Investigation of Stiffness Gain Mechanism in Florida Limestone Base Course Material

INVESTIGATION OF STIFFNESS GAIN
MECHANISM IN FLORIDA LIMESTONE
BASE COURSE MATERIAL





















By

LUIS ALFONSO CAMPOS


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

UNIVERSITY OF FLORIDA


2008

































2008 Luis Alfonso Campos


































To my Parents and Sisters and to Carrie















ACKNOWLEDGMENTS

I would like to thank Dr. Bjorn Birgisson for giving me the opportunity to work on

this research project with which most of the work was completed under. I would also like

to thank Dr. Michael C. McVay for taking this research to completion and for his

seemingly limitless knowledge and fascination in geotechnical engineering. I would also

like to thank Dr. Philip S. Neuhoff of the Department of Geology who helped shape this

project and give it a new direction. I would also like to thank Dr. Dennis R. Hiltunen and

Dr. Reynaldo Roque for serving on my supervisory committee.

I appreciate my former boss, the late M. Fred Rwebyogo, and Dr. Frank C.

Townsend's guidance which steered me towards my career in graduate school. I would

also like to thank Dr. David Bloomquist for giving me the opportunity to work on a

separate project which took me around the world to a place I would never have had a

chance to see.

I appreciate the patience and knowledge of Tanya Reidhammer with all of my

chemistry and microscopy questions. I also appreciate the cooperation from the FDOT

State Materials Office. Without their aid and experience this research would not have

been possible.

Finally, I would like to thank my family for their support throughout the years. I

also thank my friends for being such fantastic distractions and entertainment in my life.









TABLE OF CONTENTS

page

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

LIST OF TA BLES ............................. ... .............. .. .... ........... ......... .... ............ vii

LIST OF FIGURES ................ ................................. ................. .......... viii

A B S T R A C T ................................ .................. .......................... ................ .. x

CHAPTER

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

1.1 B ack g rou n d ................................................................................................... . 1
1.2 Purpose and Scope ...................... .... .............. .............................. .2
1.3 M eth odology ................................................................... ................................ . 2

2 L ITER A TU R E R E V IEW .................................................................. ..... .........................

2.1 Introduction ..................................... .......................... ..... ..... ......... 4
2 .2 B ase C ourse M materials .................................................. ........................... ...........4
2.2 Chem istry of Carbonate Cem entation....................................... ......................... 5
2.3 K elvin's Equation ....................... .................................. .......... .... ....
2.4 Com action Issues ...................... .................... ..... .. .............. ....

3 M ATERIALS AND M ETHOD S ............................................................ .......11

3.1 Selection of M materials .................. ..................................... .. ........ .... 11
3 .2 M material P rep aration ............................................................................ ................... 12
3.3 C om action P procedures ....................................................................... ..................13
3.4 Curing Procedures .................. ............................ ............ .. .. ............ 13
3.5 R esonant C olum n T testing ............................................................................. ...... 14
3.6 Scanning E lectron M icroscopy ........................................................................ .. .... 15
3.6.1 Sample Preparation ............... .......................... ............. ............. 15
3.6.2 Scanning Electron Microscopy Analysis.........................................................15
3.6.3 Im aging Softw are ......................................... ........ ........ .. .......... 16
3.7 P orosity M easurem ents ....................................................................... ........ .......... 16
3.8 X -R ay D iffraction ................................................. ...... .............. .. 17

4 RESULTS AND D ISCU SSION .................................................. ............................... 25

4.1 R esonant Colum n R results ................................................... ........ ............... .25
4.2 Scanning Electron M microscope Analysis .......................................... ............... 26
4.3 Porosity M easurem ents ........................................................................... 27
4.4 Discussion ..................................... .................. ................ .......... 29









5 CONCLUSIONS AND RECOMMENDATIONS ............ ........................................51

5 .1 C o n clu sio n s ......................................................... .............. ................ 5 1
5.2 R ecom m endations for Future W ork.................................................................. ......52

APPENDIX

A M odified Proctor and LB R R results ............................................................... ....................54

B Resonant Colum n Testing D ata......................................................................... 57

C C alcu nation s .................................................................................6 5

L IST O F R E F E R E N C E S ...................................................................................... ....................66

B IO G R A PH IC A L SK E T C H ............................................................................... .....................68






































vi









LIST OF TABLES


Table page

3-1 Descriptive data for three limestone base course materials ......................................21

3-2 Equilibrium relative humidity values for saturated aqueous salt solutions .....................21

4-1 Summary of Ocala limestone under different curing conditions................. ................31

4-2 Summary of Miami limestone under different curing conditions...................................31

4-3 Summary of Loxahatchee shell rock under different curing conditions............................32

4-4 Average bulk properties of base course materials .................................. ............... 42

4-5 Summary statistics for pore sizes from ImageJ analysis ............................................. 42

4-6 Comparison of porosity values from different methods ..............................................42

4-7 Theoretical suