 Partitioning effects due to increasing W concentration for element segregating to
the interdendritic region ........................................ ............................................49

4-16 Partitioning effects due to decreasing W concentration with the addition of 1 at%
Mo for element segregating to the dendritic region. ..............................................50

4-17 Partitioning effects due to decreasing W concentration with the addition of 1 at%
Mo for element segregating to the interdendritic region .......................................50

4-18 Partitioning effects due to the addition of 1 at% Mo for element segregating to the
dendritic region .................................................... ................. 53

4-19 Partitioning effects due to the addition of 1 at% Mo for element segregating to the
interdendritic region. ........................ .......... .. ...... ............... 53

4-20 Partitioning effects due to Ru addition for element segregating to the dendritic
re g io n ...................................... .................................... ................ 5 4

4-21 Partitioning effects due to Ru addition for element segregating to the interdendritic
re g io n ...................................... .................................... ................ 5 4









4-22 Partitioning effects due to Pd addition for element segregating to the dendritic
re g io n ...................................... .................................... ................ 5 6

4-23 Partitioning effects due to Pd addition for element segregating to the interdendritic
re g io n ...................................... .................................... ................ 5 6

4-24 Partitioning trends for elements in LMSX-1 and-7. Difference in the two alloys is
that LMSX-7 contains 3.1 wt% W and an addition of 1.6 wt% Mo......................58

4-25 Partitioning trends for elements in LMSX-6 and -8. Difference in the alloys is that
LMSX-6 contains 8.6 wt% W, 0 wt% Mo, and LMSX-8 contains 5.85 wt% W, 1.6
w t% M o .......................................................... ................. 58

4-26 Partitioning trends for elements between in LMSX-1 and-12. Difference in the two
alloys is that LMSX-12 contains 11.2 wt% Ta and 5.0 wt% Al. ...........................61

4-27 Partitioning trends for elements between in LMSX-1 and-13. Elements segregating
to the dendritic region shown. Difference in the two alloys is that LMSX-13
contains 6.00 wt% Ta and 6.15 wt% Al........................................ ............... 61

4-28 Partitioning trends for elements between in LMSX-1 and-13. Elements segregating
to the interdendritic region shown. Difference in the two alloys is that LMSX-13
contains 6.00 wt% Ta and 6.15 wt% Al....................................... ............... 62

4-29 Partitioning trends for elements between in LMSX-12 and-13. Elements
segregating to the dendritic region shown.............. .............................................. 62

4-30 Partitioning trends for elements between in LMSX-12 and-13. Elements
segregating to the interdendritic region shown. ........................................... ........... 63

4-31 Partitioning trends for elements between in LMSX-1 and-14. Elements segregating
to the dendritic region shown. Difference in the two alloys is that LMSX-14
contains 6.00 wt% Ta and an addition of 0.80 wt% Ti. ................. .................65

4-32 Partitioning trends for elements between in LMSX-1 and-14. Elements segregating
to the interdendritic region shown. Difference in the two alloys is that LMSX-14
contains 6.00 wt% Ta and an addition of 0.80 wt% Ti. ................. .................65

4-33 Partitioning trends for elements between in LMSX-1 and-15. Elements segregating
to the dendritic region shown. Difference in the two alloys is that LMSX-15
contains 5.10 wt% Al and an addition of 0.80 wt% Ti. .........................................66

4-34 Partitioning trends for elements between in LMSX-1 and-15. Elements segregating
to the interdendritic region shown. Difference in the two alloys is that LMSX-15
contains 5.10 wt% Al and an addition of 0.80 wt% Ti. .........................................66

4-35 Partitioning trends for elements between in LMSX-14 and-15. Elements
segregating to the dendritic region shown.............. .............................................. 67









4-36 Partitioning trends for elements between in LMSX-14 and-15. Elements
segregating to the interdendritic region shown. ........................................... ........... 67

4-37 Red lines indicated solidification/segregation gradients between dendrite cores
within the interdendritic region for an element that segregates to the dendrite cores.
The dendrites are represented in yellow .... ........... ...................................... 69

4-38 Elemental segregation plots based on K due to increasing Co content from 4 wt% to
12 .2 w t% ........................................................................ 7 5

4-39 Elemental segregation plots based on K due to increasing Cr content from 2.1 wt%
to 6 .15 w to% ....................................................... ................. 76

4-40 Elemental segregation plots based on K due to increasing Re content from 0 wt% to
8.9 w t% .......................................................... 78

4-41 Elemental segregation plots based on K due to increasing W content from 5.85 wt%
to 8 .6 w to% ........................................................ ................. 79

4-42 Elemental segregation plots based on K due to increasing W content from 3.1 wt%
to 5.85 wto with an addition of 1.6 wt% Mo to the alloys...................................82

4-43 Element segregation plots based on K due to increasing Mo content from 0 wt% to
1 .6 w t% ......................................................................... 8 2

4-44 Element segregation plots based on K due to increasing Ru content from 0 wt% to
3 .2 w t% ......................................................................... 8 4

4-45 Elemental segregation plots based on K due to increasing Pd content from 0 wt% to
1 .7 w t% ......................................................................... 8 4

4-46 Elemental segregation plots based on K due to decreasing W to 3.1 wt% and adding
1.6 w t % M o. ..........................................................................86

4-47 Elemental segregation plot based on K due to decreasing W to 5.85 wt% and
adding 1.6 w t% M o. ....................................... ... .... ........ ......... 86

4-48 Elemental segregation plots based on K due to increasing Ta to 11.2 wt% and
decreasing A l to 5 w t% ............................................ ................... ............. 89

4-49 Elemental segregation plots based on K due to decreasing Ta to 6.0 wt% and
increasing Al to 6.15 wt% ....... ........................... .......................................89

4-50 Elemental segregation plots based on K due to changing Ta and Al concentrations.
Compilation of Figures 4-48 and 4-49. ................. .............................................. 90

4-51 Elemental segregation plots based on K due to decreasing Ta to 6.0 wt% and a Ti
addition of 0.80 w t% ............................ ........................... .......... ................93









4-52 Elemental segregation plots based on K due to decreasing Al to 5.10 wt% and a Ti
addition of 0.80 w t% ........................ ................................ ......... ...... ............93

4-53 Elemental segregation plots based on K due to changing Ta and Al concentrations
with a Ti addition. Compilation of figures 4-51 and 4-52. ................ ..............94

4-54 Scheil curve comparison for Cr done by two different techniques........................94

4-55 Scheil curve comparison for Re done by two different techniques..........................95

4-56 Scheil curve comparison for Ta done by two different techniques........................95

5-1 Ni segregation plot for LMSX-9, -10, -1, and -11. Trendlines were added to show
degree of segregation ofNi observed as the Re content was increased...............103

5-2 Ta segregation plot for LMSX-9, -10, -1, and -11. Trendlines were added to show
degree of segregation of Ni observed as the Re content was increased...............103

5-3 Example showing data for k' and K from two idealized elemental segregation
profiles based on a normalized PDAS. The equations for each trendline are
indicated on the graph. ................................ .... .......... .............. .............. 104

5-4 LMSX-3 Scheil curves for Full and Short techniques for Cr.............................130

5-5 LMSX-3 Scheil curves for Full and Short techniques for Al.............................130

5-6 Scheil curves for Re from CMSX-4 done using the techniques described in this
stu d y ...............................................................1 3 1

5-7 Scheil curves for Re from CMSX-4 from literature.43 ...........................131

5-8 Scheil curves for Ta from CMSX-4 done using the techniques described in this
stu d y ...............................................................1 3 1

5-9 Scheil curves for Ta from CMSX-4 from literature.43 ......................................131

5-10 Scheil curves for Ti from CMSX-4 done using the techniques described in this
stu d y ...............................................................1 3 2

5-11 Scheil curves for Ti from CMSX-4 from literature.43..........................................132

5-12 Scheil curves for W from CMSX-4 done using the techniques described in this
stu d y ...............................................................1 3 2

5-13 Scheil curves for W from CMSX-4 from literature.43.......................................132

A-1 BSE image of LM SX-1 at 100x. ..........................................................................142

A-2 BSE image of LM SX-1 at 100x. ..........................................................................142









A-3 BSE image of LM SX-2 at 100x. ......................................................................143

A-4 BSE image of LM SX-2 at 100x. ......................................................................143

A-5 BSE image of LM SX-3 at 100x. ......................................................................144

A-6 BSE image of LM SX-3 at 100x. ......................................................................144

A-7 BSE image of LM SX-4 at 100x. ......................................................................145

A-8 BSE image of LM SX-4 at 100x. ......................................................................145

A-9 BSE image of LM SX-5 at 100x. ......................................................................146

A-10 BSE image of LM SX-5 at 100x. ......................................................................146

A-11 BSE image of LM SX-6 at 00x. ......................................................................147

A-12 BSE image of LM SX-6 at 100x. ......................................................................147

A-13 BSE image of LM SX-7 at 00x. ......................................................................148

A-14 BSE image of LM SX-7 at 100x. ......................................................................148

A-15 BSE image of LM SX-8 at 100x. ......................................................................149

A-16 BSE image of LM SX-8 at 100x. ......................................................................149

A-17 BSE image of LM SX-9 at 00x. ......................................................................150

A-18 BSE image of LM SX-9 at 00x. ......................................................................150

A-19 BSE image of LMSX-10 at 00x. .........................................................................151

A-20 BSE image of LMSX-10 at 00x. .........................................................................151

A-21 BSE image ofLMSX-11 at 00x. ......................................... ............... 152

A-22 BSE image ofLMSX-11 at 00x. ......................................... ............... 152

A-23 BSE im age of LM SX-12 at 100x ...................................................... ........... 153

A-24 BSE image of LMSX-12 at 100x. ............................ ..................... 153

A-25 BSE image of LMSX-13 at 00x. ...................................................... ...............154

A-26 BSE image of LMSX-13 at 00x. ...................................................... ...............154

A-27 BSE image of LMSX-14 at 100x. .................................. ............... 155









A-28 BSE image of LM SX-14 at 100x. ...................................................... ............... 155

A-29 BSE image of LM SX-15 at 00x. ......................................................................... 156

A-30 BSE image of LM SX-15 at 00x. .........................................................................156

A-31 BSE image of LMSX-16 at 00x........................................................... 157

A-32 BSE image of LMSX-16 at 100x. .........................................................................157

A-33 BSE image of LM SX-17 at 00x. .........................................................................158

A-34 BSE image of LM SX-17 at 100x. .........................................................................158

A-35 BSE image of LM SX-18 at 00x. ...................................................... ............... 159

A-36 BSE image of LM SX-18 at 00x. ...................................................... ............... 159

E-1 Scheil curve for Ni from CMSX-4. ...............................................................196

E-2 Scheil curve for Cr from CMSX-4. ...............................................................196

E-3 Scheil curve for Co from CM SX-4. ............................................ ............... 197

E-4 Scheil curve for Mo from CMSX-4. ........................................... ............... 197

E-5 Scheil curve for W in CM SX -4 ........................................................... ... .......... 198

E-6 Scheil curve for Re in CM SX-4. ........................................ ........................ 198

E-7 Scheil curve for Ta from CM SX-4..................................... ........................ 199

E-8 Scheil curve for Al from CMSX-4 ................... ....... ............. 199

E-9 Scheil curve for Ti from CM SX -4 .............................................. .....................200

F-l Scheil curves comparing full and short techniques for Ni in LMSX-3.................205

F-2 Scheil curves comparing full and short techniques for Cr in LMSX-3.................205

F-3 Scheil curves for both full and short techniques for Co in LMSX-3 ....................206

F-4 Scheil curves for both full and short techniques for W in LMSX-3 .....................206

F-5 Scheil curves for both long and short techniques for Re in LMSX-3....................207

F-6 Scheil curves for both long and short techniques for Ta in LMSX-3....................207

F-7 Scheil curves for both full and short techniques for Al in LMSX-3 ......................208









G-1 Scheil curve for Ni from CMSX-4. ........................................................................218

G-2 Scheil curve for Cr from CMSX-4. ........................................................................218

G-3 Scheil curve for Co from CMSX-4. ........................................ ..................... 219

G-4 Scheil curve for Mo from CMSX-4. ............................................. ............... 219

G -5 Scheil curve for W in CM SX -4 .......................................................................... 220

G-6 Scheil curve for Re in CMSX-4. ........................................ ......................... 220

G-7 Scheil curve for Ta from CM SX-4...................................... ......................... 221

G-8 Scheil curve for Al from CMSX-4. ........................................................................221

G-9 Scheil curve for Ti from CMSX-4. ........................................ ...................... 222


xviii















Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree Masters of Science

A NEW METHOD FOR THE MODELING OF ELEMENTAL SEGREGATION
BEHAVIOR AND PARTITIONING IN SINGLE CRYSTAL NICKEL BASE
SUPERALLOYS

By

Eric Christopher Caldwell

August 2004

Chair: Gerhard Fuchs
Major Department: Materials Science and Engineering

Ni-base superalloys are commonly used in very extreme environments where high

temperature strength, good corrosion/oxidization resistance, and microstructural stability

are required. These superalloys are made up of twelve to fifteen different elemental

additions including, but not limited to, Cr, Co, Mo, W, Re, Ta, Al, Ti, Ru, and Pd. The

combinations of these elements make casting of a superalloy difficult and undesirable

phases (the Topologically Close Packed, or TCP phases) may form in the microstructure

during casting or service.

TCP phases form due to localized concentrations of specific elements. To prevent

the formation of these undesirable phases and to maximize the alloys' properties,

solutioning heat treatments are required. Many of the solutioning heat treatment for third

generation superalloys (2 at%/ Re) are very long. The length of time has to be sufficient

to remove the elemental segregation that exists within the microstructure.









The elemental segregation exists upon casting due to alloying elements partitioning

to a specific phase (y or y') or region (dendrite core or interdendritic region). A

partitioning coefficient, k', is used to describe the partitioning behavior of the alloying

elements. k' was observed to exhibit a different partitioning behavior than was indicated

by electron microprobe line scans.

A new term based on the curvature of the segregation plot, K was used to qualify

the direction of each elements' partitioning (dendrite core or interdendritic region), and to

quantify some degree of relative segregation between all the alloying elements in each

alloy. The values for K were then plotted against varying elemental relationships and

conclusions about the segregation behavior were drawn.














CHAPTER 1
INTRODUCTION

The need for new materials is ever present and has been a driving force in

technological evolution. The gas turbine engine is a prime example of this. Due to the

extreme operating conditions within the engine, most materials as well as the processes

used to fabricate components are insufficient.

Historically the first true application of gas turbine technology was the first jet

aircraft of World War II. These aircraft were revolutionary at the time, but severely

limited operationally and cost prohibitive due to materials issues. The IME-262, the first

jet powered airplane, was powered by a Junkers Jumo 004B (Figure 1-1) turbojet engine,

generating about 2,000 pounds of thrust. However, the engine could only run for around

forty hours before it had to be replaced. This short service life was largely due to the



II


JL]770Tm


Figure 1-1: Junkers Jumo 004A turbojet engine









forged steels used in the engine. After World War II, the jet age began, and with it the

quest for higher powered and more reliable turbojet engines.

One of the key limiting components of the turbojet engine (or more simply here,

turbine) are the blades and vanes within the "hot section". The "hot section" is as the

name implies: the hot part of the engine. A turbojet operates under the thermodynamic

Brayton cycle. The efficiency of a Brayton cycle is determined by the temperature of the

first stage of the turbine. The higher the temperature of the first stage, the more efficient

and higher power the turbojet can become. Since more power is desired and the limiting

components are in the region of the turbine section, these components had to be designed

better and new materials used to reach the higher temperatures required to increase

efficiency.

The Junkers Jumo 004B blades were made of forged mild steel (SAE 1010) that

had an aluminum coating for oxidization protection.3 It should be noted that the use of

steel over other metals was due to availability of steel compared to other scarce strategic

materials. Besides being exposed to the highest temperatures within the engine, the

blades and vanes are also exposed to a very corrosive environment and at high stress

levels. This lead the early metallurgists to select the Co-based and Ni-based metals for

turbine applications, which are now called superalloys (Figure 1-2).

Many of the early improvements to superalloys came from both processing and by

alloying. The concept of investment casting was taken from the dental industry. With

this innovation came problems such as inclusions from the mold, but investment casting

was cheaper and easier to manufacture than forged components. The advent of vacuum

induction melting (VIM) by F. N. Darmara in the 1950's reduced the problem of















1100 Ta +Hf DS eutectics
Cast alloys +WandNb / IN591 DS e CMS
0 MAR M-22 I/MAR-M-002 DS CMSX-2
c ^'- MAR-M-20 j 0
10".MARM-200 /M2 M241 M24 MAf-M-200+ HfDSN
1 0 00 INlOO .---TRWVIA W --R J
S119 R INN792 IN 201 N620
Smelting l 713C C] R77 I. 3
M Udlmet 700 N11l [ IN 73B IN 935
S +0 Udlmet50 MA6R-M- ~ U t7
E*+co N1_1 '0 ..... /-
900 Waspaloy Ni l
SX40 / N90
12 N91
X750 / NB1A wrought 1Cast N1i-bse
h +AI a l I l Go-base
's NI-base
800 / HS21 u81 Wrought c0 C-bae
N0 ---- +Ti Cast L DS and SC
Hastelloy B P/M A ODS Ni-base

700 --- 199-/
1940 1950 1960 1970 1980 1990s
Figure 1-2: The change of temperature capabilities for superalloys at the approximate
time the alloy was introduced.4

inclusions to wrought processes.5 VIM made casting an even more viable alternative


because purer alloys could be made with fewer inclusions. As an added benefit, additions


of more reactive additions for solid solution strengthening (i.e., W, Nb, and later Ta)4


could be used due to the vacuum atmosphere in the processing stage. Therefore better


strength and creep resistance, and ultimately higher temperature capability, were realized


in the resulting alloys.


One of the first superalloys was Ni-20Cr, a simple solid solution strengthened


alloy. To increase the strength of this alloy, metallurgists began to add other alloying


elements, like Mo and C, to the Ni-Cr base alloy. The demand for higher temperature use


was still present, and since Cr depressed the Ni melting point, other alloying elements


such as Al had to be utilized. The Ni-Al alloys worked well with the VIM process due to


the reactivity of Al with the atmosphere and the need to keep Al in solution.


There were two potential precipitate strengthening phases that could be used for the


nickel-aluminum alloys: P-NiAl, and y'-Ni3Al. Initially, the Ni-base alloys were single


Directional
structures


MA6000









phase y, due to the FCC lattice which provided good creep resistance. It was later found

that a y matrix with y' (y' is an order phase with an L12 type structure) precipitates

produced higher strength materials and allowed operational temperatures to increase

further. The y' phase forms as a cuboidal precipitate, but the shape of the precipitate is

governed by the misfit strains between the precipitates and the matrix.6 Negative misfit

produces small cubes, and positive misfit produces spheres. A significant portion of the

strengthening of the alloys is from the y' phase, the y-y' interface, and single y' coherent

with the y matrix. The aluminum also resulted in the formation of a thin A1203 coating

on the surface which reduced the problems of corrosion in the hot sections. The resulting

alloys were the first generation superalloys. All of the elements that had previously been

added to the matrix when steels and other metals were used (i.e., Cr, W, Nb, Ti, Ta, etc.),

were all added to these new alloys. The resulting Ni-based alloys could be used up to

about 85% of their homologous temperature.4

The entire time alloy development was in progress, the processing advances were

also occurring. Due to the high temperatures, turbine blades must also withstand creep; a

slow time-temperature-stress dependant type of deformation. Investigation found that

creep life could be extended by reducing the number of transverse grain boundaries

within the component. The number of transverse grains was reduced with the

development of directional solidification in 1960.6 Directional solidification (DS) itself

was further developed by controlling the withdrawal rate of the casting, and therefore

controlling the solidification front to yield only high angle boundaries (HAB) and low

angle boundaries (LAB)7 along the direction of grain growth.









DS work was not the last of the advancements in processing. The ultimate goal of

DS was the complete elimination of grain boundaries from the cast component, to

produce a "single crystal". This was accomplished with the addition of a grain selector.8

This grain selector almost completely eliminates the HAB's and LAB's from the casting

and produces a single crystal (SX). SX technology further increased the operating

temperatures and operational lifetimes of components within a turbine.

The next key innovation was the addition of rhenium to the alloy. With the

addition of 1 atomic percent (at%) Re, there was a substantial boost in the mechanical

properties of the cast alloys. These alloys containing 1 at% Re became known as second

generation superalloys.

It is often said that "Necessity is the mother of invention," and the desire for better

operational capabilities of turbines was still the quest. Around the mid 1990's another 1

at% of Re was added to the superalloys.9 These were given the moniker of third

generation superalloys due to their Re addition, which resulted in a further increase in the

properties of the alloy. Throughout these alloy and process improvements, engineers and

designers took advantage of the increased temperature capabilities of the blade and vane

alloys. Due to the increased temperature capabilities of the materials, engine design has

taken off more. The F-119 turbojet engine is currently the state of the art and generates

35000 pounds of thrust (Figure 3).10 A very large increase when compared to that of the

early Jumo 004B (an increase of about 18 x in only 50 years).

Due to the increased additions of many high density refractory elements (nearly

20% of the weight was due to less than 10% of the additions), a relatively minor problem

began to becomes more significant. Undesirable phases began to form in the




















Figure 1-3: A modern day turbojet engine. This is the F-119 engine developed by Pratt
& Whitney for the F-22 Raptor and the F-35 Joint Strike fighter.

microstructure along specific orientations. These phases are called topologically close

packed (TCP) phases. While they did form in the earlier generation superalloys, TCP has

become more of a problem in the third generation superalloys. TCP's form at relatively

high temperature, over extended time, consists primarily of the heavy refractory

elements, and form within the microstructure of components in service. There are cases

of TCP forming upon casting (i.e. CMSX-10), but these TCP phases can be put back into

solution by solutioning heat treatments. Some of these solutioning heat treatments are

exceedingly long and take over fifty hours11 to complete. TCP are composed of many of

the refractory elements added to the alloy for strengthening, and the presence of the TCP

therefore depletes the microstructure of the key solid solution strengthening elements.

Also, TCP are inherently brittle, and are reported to be common failure initiation sites in

failed components.4

TCP are needlelike in shape when viewed in the transverse direction and disk like

when observed from the proper longitudinal orientation. Some of the common TCP

phases are o, [t, r, p, and Laves phases.12 Although relatively little is understood about

TCP formation, an understanding of the elemental partitioning during solidification could









aid in TCP prediction, alloy development, and develop better heat treatment

requirements.

Earlier analysis involved the use of a segregation partitioning coefficient, k'. This

partitioning coefficient relates the difference in the amount of an element present between

the dendrite core and the interdendritic region and has been defined as13


k'= XDendte (equation 1-1)
i,Interdendntc

where xi, dendrite is the composition in the dendrite core (in wt%) for element i, and xi,

interdendritic is the composition of element i within the interdendritic region (in wt%). Other

work has utilized partitioning coefficients by performing a Scheil analysis on the data

collected.

It is the goal of this investigation to further examine the elemental partitioning that

takes place during the solidification of a superalloy. To do this a different technique was

used to collect the data in the effort to determine how composition effects elemental

segregation. This different technique was then compared against prior work done, and

was re-examined to identify any new trends.

Two additional checks were also done. The first was Scheil-type analysis that was

preformed on one of the model alloys to see how the data collection technique in this

study compared to that typically preformed in industry. The second check done in this

investigation was then preformed on a common, commercial superalloy to determine how

the analysis used in this study compares to what is reported in open literature.

Using the compositional data collected, this new analysis technique which used

the curvature of compositional profile of the elemental segregation from dendrite core to

dendrite core. This was be done in hopes of developing a better understanding of






8


elemental segregation in a superalloy on solidification in order to develop more castable

alloys with reduced heat treatment requirements, and create new and better alloys for

future use.














CHAPTER 2
LITERATURE SEARCH

Ni-base superalloys are some of the most complex metal alloys used, and are used

in very extreme, if not hostile environments. The metallurgy of superalloys begins with

the microstructure that results from the elemental additions, and then casting and

processing. The processing of these advanced alloys has to be carefully controlled and

the steps understood to produce the optimal balance of properties and to avoid the

formation deleterious phases and an inhomogeneous microstructure. There are

inhomogentities in the elemental distribution that occur on casting of the advanced

superalloys due to elemental partitioning and segregation. This section will provide an

overview of this history and present current ideas regarding the phenomena of

segregation in third generation Ni-base superalloys.

2.1. Evolution of Nickel Based Superalloys

The development of Ni-base superalloys begins nearly 100 years ago. A simple

wrought Ni-20Cr alloy was used for electrical heating elements. They have grown

tremendously from this humble beginning and have spread in their use from heating

elements, to corrosion resistant alloys, and to high temperature applications. A specific

high temperature application for Ni-base alloys is the hot section components of aircraft

turbine engines, and industrial gas turbine (IGT) engines. The Ni alloys developed for

use in these components need to have excellent strength, creep resistance, and fatigue

resistance at high temperature, and also be resistant to oxidation and hot corrosion. The








development of these alloys requires unique alloying additions and special casting and

processing techniques.

2.1.1. The y-y' Matrix

The ability for Ni-based superalloys to tolerate high levels of alloying without

forming microstructural instabilities, and to form the unique y-y' microstructure produces

a material with unique properties. The material is composed of two phases, a y matrix

with y' precipitates spread throughout, with a coherent interface between the phases

(Figure 2-1). Figure 2-2 is the Al-Ni phase diagram showing the specific composition

range of interest for the formation of these alloys.14 The y matrix is a FCC structure and

the y' is an L12 type ordered structure (Figure 2-3). The FCC structure exhibits the

highest degree of packing with numerous slip systems which typically results in a

material that maintains arrangement for constituent atoms to maintain tensile, creep

rupture, and fatigue strength, at temperatures close to the homologous temperature.





I I---'-\ \


v


Figure 2-1: The y-y' matrix from model alloy LMSX-15. Image taken at 10kx. y matrix
and y' precipitates are labeled.










The FCC lattice also has a large range of solubility for other elements that can be used to

improve the properties of the alloy. The y' precipitate has nearly the same lattice


parameter as the y matrix making the matrix and precipitate coherent.

ALiomic PFI-L;r.n Nickel
0 Io 20 30 40 50 40 s S0 .100

1800

1500

1400 3
10L


AINL



I -








o 20 2) 3 0 40 s0 o SO o eo 9fl tOO
Al Weight Percent NLcke] Ni

Figure 2-2: Al-Ni phase diagram. The A1Ni3 field is visible at 85 87 wt% Ni.










Figure 2-3: FCC matrix shown above left and L12 ordered phase of Ni3Al (Ni shown in
black) above right.6

The benefits of the FCC or y matrix were originally discovered in steels and were

found to have the ability to be heavily alloyed. The base element for high temperature

alloys was shifted from Fe to Ni and Co because they had the ability to be alloyed to a

greater extent and the y-y' microstructure could be formed. Cr and Al were some of the









earliest additions to this base material. They acted as solid solution strengtheners,

increased environmental resistance, and increased the high temperature properties of the

alloys. The addition of Cr to the matrix increased the alloys resistance to hot corrosion,

and Al increased its resistance to high temperature oxidation.4'6

The high strength of the superalloys comes from solid solution strengthening,

precipitation hardening, and the misfit between the y and its coherent ordered

precipitated, y'. When alloying elements are added, the lattice parameters for the y and y'

both change slightly due to the alloying elements being larger or smaller than the one

they are substituting for (Hume-Rothery criteria for solid solution strengthening). The

misfit is the difference in lattice parameters between the matrix and the precipitate.

Misfit influences the shape of the y' precipitate. At low misfit strains (0.0 0.2 %), the y'

precipitates are spherical. At slightly higher misfit strains (0.5-1.0 %), the y' precipitates

are cuboidal. Finally, when the misfit is even higher (> 1.25 %), the y' precipitates are

plate-like. It is the formation of the cuboidal y' and the very fine (secondary) y' (which is

formed on ageing) that prevents dislocation bypass and forces the dislocations to 'cut'

through the ordered y' particle forming a superdislocation. The y' volume fraction is also

important because it influences alloy strength4. Alloys that have a very high y' volume

fraction (z 70% and greater) exhibit high strength, but very limited ductility, and the

opposite is true for the low y' volume fraction alloys. It is the combination of the volume

fraction, misfit, and coherency of the precipitate that bring about the high strengths of

superalloys.

There are many different elemental additions used to improve the properties of

superalloys. Among the additions are Co, Cr, Mo, W, Re, Ta, Ti, Ru, and Pd (which has









become of recent interest). Many of these elements are soluble in the Ni3Al system

(Figure 2-4).30 Each addition has various contributions it provides to the superalloy as a

whole, and summarized below

* Cobalt: Added to reduce or offset the y' solvus temperature without causing
incipient melting4'6'15, is reported to increase the microstructural stability of the
alloy9'15, reduces stacking fault energy (YSFE), and provides some solid solution
strengthening.6 Co has been reported to partition to the dendrite core.16,17,18

* Chromium: Added to increase the surface stability and prevent/minimize hot
corrosion4'6, reduces the y' solvus temperature19, reduces the anti-phase boundary
energy (YAPB) of the y' phase. Cr has been to partition to the dendrite core16'17'18 and
is a known component of TCP phases.4'6

* Molybdenum: Added to increase solid solution strengthening of the y' matrix6'18,
lower the alloy density (Mo is less dense than other elements like W), adjust the y'
volume fraction.20 Mo has been reported to partition to the dendrite core16'18'21, and
is a known component of TCP phases.4'6'12

* Tungsten: Added because it is a potent solid solution strengthener in Ni-base
alloys16'18, and W increases the incipient melting point of the alloy. W partitions to
the dendrite core and is a known component of TCP phases.6'12 W has also been
reported to increase the susceptibility of the alloy to hot corrosion.

* Rhenium: is the element that defines the difference in superalloy generations. It is
a strong solid solution strengthener22, and increases the high temperature creep
properties.18 Re is an element found in TCP phases23 and partitions to the dendrite
core.17,19,25
core.

* Tantalum: like Re is a strong solid solution strengthener.18'25 Ta is also added to
improve castability26, increase the y' volume fraction15, decreases the susceptibility
to incipient melting27, increase the anti-phase boundary energy (YAPB) of the y', and
is one of the y' former. Ta has been reported to partition to the interdendritic
region.16,18,22

* Aluminum: is the primary y' former.4'6 Al is also added to increase surface
stability and high temperature oxidation resistance4'6, and Al improves the
castability of the alloy. Al has been reported to partition to the interdendritic
region. 16'1822

* Titanium: another y' former.4'6 Ti is less dense than Ta, it increases the y' volume
fraction15, increase the anti-phase boundary energy (YAPB) of the y', and strengthens
the y' phase.4'6'16 Ti has been reported to partition to the interdendritic region.16'18










* Ruthenium: is reported to increase the microstructural stability28 and act as a solid
solution strengthener. Ru has been reported to partition to the dendrite core.16,29

* Palladium: is an element of recent investigation. Pd is added to improve the
surface stability of the alloy and act as a solid solution strengthener. Pd has been
reported to partition to the dendrite core.16'29

There are other trace elements (i.e. Hf, and B) that are added as well as many

deleterious elements (i.e. Cd, Hg, 0, and N) that have to be removed by meticulous

quality control and specialized processing procedures.

550










s4







Xs~O 40 30 A/. X 2O 10

Figure 2-4: Ni-Al-X ternary phase diagram. The Ni3Al phase fields are shown in the
phase diagram with the various other additions, indicating large regions of
solubility.

2.1.2. Casting and Specialized Processing Techniques

The original superalloys were cast using investment casting techniques from dental

prosthesis.6 Investment casting involves the pouring of the molten alloy into a pre-

formed shell mold and then breaking the shell mold away from the components after the

alloy has solidified and cooled. This left behind grains of various sizes throughout the

alloy due to different localized cooling rates. In some instances, inclusions were left in










the casting from the shell, impurities in the metal melted, or some of the alloying

elements oxidizing before the alloy solidifies (i.e. 2 Al + 3/2 02 -> A1203). For the

properties of the superalloys to increase, these problems had to be overcome.

Vacuum induction melting (VIM) overcame these problems. Developed in the

1950's by Falih N. Darmara6, VIM removed the atmosphere to keep the reactive

elements (i.e. Al and Ti) from oxidizing and leaving inclusions in the cast alloys, and

aided in removing of some of the deleterious tramp elements from the alloys. VIM also

allowed for closer control of the elemental additions. The mechanical properties

increased after VAR was used. (Figure 2-5).4

s- 50
40






M-252 V4Walsp M-252 Wapalovy
Elongalion Rupturle Slenglh
i Ai r mlt O Vcuurnmanu
Figure 2-5: The improvements in alloy elongation and rupture strength for the same
alloys (M-252 and Waspalloy) for vacuum melt and air melt.

Superalloy properties were increased with the advent of VIM and VAR, but another

advancement had to achieved to continue to increase the useful temperatures and

mechanical properties as turbine inlet temperatures continued to rise. The presence of

transverse grain boundaries was reduced with the use of directional solidification (DS).

The DS process was initially developed in the 1960's by F. VerSnyder and colleges

working at Pratt & Whitney.6 The process used was then further improved upon by G.

Chadley working at TRW.7 The improvement involved a controlled withdrawal of the

casting from the furnace. The grains nucleate on the chill plate and grow into the melt,









but the solidification interface does not change location relative to the outside of the

furnace. The solidification interfaces only moves relative to the component as it is being

cast. By controlling the withdrawal rate, which controlled the solidification front, the

only grains formed in the casting are only high angle boundaries (HAB) and low angle

boundaries (LAB).

The removal of transverse grain boundaries dramatically increased the creep

properties of the alloys. The next goal was the elimination of grain boundaries from the

alloy entirely. B. Piearch modified the molds being used for DS. He added a "grain

selector" to the lower part of the casting. This grain selector was designed to let only on

grain orientation through. This is typically the <001> orientation due to its high creep

rupture properties. When the alloy was now cast, it was a single crystal (SX) with no

longitudinal or transverse grains. Figure 2-631 shows the configuration for DS casting

techniques and Figure 2-731 shows the configuration for SX casting techniques.

As the superalloys were being cast, they began to develop a problem. A metastable

phase would develop in the microstructure over time while the alloy was in-service or on

casting due to the high refractory element content. These phases are the topologically

close packed (TCP) phases and they deplete the matrix of alloying elements when they

are formed from the constituent alloying elements.12 TCP are thought to be fracture

initiation sites due to their shape and brittle behavior. Methods like PHACOMP were

developed to create alloys that had stable microstructures that were stable (i.e., were not









Susceplor Induction
Insulation | ___ .... ..... Coil
nsulation Susceptor Induction Radil /
coil Radtilobn 0/
Sh. / ean
I Radiation
heating 0
0 0

0 Mea
0 Molten 0 mi 0
metal Rd aton Baffel
c000ing//, / Single
Ceramic Radiation Crysal
mold /, cooling Cea Crystal
mold Selector
Solidification 00 o Water-cooled Columnar grain
front chill Wateroot-led Starter Block
Motion
Figure 2-6: DS casting operation is shown on the left and SX casting operations are
shown on the right. The primary difference is the use of a constrictor or single
crystal selector.

prone to form TCP phases). As more and more refractory elements were added to the

alloy, the frequency of TCP formation increased. TCP formation was noted in some of

the early superalloys during service life, but in alloys like CMSX-10, TCP phases form

on casting due to the high refractory element content. Solutioning heat treatments are

done to remove the TCP phases from the as-cast alloys but these heat treatments are

very long (upwards of 50 hours), at high temperature (CMSX-10 is solution heat treated

at temperatures above 13500C).16 There are several different TCP phases found in

superalloys. Among these are o, |t, p, r, and the Laves phases. o and p are composed

predominately ofNi Cr, and Re, and to a lesser extent Co, W, and Mo.12

When a SX component is cast, a solidification front is formed as the dendrites grow

into the melt. The dendrites reject certain elements back into the liquid depending up

how the elements partition. This rejection is the origin of the segregation of the alloying

elements within the microstructure. With the elements not being homogeneously

distributed in the alloy, solutioning heat treatments must be preformed.









Solutioning heat treatments (solutioning for short) are done at temperatures above

the y' solvus temperatures and below the solidus temperature and at times sufficient to

have the elements become evenly distributed. The difference in these two temperatures

(y' solvus and solidus temperatures) is called the y' window. In general, alloys that have

less segregation are more easily solutioned.

There are several benefits to developing a better understanding of the segregation

of the constituent elements in a nickel base superalloy. By understanding which elements

segregate more strongly, solution heat treatments can be developed that are potentially

shorter and at lower temperature. The development of new alloys would also benefit

from this understanding, by using elements that have been shown to reduce segregation,

and therefore, reduce TCP formation.














CHAPTER 3
MATERIALS AND EXPERIMENTAL PROCEDURE

In this chapter, the materials and procedure that were used in this study are

described along with the various techniques used to analyze them.

3.1. Materials

The materials used are based on a third generation Ni-based superalloy. The

baseline alloy (LMSX-1); has a composition in weight percent (wt%) of Ni-bal, Cr-4.15,

Co-12.2, W-5.85, Re-5.9, Ta-8.6 Al-5.5, Hf-0.1. The baseline composition is related to

CMSX-10 and Rene N6, both being third generation superalloys. From this LMSX-1

baseline alloy, 17 other model alloys were designed to evaluate the effect of typical

alloying additions on the solidification behavior and properties ofNi-base superalloy

single crystals (Table 3-1). The elemental additions and the compositional ranges

selected were based on industrial experience, material development history, and current

industrial trends.

The 17 model alloys each had one to two variations from the baseline alloy so that

the influence of each type of addition could be examined. LMSX-2 and -3 were added to

study the influence of cobalt on stability, y' solvus and solid solution strengthening.

LMSX-2 contained a moderate level of Co (8 w/o) and LMSX-3 contained a low level (4

w/o Co). Note that LMSX-1 has 12 wt% Co which is similar to the Co concentration in

Rene N625, and LMSX-3 has 4 wt% Co for comparison to CMSX-10.9 Rene N6 was

developed by GE, and CMSX-10 was developed by Cannon-Muskegon. These

manufacturers have different ideas as to the effects of Co.9'25'31 LMSX-4 and -5 have









variations in the amount of chromium present in these alloys. These alloys were

developed to examine the effect of Cr content on microstructure stability, y' solvus

temperature, and surface stability. LMSX-4 has a high Cr level (6.15 w/o) and LMSX-5

contains a low level (2.1 w/o) of Cr. LMSX-6 has a high level of tungsten (8.6 w/o) to

investigate tungsten's effect on stability and solid solution strengthening. LMSX-7 and -

8 both have a 1 a/o (1.6 w/o) addition of molybdenum, to determine the effect of Mo

additions on stability and solid solution strengthening. LMSX-7 substituted 1 atomic

percent (at%) Mo for 1 at% W, so the alloy contained a reduced amount of tungsten (3.1

w/o). LMSX-9, -10, and -11 all have varying amounts of rhenium. LMSX-9 contains no

rhenium (0 w/o). LMSX-10 contains a low level of rhenium (1 at% or 2.95 wt%).

LMSX-11 has the largest amount of rhenium of all the alloys (3at% or 8.7 w/o). These

alloys are intended to cover what is essentially the first three generations of superalloy

(LMSX-9, -10, and -1) to determine the effect of the Re on stability of first, second, and

third generation superalloys. The high Re content in LMSX-11 was added to investigate

the stability of alloys with large Re additions. In LMSX-12, -13, -14, and -15, the

amounts of the y' former, Al and Ta, were varied from alloy to alloy and titanium was

substituted in the latter two. LMSX-12 and -13 have changes in the amounts of Ta and

Al to determine the effect of Ta/Al ratio variations on solvus and solidus temperatures,

elemental solidification segregation, and y' size and shape. In LMSX-14 and -15, Ti was

substituted for Ta (in LMSX-14) or Al (LMSX-15) to determine if Ti affected the alloys

solidus, solvus, segregation, and strength. The alloys LMSX-12, -13, -14, and -15 were

all intended to have a constant y' volume fraction. To begin examination of the fourth

generation superalloys, LMSX-16 and -17 both have additions of ruthenium (1.6 and 3.2









w/o respectively). It has been reported that Ru additions affect stability and solid

solution strengthening28 and these two alloy were added to investigate that claim.

LMSX-18 has a 1 a/o addition of palladium (1.7 w/o). Pd, a member of the precious

metal group (i.e. Re, Ru, Pd, Pt, Au) was also included in this study since it has also been

reported to affect microstructural stability, strength, and surface stability.32'33

The alloys were cast in single crystal bars at Precision Cast Components Airfoils

(PCC Airfoils, Minerva, OH). A commercial directional solidification furnace was used

with high gradient investment casting techniques to cast the alloys in a [001] orientation.

An inchworm type grain selector was used to produce single crystal samples. The

withdrawal rate was initially set at 6 in (15.24 cm) per hour until the grain selector was

reached. After that point, the rate was changed to 8 in (20.32 cm) per hour. The bars

were cast in cylinders with a diameter of 1.25 cm and a length of 20 cm. One mold was

processed for each alloy, and each mold contained nineteen bars. After casting, the [001]

orientation was verified by Laue backscattered x-ray techniques. For the purpose of this

investigation, samples with defects such as freckles, slivers, high angle boundaries

(HAB), and low angle boundaries (LAB) were not used.

3.2. Metallography

After receipt of the bars, specimens were sectioned for metallographic evaluation.

A LECO CM-20 cut-off wheel, using a LECO 3025 blade (rated for HRC 45-60) was

used to perform all sectioning of the bars. The bar was cut in the middle, and starting

from the cut mid-section ends, another cut was made to leave behind a small disk 1.25 cm

in diameter and z 0.5 cm thick. This disk was then sectioned in half to produce two

semi-circular specimens for microstructural characterization.












Table 3-1:


Compositions of the 18 model alloys in weight percent (wt%). Highlighted regions indicate changes made from baseline.
Com positions ofRene N6 and CMSX-10 sao n


.V l..ll.1r L II Jll V.I I\.'IIU UllV ^II T.1VI*IUI IV LI VV s .l.t U.~llrU I JJll..
Alloy ID Ni Cr Co Mo W Ta Re Al Ti Hf Ru Pd Comments
LMSX-1 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 Baseline
61.95 5.00 13.00 2.00 3.00 2.00 13.00 0.05 Atomic % Composition
LMSX-2 Bal 4.10 8.00 5.85 8.60 5.90 5.55 0.10 Reduced Co (8 at%)
LMSX-3 Bal 4.10 4.00 5.85 8.60 5.90 5.55 0.10 Minimum Co (4 at%)
LMSX-4 Bal 6.15 12.20 5.85 8.60 5.90 5.55 0.10 High Cr (7 at%)
LMSX-5 Bal 2.10 12.20 5.85 8.60 5.90 5.55 0.10 Low Cr (3 at%)
LMSX-6 Bal 4.10 12.20 8.60 8.60 5.90 5.55 0.10 High W (3 at%)
LMSX-7 Bal 4.10 12.20 1.60 3.10 8.60 5.90 5.55 0.10 Low W (1 at%) + 1 at%
Mo
LMSX-8 Bal 4.10 12.20 1.60 5.85 8.60 5.90 5.55 0.10 +1 at% Mo
LMSX-9 Bal 4.10 12.20 5.85 8.60 0.00 5.55 0.10 0 at% Re
LMSX-10 Bal 4.10 12.20 5.85 8.60 2.95 5.55 0.10 1 at% Re
LMSX-11 Bal 4.10 12.20 5.85 8.60 8.70 5.55 0.10 3 at% Re
LMSX-12 Bal 4.10 12.20 5.85 11.20 5.90 5.00 0.10 High Ta
(4at%), Low Al (12 at%)
LMSX-13 Bal 4.10 12.20 5.85 6.00 5.90 6.15 0.10 Low Ta
(2 at%), High Al (14 at%)
LMSX-14 Bal 4.10 12.20 5.85 6.00 5.90 5.65 0.80 0.10 Low Ta
(2 at%) + lat %Ti
LMSX-15 Bal 4.10 12.20 5.85 8.60 5.90 5.10 0.80 0.10 Low Al
(12 at%) + 1 at% Ti
LMSX-16 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 1.60 +1 at% Ru
LMSX-17 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 3.20 +2 at% Ru
LMSX-18 Bal 4.10 12.20 5.85 8.60 5.90 5.55 0.10 1.70 +1 at% Pd
CMSX-10 Bal 3.00 4.00 0.60 6.00 8.00 6.00 5.75 0.10
Rene N6 Bal 4.50 12.50 1.10 5.75 7.50 6.00 5.35 0.15









Once the specimens were cut, they were mounted using a LECO PR-10 mounting press.

The specimens were mounted in 3.175 cm (1.25 inch) mounts using diallyl phthalate and

labeled as LMSX-X as cast, where X indicated the specific alloy identification number.

With the metallographic specimens mounted, they were then leveled, ground, and

polished to a mirror-like finish. The leveling of the specimens was done using a LECO

BG-20 belt grinder with a water cooled 240 grit belt. The edges of the specimen mounts

were first chamfered to ease handling and lessen hydroplaning during polishing.

Leveling was done until there was no diallyl phthalate covering the specimen and there

were no raised spots obvious on the sample.

All of the grinding and polishing was done using a LECO VP-20 Vari/Pol, operated

at z 300 rpm, and water was used to lubricate and cool the specimen. Standard

metallographic practices for grinding and polishing were used to prepare the specimen33

and a Branson 1200 ultrasonic sink was used for ultrasonic cleaning of the specimens

between polishing steps.

Two techniques were evaluated for grinding and polishing. The first technique was

considered the "standard" technique, which has been typically used by the University of

Florida Materials Science and Engineering Department, and the second was an advanced

technique initially developed by Struers Inc and further modified for this study.

The "standard" technique was done on LMSX-1, -2, -3, -4, -5, -9, -10, -11, -16, -17,

and -18. Grinding was done using wet-dry alumina grinding disks beginning with 240

grit, followed with 320, 400, 600, and finally 800 grit. This was followed with two rough

polishing steps. Rough polishing was done using 20.32 cm (8 in) billiard cloths with first

15 |tm and then 5 |tm alumina suspended in water. Fine polishing was done using LECO









Micron cloths with first 1 |tm and then 0.3 |tm alumina suspended in water. All

specimens were polished to a mirror-like finish and examined optically for scratches.

The advanced technique was done on LMSX-6, -7, -8, -12, -13, -14, and -15. The

grinding steps were done using Struers MD-Piano 600 and MD-Piano 1200 grit magnetic

grinding disks. The particulate was imbedded into the disk itself and only needed to be

dressed between specimens to maintain the proper grit size. Rough polishing was done

using a Struers MD-Mol magnetic disk with the appropriate MD-mol solution. This

solution was water based and needed either little or no extra water for lubrication. The

final polishing was done in the same manner as the standard technique. Again, all

specimens were polished to a mirror-like finish and examined optically for scratches.

Although no specimen was done using both techniques, the final requirement was

the same: a mirror-like finish without scratches. This was easily attainable with both

techniques given sufficient time. The advanced technique, using the magnetic disks,

offered reduced grinding and polishing times, less mess, fewer steps, and a decreased

chance of cross contamination between grit sizes. The advanced technique has the

setback of increased time if a step is not done properly due to the large changes in grit

sizes used. If done correctly, specimen preparation time was reduced from 45 min to

20 min.

3.3. Scanning Electron Microscopy/Backscatter Electron Microscopy

Electron microscopy was first done using a JOEL SEM 6400. The instrument was

operated with an accelerating voltage of 15 keV and a working distance of 15 mm. The

instrument was primarily operated in the backscattered mode. Using the backscattered

electron (BSE) imaging, 20 images were taken of each specimen in the as-cast condition.









The images were taken in a grid like manner of four-by-five. The images were 1 mm

apart in the "y" direction and 2 mm apart in the "x" direction. These images were taken

to calculate the primary dendrite arm spacing (PDAS). Figures 3-1 and 3-2 are

representative of the BSE images taken to determine the PDAS. Appendix A contains

additional images from this portion of this investigation.











X






Figure 3-1: BSE image of LMSX-1 taken at 100x equivalent.










Y

X 3






Figure 3-2: BSE image of LMSX-13 taken at 100x equivalent









3.3.1. Electron Microprobe Analysis

The remainder of this investigation of the segregation behavior of these alloys was

done using electron microprobe analysis (EMPA). The instrument used for this

examination was a JOEL 733 Superprobe. The instrument was operated with an

accelerating voltage was 15 keV, a take-off angle of 400, a spot size of 1 tm and a

beam current 20 nA. Each point in the EMPA was measured by wavelength dispersive

spectroscopy (WDS) and measured for 10 seconds per point.

Specific calibration for Ni, Cr, Co, Mo, W, Re, Ta, Al, Ti, Ru, Pd, and Hf were all

used as references. To expedited the scanning times, as many different crystals as

possible were used while maintaining the best line (Kc, Lc, or Mc) to scan. A LiF

crystal was used to measure intensities for Ni, Cr, and Co. The compositional analysis

for these elements was based on the Kc lines. To measure intensities for W, Re, Ta, Hf,

and Al, a TAP crystal was used. To determine the chemical analysis of these elements,

the Kc line for Al was measured, and the La lines were used for all the others on this

crystal. Finally, a PET crystal was used to measure intensities for Ru, Mo, and Ti, with

chemical composition based on the Kc line for Ti and the La lines for Ru and Mo.

A small computer routine for the microprobe had to be used to perform the line

scans, along with some of the proper settings. Due to the age of the equipment, some of

the line scan routines had to be varied to detect specific elements. These routines are

found in Appendix B.

A problem occurred with measuring some of the trace elements due to the age of

the software. The trace elements of Mo in LMSX-7 and -8, Ti in LMSX -14 and -15, and









the Ru in LMSX-16 all required a specific step to be added to this routine to properly

measure the peak.

Line scans were used to measure composition and segregation within the

microstructure. A line of 30 points was scanned running between two dendrite cores

through the interdendritic region. Care was taken to avoid any secondary and tertiary

dendrite arms. Image 3-3 contains an example of one of the line scans examined. The

typical length of each line scan was z 300 |tm. Three scans were done on each specimen

and all the data was entered by hand, again due to the age of the equipment. A total of 90

points were scanned for each specimen. This technique is a variation of that used by

Pollock et. al.34

The technique to measure/quantify solidification segregation was developed by M.

N. Gungor36 and is commonly found to be the industry standard. This technique involves

a grid of point scans across the specimen, all equally spaced. To check the validity of the

new method of using line scans, the grid method was used on LMSX-3. The PDAS of


Figure 3-3: BSE photo of LMSX-1 taken at 100x equivalent. Yellow line indicates
location of the line scan preformed.









LMSX-3 was measured at 253.4 |tm and a slightly larger spacing of 265.0 |tm was used

for the spacings between points in the line scans. Fifteen line scans of fifteen points were

used with the larger spacings used for a total of 225 points scanned.ll This atomic

percent and normalized weight percent data were then entered into a spreadsheet by hand

for analysis.

3.3.2. Verification of Applicability of Analysis

To provide an independent check of this investigation, a piece of as-cast CMSX-4

was sectioned, mounted, and polished (using the standard technique) to an optically

verified mirror like finish. CMXS-4 was used due to availability of the as-cast sample.

The composition of CMXS-4 is listed in Table 3-2. The EMPA was preformed in a

similar fashion to that described above to see if the techniques described above were

applicable to current production alloys and to broaden the possible spectrum of further

understanding of trends found in this experiment.


Table 3-2: Composition of CMSX-4 in wt%.4,6
Alloy ID Ni Cr Co Mo W Ta Re Al Ti Hf
CMXS-4 Bal 6.5 9.0 0.6 6.0 6.5 3.0 5.6 1.0 0.10















CHAPTER 4
EXPERIMENTAL RESULTS

For clarity, the results of this investigation are broken down into three parts. First,

the primary dendrite arm spacing (PDAS) will be discussed. Then the observations of the

electron microprobe analysis are evaluated. Finally, the two electron microprobe analysis

techniques will be compared and evaluative.

4.1. Primary Dendrite Arm Spacing

Twenty 100x images (or fields of view) taken of each of the 18 model alloys were

used to calculate the primary dendrite arm spacing (PDAS). Due to the natural

variabilities in dendrite arm spacings, from 6 to 8 measurements were taken from each

field of view, but the number was held consistent for all fields for that alloy. Figure 4-1

is one of the 100x BSE images from LMSX-12. The black lines drawn on the image are

examples of the lines used to measure the PDAS. This procedure was repeated for all

twenty fields of view, and then the final values were tabulated. To make measuring

easier, the micron bar on the image was measured and used as a standard. It was

measured at 5.4 cm and indicated 500 |tm long. This allowed a machinist's scale to be

used to make all the measurements directly from the field of view and then ratioed back

to the actual size. The average, standard deviation, and median values were all

calculated. Table 4-1 contains the results from these calculations. This was done to

develop an understanding of the accuracy in calculating the PDAS from the EMPA line

scans.









All of the measured PDAS standard deviations were relatively large, and all but

two of the PDAS measurements fell to within one standard deviation of the mean. The

exceptions were LMSX-10 and -17. Of the remaining sixteen alloys, six of the measured

PDAS were very close (about 20 |tm difference) to those calculated from the line scans.

Another eight of the measurements were within about 50 |tm of one another. The only

alloys that exhibited a variation in PDAS greater than 70 |tm (other than LMSX-10 and-

17) were LMSX-1 and -2. LMSX-1 had the highest standard deviation for PDAS of the

eighteen alloys.



















Figure 4-1: BSE image of LMSX-13. Black lines added to image were where PDAS
measurements were taken.

4.2. Electron Microprobe Analysis

To quantify and characterize the inhomogeneties and segregation in the

microstructure that occur during solidification, a lengthy analysis was preformed to

develop a better understanding of the elemental interactions and solidification behavior.

The electron microprobe analysis (EMPA) results are broken down into three sections.

The first section contains the results of the line scan technique and how they relate to the









Table 4-1: PDAS measurements from EMPA and from hand calculations. Standard
deviation is shown for hand calculations. All measurements are in |tm.
LMSX- 1 2 3 4 5 6 7 8 9
EMPA 287.66 267.39 250.94 259.61 262.91 225.52 307.24 262.31 367.90
Measured 374.33 343.00 253.47 294.35 310.84 281.65 331.78 320.62 381.86
St Dev 104.1 98.7 64.3 84.0 87.1 97.5 80.7 74.1 84.5

LMSX- 10 11 12 13 14 15 16 17 18
EMPA 271.41 223.59 275.72 257.35 226.80 290.93 247.51 174.70 258.09
Measured 360.23 258.52 325.85 280.03 281.48 286.40 284.51 268.91 271.53
StDev 116.1 61.0 79.5 79.8 72.4 78.2 61.7 79.9 70.1
elemental segregation and partitioning for the eighteen model alloys. The next section

contains the results from the grid scan of LMSX-3. Finally, the data from the line scans

from CMSX-4 are presented. The data was measured in atomic percent (at%) and then

converted to normalized weight percent (wtO) and recorded.

Within these eighteen model alloys, a total of fifteen relationships were observed.

Eight of these relationships could be directly related to the variation of a single elemental

addition. The remaining seven show the interactions that appear to be present from alloy

to alloy based on the variation of only two elements (i.e. Ta and Al both varied from

baseline). The relationships observed that relate to elemental variations are as follows:

* Cobalt. By comparing LMSX-1, -2, and -3.
* Chromium. By comparing LMSX-1, -5, and -5.
* Rhenium. By comparing LMSX-1, -9, -10, and -11.
* Ruthenium. By comparing LMSX-1, -16, and -17.
* Tungsten. By comparing LMSX-1 and 6.
* Molybdenum. By comparing LMSX-1 and -8
* Palladium. By comparing LMSX-1 and -18.
* Tungsten with a Molybdenum addition. By comparing LMSX-7 and -8.

The remaining relationships that were observed were examined to qualify the interactions

that might be present in the systems where two elemental additions were varied. These

systems are listed as follows:









* Variation of Tantalum and Aluminum from the baseline. LMSX-1, -12, and
LMSX-1, -13.

* Variation between Tantalum and Aluminum. LMSX-12 and -13.

* Variation of Tantalum and Aluminum from the baseline with an addition of
Titanium. LMSX-1, -14, and LMSX-1, -15.

* Variation between Tantalum and Aluminum with an addition of Titanium. LMSX-
14 and -15.

* Variation between decreasing Tungsten and increasing Molybdenum. LMSX-1, -7
and -6, -8.

As noted previously, all final data from the line scans is presented in normalized

weight percent (wt%).

4.3. Elemental Segregation and Partitioning

Three line scans from dendrite core to dendrite core through the interdendritic

region were preformed on one specimen from each of the model alloys. The composition

of each point along the line in each alloy was determined. The average values for each

element for the three line scans for each specimen were calculated. Appendix C contains

the average EMPA results for the eighteen model alloys. Nearly all the elements in all

the alloys exhibit some degree of segregation; however the degree and direction

dendriticc or interdendritic) of the segregation varied. A partitioning coefficient (k') was

calculated from the average values of each element from the set of line scans from each

alloy

The partitioning coefficient parameter is indicative of the degree of segregation

during solidification and tendency for an element to segregate to either the dendrite core

or the interdendritic region and how much upon casting. k' is defined as


k'= XDendrite (Equation 1-1)
i,Interdendrtec









where xi, dendrite is the composition (in wt%) at the dendrite core and xi, interdendritic is the

composition (in wt%/) roughly equidistant between both dendrite cores.11 16,36-40 The

points chosen for the determination of the segregation partition coefficient came from

either end of the line scan (i.e. the dendrite core). The interdendritic value was chosen

from either of the midpoint of this average scan, with one exception. When the minimum

or maximum compositional level did not occur at the midpoint, this interdendritic value

was taken from a trendline. If the mid points did not lie reasonably near the trendline, the

next point on the line was chosen. This was done to avoid the possibility that the mid-

points chosen would not indicate the actual degree of segregation as shown by the

trendlines of the actual data was as indicated. Table 4-2 contains the k' values calculated

from this method. Data listed as k'A is the data collected by F. Fela.16 The partitioning

coefficients calculated in this study are reported as k'B.

A k' less the unity indicates a tendency of this element to segregate to the

interdendritic region; whereas a k' greater than unity indicates segregation to the dendrite

core.11,16,36-38 Graphs were then developed to show the variations of k' as the

composition was varied in this investigation. Figures 4-2, 4-3, and 4-4 graphically

illustrates how k'A and k'B compared to one another for LMSX-1, -13, and -18 as

examples.

From the comparisons, it can be seen that although the segregation behavior in both

studies indicate similar directions of segregation, the magnitudes varied particularly for

Re. The magnitude difference can be attributed to differences in the location used to

measure composition within the specimen being locally different from one another.

However, it is clear that the segregation trends represented by k' largely holds true for









both k'A and k'B. The y' former, Ni, Al, Ta, and Ti, all segregated to the interdendritic

region, and the y solid solution strengtheners, Cr, Co, W, and Re segregated to the

dendritic region. Although the segregation behavior was similar in both studies, there

was a discrepancy in the segregation behavior of Mo in LMSX-8 (+ 1 at% Mo). k'A

indicated that Mo segregated to the dendritic region, whereas k'B indicated Mo

segregated to the interdendritic region. Figure 4-5 contains the graph that compares the

results of both k'A and k'B. Figure 4-6 is the graph for LMSX-8 that was used to identify

the points for the k' partitioning analysis. The points chosen for the k' analysis are

shown as large open circles on the graphs. In addition, a second order trend line was

plotted to aid in visualizing the segregation behavior. For comparison, a similar graph for

Al from LMSX-1 and -18 is shown with the same data points used for calculation of k'

labeled as in Figure 4-7.












Table 4-2


Showing weight percentages of each respective element in each alloy from the dendrite core and the interdendritic region,
na d the calculated k' value for both te )


Alloy Ni Cr Co Mo W Re Ta Al Ti Ru Pd
Dendritic 56.04 4.07 13.04 6.83 10.49 4.86 4.33
Interdendritic 61.76 3.93 11.40 4.31 3.38 10.08 5.74
LMSX-1
k'B 0.91 1.04 1.14 1.58 3.10 0.48 0.75

Dendritic 59.96 4.27 9.04 6.73 10.85 5.02 4.67
Interdendritic 63.85 3.56 7.64 4.29 3.57 10.38 6.39
LMSX-2
k'B 0.94 1.20 1.18 1.57 3.04 0.48 0.73

Dendritic 64.90 3.91 4.33 6.71 10.79 4.98 4.46
Interdendritic 69.00 3.66 3.52 3.58 2.22 11.35 6.33
LMSX-3
k'B 0.94 1.07 1.23 1.87 4.86 0.44 0.70

Dendritic 54.87 6.35 13.37 6.67 9.72 4.26 4.46
Interdendritic 59.16 6.07 11.19 4.38 3.16 9.29 5.48
LMSX-4
k'B 0.93 1.05 1.19 1.52 3.08 0.46 0.81

Dendritic 60.75 2.59 13.37 5.79 9.29 3.69 4.51
Interdendritic 64.88 2.65 12.87 3.54 3.59 6.86 5.79
LMSX-5
k'B 0.94 0.98 1.04 1.64 2.59 0.54 0.78

Dendritic 57.17 4.67 13.97 8.44 9.17 3.43 4.56
LMS6 Interdendritic 61.76 4.54 12.01 4.47 3.41 8.46 6.61
k'B 0.926 1.029 1.163 1.888 2.689 0.405 0.690












Table 4-2 (Cont.) showing weight percentages of each respective element in each alloy from the dendrite core and the interdendritic
region, and the calculated k' value A (in blue), and B (in orange).
Alloy Ni Cr Co Mo W Re Ta Al Ti Ru Pd
Dendritic 60.3 4.74 13.65 1.61 2.88 8.64 3.97 4.72
LMSX- Interdendritic 62.48 4.29 12.89 1.82 2.04 3.67 7.37 5.65
7 k'B 0.97 1.10 1.06 0.88 1.41 2.35 0.54 0.84

Dendritic 57.75 4.44 13.71 1.54 5.55 8.59 3.91 4.71
LMSX- Interdendritic 61.5 4.3 12.97 1.88 3.81 3.47 7.75 5.56
8 k'B 0.94 1.03 1.06 0.82 1.46 2.48 0.50 0.85

Dendritic 64.35 3.79 12.82 7.39 0 5.62 4.70
LMSX- Interdendritic 63.79 3.79 11.59 4.57 0 9.25 5.45
9 k'B 1.01 1.00 1.11 1.62 0.00 0.61 0.86

Dendritic 60.31 3.83 13.53 6.91 5.69 5.32 4.60
LMSX- Interdendritic 62.62 3.59 11.38 4.32 1.67 10.65 5.53
10 k'B 0.96 1.07 1.19 1.60 3.41 0.50 0.83

Dendritic 54.30 4.63 13.62 4.82 13.81 3.29 4.40
LMSX- Interdendritic 62.62 3.61 10.92 2.79 2.06 9.79 6.80
11 k'B 0.87 1.28 1.25 1.73 6.70 0.34 0.65

Dendritic 57.53 4.41 13.89 5.97 8.85 5.26 4.36
LMSX- Interdendritic 61.26 3.90 12.03 3.80 3.31 9.76 5.68
12 k'B 0.94 1.13 1.15 1.57 2.67 0.54 0.77












Table 4-2(Cont.) showing weight percentages of each respective element in each alloy from the dendrite core and the interdendritic
region, and the calculated k' value A (in blue), and B (in orange).
Alloy Ni Cr Co Mo W Re Ta Al Ti Ru Pd
Dendritic 59.49 4.14 13.36 5.69 9.97 2.18 5.07
LMS Interdendritic 67.13 4.63 11.14 2.75 1.70 6.42 7.37
LMSX-13
k'B 0.89 0.89 1.20 2.07 5.86 0.34 0.69

Dendritic 61.75 4.72 13.97 5.25 7.30 1.93 4.12 0.48
Interdendritic 66.52 3.96 12.66 2.87 2.34 4.38 5.70 1.15
LMSX-14
k'B 0.93 1.19 1.10 1.83 3.12 0.44 0.72 0.42

Dendritic 58.23 4.32 13.82 5.72 9.66 3.58 4.19 0.42
Interdendritic 63.99 3.78 11.32 2.99 2.40 8.04 5.94 1.13
LMSX-15
k'B 0.91 1.14 1.22 1.91 4.03 0.45 0.71 0.37

Dendritic 57.37 4.52 14.51 5.11 9.35 3.55 4.59 1.63
Interdendritic 61.41 4.04 12.17 3.36 3.16 7.53 4.52 1.38
LMSX-16
k'B 0.93 1.12 1.19 1.52 2.96 0.47 1.02 1.18

Dendritic 55.41 4.24 13.69 5.77 9.66 3.52 4.52 3.59
Interdendritic 61.49 3.68 10.97 3.10 1.68 10.11 6.34 3.11
LMSX-17
k'B 0.90 1.15 1.25 1.86 5.75 0.35 0.71 1.15

Dendritic 57.23 4.13 13.86 6.06 10.12 3.84 4.41 0.80
LMS 8 Interdendritic 61.84 3.71 11.22 2.91 2.23 8.74 6.47 2.95
k'B 0.93 1.11 1.24 2.08 4.54 0.44 0.68 0.27









With k'B exhibiting the same trend as k'A, the composition effects and some of the

elemental interactions were plotted. When examining the effect of elemental variations,

all the compositional effects were compared directly to the baseline alloy LMSX-1. Note

that k'B is calculated using equation 1-1, however the data used in this calculation was

obtained from data collection method described in this paper.

4.3.1. Cobalt Partitioning

The effects of cobalt variations (LMSX-1, -2 and -3; 12.2 wt% Co, 8.0 wt% Co,

and 4.0 wt% Co respectively) on the k'B values were all of the elements in the alloy were

plotted against increasing Co content. From this graph (Figure 4-8), it can be seen that

increasing Co content decreased the segregation of the elements that partition to the

dendrite core. The largest decrease in segregation occurs with Re followed by W, Co

itself, and finally Cr. The effect on Cr is a very small decrease in segregation over the

range of 4 wt% to 12.2 wt% Co. Whereas the effect of Re decreased markedly as the Co

level is increased to the 8 wt% Co, and then remains constant with further increasing Co.

It should be noted that the increase in Co content in these alloys results in a decreased

segregation of Co itself, but only slightly.

When looking at the elements that segregate to the interdendritic region (Figure 4-

9), increasing the Co content also decreased the segregation of Al and Ta, but slightly

increased the segregation of Ni. The decrease in partitioning for Al with increasing Co

content greater than that for Ta, but the Ta follows the same trend as Re does in that the

degree of segregation is decreased to the 8 wt% Co point and then becomes essentially

constant. As was stated, the segregation of Ni increased with increasing Co, but Ni is the

only element that was observed to exhibit increased segregation when increasing Co

content.









4.3.2. Chromium Partitioning

The alloys with varying chromium content were the second group examined. This

series of alloys consists of LMSX -5, -1, and -4 (2.1 wt% Cr (3 at%), 4.1 wt% Cr (5 at%),

and 6.15 wt% Cr (7 at%) respectively). The effects of this addition on the elements in the

alloy (Ni, Cr, Co, W, Re, Ta, and Al) was examined and characterized. Increasing the Cr

concentration increased the segregation of Re, Co, and Cr. The increase in Re

segregation, being the most consistent and pronounced when compared to that of Co and

Cr. Co partitioning increased as Cr content was increased, and the Cr partitioning did

increase slightly. In the baseline alloy, LMSX-1, and the high Cr content alloy, LMSX-4,

Cr was observed to partition to the dendrite core. But in the low Cr alloy (LMSX-5), Cr

was observed to segregate to the interdendritic region. W had a different response to this

change in concentration; as Cr content increased, the W partitioning decreased. The

partitioning coefficient for Co at the 2.1 wt% Cr was the lowest found in this

investigation indicating that Co partitioned the least in this alloy. Figure 4-10 shows the

effect graphically of increasing Cr concentration on the segregation of elements

partitioning to the dendritic region.








40




k' Comparison for LMSX-1

35




mTechnLque A
hTechnique B
25


2


15








05


NI Cr Co W Re Ta Al

Figure 4-2: k' values for LMSX-1 for techniques A (orange) and B (blue). The green
line is at k' = 1.


k' Comparison for LMSX-13



mTechnlque A
mTechnlque B







4


3


2







NI Cr Co W Re Ta Al

Figure 4-3: k' values for LMSX-13 for techniques A (orange) and B (blue). The green
line is at k' = 1








41




k' Comparison for LMSX-18


ETechnique A
ETechnique B


Ni Cr Co W Re


Figure 4-4: k' values for LMSX-
line is at k' = 1.





600

ETechnique A
ETechnique B
5 00



400



S3 00
Differel


200



1 00



0 00


Ta Al Pd


18 for techniques A (orange) and B (blue). The green


k' Comparison for LMSX-8


Ni Cr Co Mo W Re


Figure 4-5: k' values for LMSX-8 for techniques A (orange) and B (blue). The green

line is at k' = 1. The difference is noted by a circle.








42




Plot of Molybdenum Segregation in LMSX-7 and -8
with Normalized PDAS
250 -




200

-U-." -- .- _--__.
==
150
0



1 00

LMSX-7
LMSX-8
PLMSX-8

0 -5




00
0 02 04 06 08 1
Normalized PDAS

Figure 4-6: Mo segregation plot for LMSX-7 and -8. White points were used in k'B

analysis. Second order trendlines are also shown for both alloys.


Plot of Aluminum Segregation in LMSX-1 and -18
with Normalized PDAS
700
0
650


600
650 //---------------- ------------------







3 50
O / \ 41














300
0 02 04 06 08
Normalized PDAS

Figure 4-7: Al segregation plot for LMSX-1 and -18 shown for comparison. White

points were used in k'B analysis. Second order trendlines are also shown for

all alloys.









The effect of increasing Cr on elements that partition to the interdendritic region is

shown in Figure 4-9. The partitioning behavior of Ni, Al, and Ta due to varying the Cr

concentration was not consistent. Ta showed a linear increase in partitioning as the Cr.

The partitioning of Ni did not appear to be affected by the change in Co content. The

graph in Figure 4-11 shows a decrease in the partitioning coefficient, but the variation are

small and may be due to experimental data scatter. The effect of Cr content on the

partitioning of Al was still different than that of Ni and Ta. Al partitioning decreased as

Cr content increased.

4.3.3. Rhenium Partitioning

Alloys LMSX-9, -10, -1 and -11 were used to evaluate the changes in partitioning

due to increasing Re content. LMSX-9 is a first generation superalloy with 0 wt% Re,

LMSX-10 is a second generation superalloy with 1 at% Re (- 3 wt%), LMSX-1 is the

baseline and is a third generation superalloy with 2 at% Re (- 6 wt%), and LMSX-11 is a

model alloy with 3 at% Re (z 9 wt%) and was added to examine the effect of a large Re

additions on alloy stability. Figure 4-12 contains the k'B curves for elements segregating

to the dendritic region, and Figure 4-13 contains the k'B curve for elements that segregate

to the interdendritic region.

Of the elements segregating to the dendrite cores, Re shows the largest increase in

partitioning due to the increase in Re concentration. The partitioning coefficient for Re

in LMSX-11 (8.95 wt% Re) was the largest k' value observed in this experiment. Cr and

Co also exhibit increasing segregation levels when the Re content was increased up to the

5.95 wt% Re (LMSX-1) concentration. At the highest Re concentration, the Co showed a

slightly greater propensity to partition to the dendrite core.









44





Partitioning Effect with Varying Co


6000




5 000
"-- *--Cr
S----CO

4000




". 3000




2 000

40 --------------------- ----------------


1000 ---



0 00
2 4 6 8 10 12 14
wt% Co


Figure 4-8: Partitioning effects due to increasing Co concentration for elements showing

a preference to segregate to the dendritic region.



Partitioning Effect with Varying Co


1 000

0 0 0 ^ -----------------------------------' ------
0900


0 800


0 700 A------A -- -


0 600


0500


0400


0300


0200


0 100


0000
2 4 6 8 10 12 14
wt% Co


Figure 4-9: Partitioning effects due to increasing Co concentration for elements showing

a preference to segregate to the interdendritic region.















Partitioning Effect with Varying Cr


3500



3 000



2500
-- CO


2 00



1 500



1 000



0 500



0 000
1 2 3 4 5 6
wt% Cr


Figure 4-10: Partitioning effects due to increasing Cr concentration for elements showing

a preference to segregate to the dendritic region.



Partitioning Effect with Varying Cr


1 000


0900


0 800 --
0800 A-..-...----- . .... A

0 700


0 600 -M-Ta


a. 0 500


0 400


0 300


0200


0 100


0000
1 2 3 4 5 6 7
wt% Cr


Figure 4-11: Partitioning effects due to increasing Cr concentration for elements showing

a preference to segregate to the interdendritic region.









The Cr continued to exhibit a limited degree of segregation to the dendritic core, and the

final k'B values for Cr and Co for LMSX-11 (8.9 wt% Re) were virtually the same.

LMSX-11 contained the most severe segregation and, therefore the highest partitioning

coefficients for Cr, Co, and Re for this investigation.

Increased Re contents also resulted in an increasing segregation ofNi, Ta, and Al.

Ta showed the greatest degree of segregation for these three elements, followed by Al,

and then Ni. Ni showed a linear decrease in k'B (increasing segregation) as the Re

concentration was increased. Ta and Al showed somewhat parabolic decreasing trends in

k' as the Re content increased. Unlike in the Re bearing alloys, Ni partitioned to the

dendritic region for LMSX-9 (0 wt% Re). LMSX-11 showed the greatest amount of

partitioning in Ni, Al, and Ta for this investigation. In general, the segregation behavior

of all of the elements was reduced to its lowest levels in the 0 wt% Re (LMSX-9) alloy,

and the highest levels in the 8.9 wt% (LMSX-11) alloy.

4.3.4. Tungsten partitioning

The effects of increasing the W concentration were also evaluated in this

investigation by comparing LMSX-1 (5.85 wt% W) and LMSX-6 (8.9 wt% W). Figures

4-14 and 4-15 show the changes in the partitioning coefficient for the base elements (Ni,

Cr, Co, W, Re, Ta, and Al) as the concentration of W is increased. W had a variety of

effects on the elements that commonly segregate to the dendritic regions (Re, W, Co, and

Cr). The first effect noted was that the increased concentration of W, also resulted in an

increased W partitioning coefficient. This was the only element with k'B greater than one

(i.e. elements that partitioned to the dendrite core) that showed an increase in this

segregation. Co and Cr were unchanged as the W concentration was increased.









Somewhat unexpectedly, the increase in W content resulted in a decrease in the

segregation of Re.

Similar to the varied segregation behavior in the dendritic segregating elements, the

elements segregated to the interdendritic region also showed very different responses.

Raising the W levels in the alloy caused Ta and Al to segregate to a greater extent, with

Ta exhibiting a greater degree of segregation than Al. In a pattern similar to that shown

by Re for this series, the partitioning of Ni decreased (k'B approaching one) with

increasing W content.

4.3.5. Tungsten Partitioning with an Addition of Molybdenum

LMSX-7 and -8 both had a 1 at%/ Mo addition to evaluate the effects of Mo on the

segregation behavior of the alloys. In addition, the W concentration in LMSX-7 was

decreased to 3.1 wt% (1 at%). Re, W, Cr, and Co all segregated to the dendrite core

regions of the as-cast structure (Figure 4-16). As the W concentration was decreased

from 5.85 wt% to 3.1 wt%, Re showed the largest decrease in segregation of the elements

in this alloy. The segregation behavior of W itself was also decrease slightly. The

partitioning behavior of Co was unaffected by the decrease in W concentration. The

degree of Cr segregation increased as the W concentration decreased. Mo, Ni, and Ta all

exhibited a decreased degree of segregation as the W concentration was decreased. The

change in W had no obvious effect on the Al segregation behavior. The lowest k'B

values for W and Re (indicating the least amount of segregation) in this investigation

were found in LMSX-7. Figure 4-17 clearly illustrates the effect of decreasing W

concentration the segregation behavior ofNi, Ta, Mo, and Al.









48




Partitioning Effect with Varying Re


8000


7 000
Cr
-Co
6000 --W


5000


2. 4000


3000


2 000
A 00- ----------------- -----------------t-h----------------A





0 uuuI
0 1 2 3 4 5 6 7 8 9 10
wt% Re


Figure 4-12: Partitioning effects due to increasing Re concentration for elements showing

a preference to segregate to the dendritic region.



Partitioning Effect with Varying Re


1 200 -



1 000 -




0800 -, --4



0 0600



0 400 -



0200





0 1 2 3 4 5 6 7 8 9 10
wt% Re


Figure 4-13: Partitioning effects due to increasing Re concentration for elements showing

a preference to segregate to the interdendritic region.









49





Partitioning Effects with Varying W





35000 '------------ -------------------------


2 500
*- -Cr




d- W
2000 Re
-A





- -- - --*
1 500



1 000 -



0 500



0000
5 55 6 65 7 75 8 85 9 95
wt% W


Figure 4-14: Partitioning effects due to increasing W concentration for element

segregating to the dendritic region.



Partitioning Effects with Varying W


1 000


0 900


0 800


0 700 .


0 600


S0 500 -


0400 -


0 300


0200 -


0 100


0000
5 55 6 65 7 75 8 85 9 95
wt% W


Figure 4-15: Partitioning effects due to increasing W concentration for element

segregating to the interdendritic region.









50




Partitioning Effects with Varying W
(Mo added)


300



250



200



S1 50



1 00


2 25 3 35 4 45
wt% W


5 55 6 65 7


Figure 4-16: Partitioning effects due to decreasing W concentration with the addition of 1

at% Mo for element segregating to the dendritic region.



Partitioning Effect with Varying W (Mo added)


U- -'- -- -


--*-- N i
-- Mo
- -A Ta
-4-0- Al


A ------- - - --. --- .-. .-. -A


000 1
2 25 3 35 4 45 5 55 6 65 7
wt%


Figure 4-17: Partitioning effects due to decreasing W concentration with the addition of 1

at% Mo for element segregating to the interdendritic region.


1 20




1 00




080




, 060




040


020


--M -Co







7 A-- W
i i ------------









4.3.6. Molybdenum Partitioning

By examining the segregation behavior of the baseline (LMSX-1) and LMSX-8

alloys, the effect of a single addition of Mo could be observed. The elemental

segregation behavior of elements that partition to the dendritic regions is shown in

Figure 4-18 and Figure 4-19 illustrates the segregation behavior of elements that partition

to the interdendritic region. The addition of 1 at% Mo decreased the overall segregation

of nearly every element in the alloy. k'Re decreased the most substantially followed by

k'w, and finally k'co. Cr partitioning was virtually unaffected by the addition of Mo to

this alloy.

The elements that exhibited partitioning coefficients (k') less than one, also

exhibited a similar segregation behavior with the addition of 1 at% (1.6 wt%) Mo. The

segregation of Al was observed to decrease to the greatest degree followed by Ni and

finally Ta. Mo was observed to partition to the interdendritic regions, and partitioned

more strongly than Al and less than Ta.

4.3.7. Ruthenium Partitioning

Ruthenium has become an alloying addition of great interest and is currently being

added to the newer superalloys28,39', which are called fourth generation superalloys. To

investigate the effect of Ru, two alloys were included in the alloy design matrix (see

Table 3-1). The first was LMSX-16, which was the baseline LMSX-1 alloy with an

addition of 1 at% Ru (1.6 wt%). The second alloy, LMSX-17, contained 2 at% Ru (3.2

wt%). The addition of 1 at% Ru had no affect on Re segregation. However, when the Ru

content was increased to 2 at%, Re begins to partition more dramatically. The remaining

elements with k'B greater than one (i.e. partition to the dendrite core) all show essentially

linear trends (Figure 4-20) for all three Ru concentrations (LMSX-1 (0 at% Ru), LMSX-









16 (1 at% Ru), and LMSX-17 (2 at% Ru)). Cr segregated to a lesser degree than Re for

all of the alloys in this study, and showed a linear increase in segregation as the Ru

concentration increased. The k'B values for Co and W both increased by a similar

amount with the increase in Ru content. With the increase in Ru, Ru itself showed a

decrease in its segregation behavior. The k'B for Co in LMSX-17 was the largest value

found for Co in this investigation, indicating that Ru strongly influences the segregation

behavior of Co.

Of the elements segregating to the interdendritic region in LMSX-1, -16, and -17,

Ta showed the greatest degree of segregation followed by Al and finally Ni (Figure 4-

21). The segregation of Ta does not change until the Ru content was greater than 1.6

wt% (1 at%). When the Ru concentration was increased above 1 at%, Ta began to

segregate to the interdendritic region more substantially than at lower Ru concentrations.

Al followed a similar pattern to Ta, but not as strongly. It should also be noted that Al

segregation behavior seemed to be reversed in the 1 at%/ Ru alloy since Al was observed

to segregate to the dendritic region in LMSX-16. Ni was the only element that was

relatively unaffected by the addition or Ru, and exhibited only a slight trend towards

increased segregation with the increasing Ru content.

4.3.8. Palladium Partitioning

The effect of Pd, a precious metal group element, was examined using LMSX-18 (1

at% Pd). Of the elements that exhibited tendencies to segregate to the dendrite cores, Re

was affected the most by the Pd addition, and then followed by W (Figure 4-22). Both

Re and W showed increased segregation as Pd was introduced into the alloy. Although

Cr and Co partitioning both increased with the increasing Pd content, it was not to the

extent of the increase observed in W and Re.









53




Partitioning Effect with Varying Mo

3500



3000


2 5 0 0 0--











2 000
31000 .-- .------------------------------














0 000
0 02 04 06 08 1 12 14 16 18
wt% Mo


Figure 4-18: Partitioning effects due to the addition of 1 at% Mo for element segregating

to the dendritic region.



Partitioning Effects with Varying Mo

1 000 -

09004-
0 800 . . . . ..-- '---------- ----
0 800





-HT
0 700

0600 T

0500 --

0 400 Al

0300 -AI

0200

0 100

0000
0 02 04 06 08 1 12 14 16 18
wt% Mo


Figure 4-19: Partitioning effects due to the addition of 1 at% Mo for element segregating

to the interdendritic region.









54




Partitioning Effect with Varying Ru


1 UUU -


0 900


0 800


0 700


0600


0 500 1 2 3


0 400 "
--a

CoAl
0300


0200


0 100




wt% Ru


Figure 4-20: Partitioning effects due to Ru addition for element segregating to the

dendritic region.



Partitioning Effect with Varying Ru











-a- Re
S000


4 000





2000

UUU- -


wt% Ru


Figure 4-21: Partitioning effects due to Ru addition for element segregating to the

interdendritic region.









The presence of Pd in the alloy (LMSX-18) caused a decrease in segregation of Ni

to the interdendritic regions (Figure 4-23). Segregation for Al and Ta both increased due

to the addition of 1.7 wt% (1 at%) Pd, and their increases were similar in magnitude.

From the k'B values calculated, Pd itself segregated heavily to the interdendritic region.

4.3.9. Tungsten and Molybdenum Partitioning Interactions

Although the segregation behaviors of alloys with an increasing W content

(LMSX-1 and -6), with an addition of Mo (LMSX-1 and -8), and with decreasing W

content with an addition of Mo (LMSX-7 and -8) were discussed, the segregation

behavior due to substituting Mo for W was evaluated (LMSX-1 and -7, and LMSX-6 and

-8) for interactions and consistency. These graphs from this evaluation are presented in

See Figure 4-24.

The first alloys compared were between LMSX-1 (5.85 wt% W, 0 Wt% Mo) and

LMSX-7 (3.1 wt% W, 1.6 wt% Mo). The segregation behavior for those elements whose

partitioning coefficient, k'B, value is greater than one are Re, W, Cr, and Co. The

substitution of 1 at% Mo for 1 at% W caused a decrease in the segregations of Re, W,

and Co. The decrease in segregation for Re was the most significant followed by W and

finally Co, which showed only a slight decrease in segregation. Cr segregation increased

slightly due to this alloy modification. All of the elements that segregated to the

interdendritic region exhibited a decrease in partitioning due to the decrease in W content

and the Mo addition. The partitioning of Al was reduced to the greatest degree, followed

by Ni. The degree of segregation observed for Mo was intermediate to Al and Ni, but

since it is only one point no further observation can be made. The segregation of Ta was

also decreased, but not to the extent of Ni.









56




Partitioning Effects due to Pd Addition


1 o00


090


0 80

07 ------------------^ -----










----Ta
0 30 ~A-l


020


0 10

00
0 02 04 06 08 1 12 14 16 18
wt% Pd


Figure 4-22: Partitioning effects due to Pd addition for element segregating to the

dendritic region.



Partitioning Effects due to Pd Addition


500 -


450Co


400


350


3004




200 -- Re


1 50







u uu
0 02 04 06 08 1 12 14 16 18
wt% Pd


Figure 4-23 Partitioning effects due to Pd addition for element segregating to the

interdendritic region.









To verify the trends shown in decreasing W content with an addition of Mo,

LMSX-6 (8.6 wt% W, 0 wt% Mo) and -8 (5.85 wt% W, 1.6 wt% Mo) were compared.

All of the trends noted in the LMSX-1 and -7 comparison were present in the evaluation

of LMSX-6 and -8 (Figure 4-25), but the magnitudes had changed. The segregation

behavior of Re was still observed to decrease with decreasing W content, but at a lower

rate than the alloys with a lower concentration ofW. W exhibited more initial

segregation due to the increased W content of LMSX-6, but decreased to nearly the same

k'B values for both LMSX-7 and -8 indicating an increased segregation at high W

concentrations. Ta and Ni both exhibited greater decreases in segregation behavior when

the W content was reduced from 8.6 to 5.85 wt% and 1.6 wt% Mo was added. However,

Ta and Ni were both initially more segregated in LMSX-6 than LMSX-1. The

segregation behavior of Co was observed to decrease more, but like Ni and Ta, was to a

greater extent segregated in LMSX-6 than LMSX-1. Cr and Al segregation did not

indicate any change due to decreasing W from a high content to an intermediate content

combined with adding Mo. When comparing the degree of segregation in these four

alloys (LMSX-1, -6, -7 and -8), LMSX-8 exhibited the least amount of segregation.

4.3.10. Tantalum and Aluminum Partitioning Interactions

The next group of interactions observed come from those alloys that had varying

amounts of both Ta and Al (LMSX-12 and -13). LMSX-12 is a modified baseline alloy

with 4 at% Ta (11.2 wt%/, termed high Ta) and 12 at% Al (5 wt%, termed low Al).

LMSX-13 contained a reduced Ta content (2 at%, 6 wt% termed low Ta) and an

increased Al concentration (14 at%, 6.15 wt% termed high Al). Comparing the elements

of these alloys to one another as well as the baseline (LMSX-1) was done to characterize







58



Partitioning Interactions due to Decreasing W and a Mo Addition


Alloy (LMSX-X)


Figure 4-24: Partitioning trends for elements in LMSX-1 and-7. Difference in the two
alloys is that LMSX-7 contains 3.1 wt% W and an addition of 1.6 wt% Mo.


Partitioning Interactions Due to Decreased W and a Mo Addition


Alloy (LMSX-X)


Figure 4-25: Partitioning trends for elements in LMSX-6 and -8. Difference in the alloys
is that LMSX-6 contains 8.6 wt% W, 0 wt% Mo, and LMSX-8 contains 5.85
wt% W, 1.6 wt% Mo.









the interactions. Recall that all of these alloys have similar volume fractions ofy', so the

alloy modifications are only intended to alter the composition of the phases.

The increase in Ta to 11.2 wt% coupled with a decrease in Al to 5 wt% (LMSX-1

to LMSX-12) resulted in a variety of effects on the elements in the alloys (Figure 4-26).

Increased Ta and decreased Al contents caused a decrease in the segregation of Re, but

Re remained the most segregated element present in this alloy. Ta showed the second

greatest decrease in segregation which is surprising since the amount of Ta was increased

by 1 at% (z 3 wt%). The only other element that showed some effect due to this change

was Cr, whose partitioning increased. The other elements in the system, W, Co, Ni, and

Al did not show any significant change in segregation due to the modification in alloy

chemistry.

To continue to evaluate the role of the y' former, another combination of alloys

was used to begin to examine partitioning interactions (LMSX-1 and -13). The

difference in chemistry for these two lies in LMSX-13 which contains a reduced quantity

of Ta (from 8.9 wt% down to 6 wt%) and an increase in Al (from 5.55 wt% up to 6.15

wt%). The overall trend for this alloy modification was an increase in segregation for all

elements except for Cr which began to segregate to the interdendritic region. The largest

increase in segregation of the elements that exhibited dendritic segregation, was in the

segregation for Re, which nearly doubled. The next greatest increase in segregation was

observed in W. Co was the only element that did not appear to be affected by the change

in alloy chemistry (Figure 4-28). Ta also exhibited a significant increase in segregation of

those elements that had a k'B less than one. However, the segregation of Ta was

significantly lower in magnitude in comparison to Re. Al segregation also increased to a









lesser extent than Ta. Ni exhibited a slight increase in partitioning due to this change in

chemistry (Figure 4-29).

LMSX-12 was also compared directly to LMSX-13 to further characterize these

alloy modification effects (Figures 4-30 and 4-31). Not surprisingly, the trends reported

for the LMSX-1 to LMSX-13 interactions were to be observed when examining LMSX-

12 and LMSX-13. Re segregation increased again, and by a factor of more than two. W

segregation also increased, but not to the degree of Re. Again, Co partitioning appeared

unaffected by these alloy modifications. The segregation to the interdendritic region

increased to the largest degree for Ta. Al segregation did increase, but not to the extent

of Ta, and the degree of Ni increased the least.

4.3.11. Tantalum and Aluminum Partitioning Interactions with an Addition of
Titanium

Ta and Al are not the only y' former in Ni-base superalloys. Ti is also

considered to be a y' former. The baseline alloy, LMSX-1, was modified again with Ti

additions for either Ta or Al, to continue to look at the effects of the y' former.

LMSX-14 is LMSX-1 with an addition of 0.80 wt% (1 at%) Ti and a decrease in

Ta from 8.9 wt% (3 at%) down to 6.0 wt% (2 at%) This change in alloy chemistry

changed the segregation of W and Cr causing them both to segregate more to the dendrite

core, with W segregating more strongly than Cr. Re and Co segregation patterns had no

observable change in this comparison (Figure 31). Ta and Al both showed about the

same increase in partitioning to the interdendritic region from the baseline to this

modified chemistry. Ti itself exhibited the strongest segregation to the interdendritic

region. The partitioning behavior of Ni decreased slightly due to these alloy

modifications (Figure 32).








61




Partitioning Interactions Due to Increasing Ta and Decreasing Al


Alloy (LMSX-X)


Figure 4-26: Partitioning trends for elements between in LMSX-1 and-12. Difference in
the two alloys is that LMSX-12 contains 11.2 wt% Ta and 5.0 wt% Al.


Partitioning Interactions Due to Decreasing Ta and Increasing Al

700


6 00


500


4 00


300


200


100


000
1 13
Alloy (LMSX-X)

Figure 4-27: Partitioning trends for elements between in LMSX-1 and-13. Elements
segregating to the dendritic region shown. Difference in the two alloys is that
LMSX-13 contains 6.00 wt% Ta and 6.15 wt% Al.








62




Partitioning Interactions due to Decreasing Ta and Increasing Al













- I


1 00

090

080

070

060

." 050

040

030

020

0 10

000


Alloy (LMSX-X)

Figure 4-28: Partitioning trends for elements between in LMSX-1 and-13. Elements
segregating to the interdendritic region shown. Difference in the two alloys is
that LMSX-13 contains 6.00 wt% Ta and 6.15 wt% Al.


Partitioning Interactions due to Variations in Ta and Al


12 13
Alloy (LMSX-X)


Figure 4-29: Partitioning trends for elements between in LMSX-12 and-13. Elements
segregating to the dendritic region shown.







63



Partitioning Interactions due to Varying Ta and Al

1 00

090

080



060

". 050

040

030

020

0 10

000
12 13
Alloy (LMSX-X)

Figure 4-30: Partitioning trends for elements between in LMSX-12 and-13. Elements
segregating to the interdendritic region shown.

The effect of substituting Ti for Al was evaluated with LMSX-1 and -15, in which


the y' former were again modified (Figure 33 and 34). LMSX-15 is a variant of LMSX-


14 in that it contains the same addition of 1 at% (0.80 wt%) Ti, but LMSX-15 also had a


reduction in Al from 5.10 wt% (13 at%) Al down to 5.0 wt% (12 at%). Of elements


segregating to the dendrite, Re again showed the largest increase in segregation due to the


alloy modification, followed by W. Cr segregation also increased, but only slightly, and


Co showed even less of a change than Cr due to this alloy modification. Ta and Al both


showed the same degree of increase in segregation with the substitution of Ti for Al. Ni


appeared to be unaffected by this modification in alloy chemistry. Ti itself again


segregated to the interdendritic region, more strongly than any other element.


Using the combination of LMSX-14 and LMSX-15, it is now possible to observe


the interactions between Ta and Al with the Ti addition being constant. When









comparing, LMSX-14 and -15, Re showed a large increase in segregation due to the

increased Al content, decreased Ta content, and the Ti addition. W and Co exhibited an

increase in k'B of similar magnitude due to the change in Ta and Al concentrations with

Ti in the matrix. The segregation of Cr had no appreciable change with the modification

in alloy chemistry. Ti showed a greater degree of segregation than any other addition that

partitioned to the interdendritic region. The k'B for Ti in LMSX-15 was slightly lower

than that of LMSX-14 indicating an increase in partitioning with increasing Ta and

decreasing Al contents. Ni and Al both exhibited similar increases in segregation with

alloy modifications. Ta showed no change in segregation due to these changes in base

alloy chemistry.

4.4. Segregation Behavior

The use of partitioning coefficients to describe the segregation of elements in an as-

cast alloy is useful to understand castability, defect formation, and heat treatment

requirements. However, the magnitude of segregation obtained from the calculation of

the partitioning coefficient may not be indicative of the degree of segregation that is

occurring. Also, in an element that shows a relatively wide scatter and no visible

partitioning preference, (i.e. Cr in this experiment) the actual partitioning, dendritic or

interdendritic, that is occurring may not be accurate in all cases.

The line scans used in this study, develop a graphical representation of the

compositional variations that occur, due to segregation after solidification and some

degree of back diffusion have occurred. Figure 4-37 depicts this segregation between

dendrites as a surface that has a varying composition depending on the distance from the

dendrite itself. The curved lines between the dendrite cores is an idealized representation














Partitioning Interaction due to Decreasing Ta with a Ti Addition

3 50



300



250

Cr
---WCo
2 00 -- ---



1 50



1 00








1 14
Alloy (LMSX-X)


Figure 4-31: Partitioning trends for elements between in LMSX-1 and-14. Elements

segregating to the dendritic region shown. Difference in the two alloys is that

LMSX-14 contains 6.00 wt% Ta and an addition of 0.80 wt% Ti.



Partitioning Interaction due to Decreasing Ta with a Ti Addition

1 00

090

080


070 1 --N -

060

S050

0 40

030








1 14
Alloy (LMSX-X)


Figure 4-32: Partitioning trends for elements between in LMSX-1 and-14. Elements

segregating to the interdendritic region shown. Difference in the two alloys is

that LMSX-14 contains 6.00 wt% Ta and an addition of 0.80 wt% Ti.









66




Partitioning Interaction Due to Decreasing Al and a Ti Addition

4 50


400-


350


300 -
Cr
250 --- Co
-W
-0- Re
200


1 50









1 15
Alloy (LMSX-X)


Figure 4-33: Partitioning trends for elements between in LMSX-1 and-15. Elements

segregating to the dendritic region shown. Difference in the two alloys is that

LMSX-15 contains 5.10 wt% Al and an addition of 0.80 wt% Ti.



Partitioning Interaction Due to Decreasing Al and a Ti Addition

1 00

090

080

070

e Ta
0 60-A

A Tl
050

0 40
A

0 30








1 15
Alloy (LMSX-X)


Figure 4-34: Partitioning trends for elements between in LMSX-1 and-15. Elements

segregating to the interdendritic region shown. Difference in the two alloys is

that LMSX-15 contains 5.10 wt% Al and an addition of 0.80 wt% Ti.









67





Partitioning Interactions Due to Varying Ta and Al with an Addition of Ti


400


350


3 00
-Cr
-Co
250--
-4----Re
2 00


I 5O


Alloy (LMSX-X)


Figure 4-35: Partitioning trends for elements between in LMSX-14 and-15. Elements

segregating to the dendritic region shown.


Partitioning Interactions Due to Varying Ta and Al with an Addition of Ti


1 00


090


080


070 -


0 60


". 050


040


030


-@-Ta
--Al


Alloy (LMSX-X)


Figure 4-36: Partitioning trends for elements between in LMSX-14 and-15. Elements

segregating to the interdendritic region shown.


r --------rf


I '"'









of solidification, back diffusion, and segregation of an element that segregates to the

dendrite core. Note that the composition of the interdendritic region is depleted in the

element while the core is enriched. Also it should be noted that the

solidification/segregation lines are represented by curves. The use of curves was based

on the observation of the general trends of the data points determined by EMPA.

For each set of EMPA data points, a second order trendline was determined and

then the equation that describes the trendline was determined. This was done for a

normalized primary dendrite arm spacing (PDAS). Using this second order equation, the

curvature for the trendline was determined.

Curvature is defined as "the amount by which a curve, surface, or other manifold

deviates from a straight line.42" Mathematically, curvature, or K comes from the second

derivative of an equation, or more explicitly, 42

a2y
82
K= 2 equation (4-1)




But this can be simplified to just the second derivative as previously mentioned due to the

desire to determine the maximum value for the given equation. Thus, putting this in

terms of the trendline equations, it is simply 2a (where a is from ax2 + bx + c from the

trendline equation) because the only point of concern is at the apex which can be

considered x = 0. It should be noted that care should be taken with the calculation of the

curvature, K. The sign ofK is determine by the line scan itself. Since the line scans in

this experiment were done from dendrite core to dendrite core through the interdendritic

region, one combination of positive and negative curvature values is achieved. If the









scan were done from the interdendritic region, through the dendrite core, and back into

the interdendritic region, another combination of positive and negative K's are returned

which are the opposite sign of the first example. By doing the scans dendrite core to

dendrite core, the resultant signs reflect those done by the previous k' analysis in this and

other studies.


















Figure 4-37: Red lines indicated solidification/segregation gradients between dendrite
cores within the interdendritic region for an element that segregates to the
dendrite cores. The dendrites are represented in yellow.

With the trendline equations determined, the K could be calculated. K was used to

explain the segregation behavior in the various alloys. The curvature, K, values were

calculated and then plotted against the following:

* Cobalt. By comparing LMSX-1, -2, and -3.

* Chromium. By comparing LMSX-1, -5, and -5.

* Rhenium. By comparing LMSX-1, -9, -10, and -11.

* Ruthenium. By comparing LMSX-1, -16, and -17.

* Tungsten. By comparing LMSX-1 and 6.

* Molybdenum. By comparing LMSX-1 and -8









* Palladium. By comparing LMSX-1 and -18.

* Tungsten with a Molybdenum addition. By comparing LMSX-7 and -8.

* Variation of Tantalum and Aluminum from the baseline. LMSX-1, -12, and
LMSX-1, -13.

* Variation between Tantalum and Aluminum. LMSX-12 and -13.

* Variation of Tantalum and Aluminum from the baseline with an addition of
Titanium. LMSX-1, -14, and LMSX-1, -15.

* Variation between Tantalum and Aluminum with an addition of Titanium. LMSX-
14 and -15.

* V Variation between decreasing Tungsten and increasing Molybdenum. LMSX-1,
-7 and -6, -8

Table 4-3 contains the K values and the k'B values for comparison purposes.

Similar to previous results, the trend of k' greater than unity indicated segregation to the

dendrite core, along with K greater than zero was consistent for partitioning to the

dendritic regions for the eighteen model alloys.11,35 Similarly, the trend of k' less than

unity and K less than zero was also consistent with previous results for the eighteen

model alloys, indicating consistency in determining overall segregation path to the

interdendritic regions. Although most results for these comparisons were similar, there

was some disagreement in the elements that showed only a weak segregation preference

between the dendritic and interdendritic region.

4.4.1. Cobalt Segregation Behavior

The K value was calculated for each element in each of LMSX-1, -2, and -3 and

then plotted against increasing Co concentration. Figure 4-38 shows the extent of change

of K resulting from this compositional variation. Cr, Ni, W, and Re all partitioned to the

dendritic region, and Al, Ni, and Ta all segregated to the interdendritic region. The









elements W, Re, Ta, and Al all show a decrease in their segregation as the Co content

was increased. Co and Ni segregated slightly more. Cr segregation did not change

significantly. Re segregates more than any of the elements in these alloys over all

concentrations of Co, and exhibited a maximum in segregation at 4 wt% Co. Re

segregation decreased slightly with the addition of 4 wt% Co to the alloy (for a total of

8 wt% Co). With 12.2 wt% Co present in the alloy, the KRe dropped to the lowest level in

this study. Ta showed the next greatest effect due to increasing Co content. The increase

in Co from 4 wt% to 8 wt% showed little effect on Ta, but the segregation began to

decrease (become less negative) when the Co concentration was increased to 12.2 wt%.

Ni showed the third greatest segregation behavior in this series of alloys. The

increase in Co concentration caused an initial increase in partitioning of Ni when Co was

increased from 4 wt% to 8 wt%. The remaining increase in Co had no further effect on

the segregation ofNi. W showed a linear decrease in segregation as the Co content was

increased from 4 wt% to 12.2 wt%. The segregation of Co followed a more expected

trend of increasing as the concentration of it increased in the system from 4 wt% to 8

wt% Co, but did not change beyond the 8wt% Co concentration. Kco in LMSX-3 was the

lowest value for Co found in this part of this investigation. The partitioning of Al was the

opposite of the trend observed by Co. There was no change in Al segregation from 4

wt% Co to 8 wt% Co, and then the partitioning decreased with further additions of Co.

4.4.2. Chromium Segregation Behavior

LMSX-4, -1, and -5 were used to evaluate the segregation behavior of the elements

in the alloys with varying Cr contents. LMSX-5 contained 2.1 wt% Cr and LMSX-4

contained 6.15 wt% Cr. This analysis is presented from the low Cr content alloy to the









high content alloy (Figure 4-39). When the analysis was preformed, Re was observed to

exhibit the greatest degree of segregation and it partitioned to the dendritic region. The

low and baseline levels of Cr had little effect on the segregation behavior, but the

addition of 4.15 wt% Cr to the high Cr (LMSX-4, 6.15 wt% Cr) brought about a decrease

in Re segregation. Ta segregated to the interdendritic region and was the second most

strongly segregated element. As Cr was added, the partitioning of Ta increased and then

remained relatively constant. The addition of Cr brought about a decrease in the third

most heavily partitioned element, Ni, which segregated to the interdendritic region. As

the Cr content was increased, the partitioning of Ni decreased in a linear manner. W

partitioned to the dendritic region and its segregation decreased linearly as the Cr content

increased. Co and Cr both segregated to the dendrite cores, and both showed only slight

increases in segregation due to increasing Cr content. However, Co did segregate more

strongly than Cr over the entire range of compositions evaluated. Cr exhibited a

complete change in segregation. In high Cr alloy (LMSX-4, 6.15 wt% Cr) and the

baseline, Cr was observed to segregate to the dendritic regions. Whereas in low Cr

content alloys (LMSX-5, 2.1 wt% Cr) was observed to segregate to the interdendritic

region. The increasing the Cr content caused Al to segregate to a slightly less, and Al

segregated to the interdendritic region. Kcr in LMSX-5 was almost zero indicating no

preference in segregation.












Table 4-3: Comparison of values calculated by k'B and K.
Alloy Method Ni Cr Co Mo W Re Ta Al Ti Ru Pd
1 K -32.91 0.75 10.02 16.55 47.80 -44.98 -9.12
k'B 0.91 1.04 1.14 1.58 3.10 0.48 0.75
2 K -31.31 2.39 11.60 19.58 55.81 -44.98 -12.59
k'B 0.94 1.20 1.18 1.57 3.04 0.48 0.73
3 K -27.81 0.88 5.29 22.36 57.96 -45.69 -13.01
k'B 0.94 1.07 1.23 1.87 4.86 0.44 0.70
4 K -21.36 1.82 9.59 13.90 40.77 -35.69 -8.98
k'B 0.93 1.05 1.19 1.52 3.08 0.46 0.81
5 K -35.63 -0.20 9.59 17.64 47.36 -27.00 -9.12
k'B 0.94 0.98 1.04 1.64 2.59 0.54 0.78
6 K -41.48 1.71 14.39 29.20 49.66 -38.49 -14.91
k'B 0.93 1.03 1.16 1.89 2.69 0.41 0.69
7 K -15.25 0.18 9.31 -2.63 5.29 39.58 -28.92 -7.55
k'B 0.97 1.10 1.06 0.88 1.41 2.35 0.54 0.84
8 K -25.39 1.06 10.64 -1.39 12.75 39.99 -28.65 -9.11
k'B 0.94 1.03 1.06 0.82 1.46 2.48 0.50 0.85
9 K 1.26 -2.27 5.49 17.99 0.00 -25.92 -4.15
k'B 1.01 1.00 1.11 1.62 0.00 0.61 0.86
10 K -16.92 2.35 14.02 22.23 31.82 -45.59 -7.82
k'B 0.96 1.07 1.19 1.60 3.41 0.50 0.83
11 K -65.36 5.71 16.86 15.51 86.65 -42.52 -16.80
k'B 0.87 1.28 1.25 1.73 6.70 0.34 0.65
12 K -28.80 2.81 13.11 16.91 47.08 -40.80 -10.27
k'B 0.94 1.13 1.15 1.57 2.67 0.54 0.77












Table 4-3 (cont.): Comparison of values calculated by k'B and K.
Alloy Method Ni Cr Co Mo W Re Ta Al Ti Ru Pd
13 K -50.02 -1.89 11.24 22.54 59.26 -25.75 -15.32
k'B 0.89 0.89 1.20 2.07 5.86 0.34 0.69
14 K -41.27 0.64 10.70 22.41 43.09 -18.99 -11.04 -5.59
k'B 0.93 1.19 1.10 1.83 3.12 0.44 0.72 0.42
15 K -30.16 2.07 13.03 19.63 46.81 -30.01 -9.43 -7.14
k'B 0.91 1.14 1.22 1.91 4.03 0.45 0.71 0.37
16 K -33.63 1.62 11.37 16.01 46.51 -31.27 -11.31 0.84
k'B 0.93 1.12 1.19 1.52 2.96 0.47 1.02 1.18
17 K -49.64 5.45 17.68 20.62 64.85 -46.59 -15.08 2.75
k'B 0.90 1.15 1.25 1.86 5.75 0.35 0.71 1.15
18 K -30.19 3.28 18.05 22.04 57.72 -36.08 -15.76 -19.12
18 B 0.93 1.11 1.24 2.08 4.54 0.44 0.68 0.27
k'B 0.93 1.11 1.24 2.08 4.54 0.44 0.68 0.27












4.4.3. Rhenium Segregation Behavior


Re is the element that defines the different generations of superalloys and this part


of the investigation deals with the effects of segregation due to increasing Re content


from 0 wt% Re (LMSX-9, a first generation model superalloy), to 3 wt% Re (LMSXS-


10, a second generation model superalloy), and finally reaching 6 wt% Re (LMSX-1), a


third generation model superalloy. To begin to understand the effect of larger quantities


or Re on an alloy, an additional 3 wt% Re was added in LMSX-11. This discussion will


be related in terms of increasing Re content from 0 wt% to 8.9 wt%. See Figure 4-40 for


graphical representation of the presented information.


Normalized Partitioning due to Co

8000


6000 -

--- N
4000 --Cr
A Co

20 00 -- Re -
W Ta

000
4 6 8 10 12 1

-20 00


-40 00 -


-60 00
wlo Co

Figure 4-38: Elemental segregation plots based on K due to increasing Co content from 4
wt% to 12.2 wt%.












Normalized Partitioning due to Cr

6000

50 00



30 00

20 00


X)- Re
000 ----Ta
Al 2 3 4 5 6
1000

-20 00

3000

-40 00

-50 00
wlo Cr

Figure 4-39: Elemental segregation plots based on K due to increasing Cr content from
2.1 wt% to 6.15 wt%.

Re was the most segregated element in the alloys examined in this series, and the


degree of segregation increased as more Re was added to the system. Re segregated to the


dendritic region, and the K for Re in LMSX-11 was the largest observed in this study. Ta,


which partitioned to the interdendritic region exhibited an initial increase in segregation


when 1 at% Re was added to the system. After this point, the segregation varied, but


remained relatively constant and did not increase further. Ni was found to segregate to


the dendrite core in LMSX-9 (0 wt% Re), and then began to partition to the interdendritic


region, with increasing Re content. The final addition of Re (to 8.9 wt%) caused a large


increase in the segregation behavior of Ni, and KNi became more negative than that of KTa


indicating even more Ni segregation was occurring than Ta. W showed less segregation


than Ni, and it segregated to the dendritic region. The increase in Re did not affect the


segregation behavior of W significantly. The overall behavior of W was nearly constant,









although a slight decrease in segregation was observed. Co initially showed very little

segregation in LMSX-9, but the addition of 1 at% Re increased its partitioning to the

dendritic core. Further additions of Re brought about a slight increase in segregation in

Co. Al segregated to the interdendritic region, and the segregation behavior for Al did

not change from the 0, 1, and 2 at% Re concentrations. The addition of the final 1 at%

Re caused the segregation to increase slightly. Cr was observed to segregate to the

interdendritic region in LMSX-9, but after Re was added, it began to segregate to the

dendritic region. As the Re content was increased, a slow, linear increase in the

segregation of Cr was observed.

LMSX-11 contained four of the strongest segregating elements in this entire

investigation. Ni and Al were the most heavily segregated to the interdendritic region,

and Re were the most heavily segregated to the dendritic core followed by either W and

Co, both of which were observed to have the same degree of segregation. However,

minimums in the segregation behavior of several elements were observed in the low Re

alloys. KA1 was the lowest in LMSX-9, and KRe was at its lowest in LMSX-10.












Normalized Partitioning due to Re

100




60

40

-U-Cr
20 CO
-4 .. ..----------- w -- -- -





wo ReR








Figure 4-40: Elemental segregation plots based on K due to increasing Re content from 0
wt% to 8.9 wt%.
-40

-60

-80
wlo Re


Figure 4-40: Elemental segregation plots based on K due to increasing Re content from 0
wt% to 8.9 wt%.


4.4.4. Tungsten Segregation Behavior

W was studied at two levels: the baseline LMSX-1 (5.85 wt% W) and an increased


level ofW in LMSX-6 (8.6 wt% W). The first observation was that by increasing the W


concentration, all of the elements in the alloys (Ni, Cr, Co, W, Re, Ta, and Al) segregated


more strongly (Figure 4-41). Re, W, Co, and Cr all segregated to the dendrite core. The


degree of segregation was also in this order with Re being the most heavily partitioned,


and Cr being the least partitioned. Ta, Ni, and Al all partitioned to the interdendritic


region. At the low W level (5.85 wt%), Ta segregated the most strongly, followed by Ni


and then Al. When segregation was examined at the high W level (8.6 wt%), Ni and Ta


switched making Ni the most heavily partitioned element segregating to the interdendritic


region. In LMSX-6, W was found to segregate more strongly than in any other alloy in


this study.












Normalized Partitioning varying W

6000

\-Q--NI
-H--Cr
40 00-



2000 Al
-X-W





r 000 -
5.5 6 6.5 7 7.5 8 8.5 9 95

-20 00



-40 00



-60 00
wlo W


Figure 4-41: Elemental segregation plots based on K due to increasing W content from
5.85 wt% to 8.6 wt%.


4.4.5. Tungsten Segregation Behavior with an Addition of Molybdenum


With the addition of 1 at% Mo, LMSX-7 and -8 could be compared to examine the


effects of partitioning with a variation in W. The difference in these to alloys is the


reduced W content of LMSX-7 to 3.1 wt% from 5.85 wt%.


Increasing the W content had little effect on the two most heavily segregated


elements (Figure 4-42). Re, the most heavily segregated of all, remained segregated to


the dendrite core regions. Ta, the second most heavily segregated element, still


segregated to the interdendritic region. Ni was still segregating to the interdendritic


regions and partitioned more strongly as W was added. The increase in KNi with


increasing W was the largest observed in this set of alloys. Initially, Co partitioned more


than W itself to the dendritic region. But after increasing the W concentration, W


segregated more strongly than Co. Al segregated to the interdendritic region. As the W









content was increased, Al began to partition to a slightly greater degree, but not to the

extent of the other elements with the exception of Re and Ta. Cr showed only a small

increase in its behavior of partitioning to the dendritic region, as W was added. Mo,

which partitioned to the interdendritic region, exhibited less segregation as more W was

added to the system. The lowest degree of W segregation, Kw, in this study was observed

in LMSX-7.

4.4.6. Molybdenum Segregation Behavior

Using the baseline LMSX-1 (0 wt% Mo) and comparing it to LMSX-8 (1.6 wt%

Mo), the segregation behavior of Mo could be ascertained. Of the elements that

segregated to the dendrite core region, Re segregated the most, followed by W, then Co,

and finally Cr (Figure 4-43). The elements that segregated to the interdendritic region

were Ta, Ni, Al, and Mo (in order from greatest degree of segregation to least). Re was

the most heavily segregated, and Ta was the second most segregated. The addition of Mo

caused both Re and Ta to segregate less, and by about the same amount. This change in

chemistry also led to a decrease in the segregation Ni and to a lesser degree, W. Al and

Cr had no observable change in segregation behavior due to the addition of 1 at% Mo.

The segregation of Co increased slightly with the addition of Mo.

4.4.7. Ruthenium Segregation Behavior

LMSX-16 and -17 both contained an addition of 1 and 2 (1.6 and 3.2) at% (wt%)

Ru respectively. Analyses were done on the EMPA data to determine the effect of an

addition of Ru on the partitioning of all elements contained in these alloys, and compared

The elements that segregated to the dendritic region (in order of greatest to least) were

Re, W, Co, Cr, and Ru (Figure 4-44). All the other elements (Ni, Ta, and Al) partitioned

to the interdendritic region. The initial addition of 1 at% Ru only showed an effect on the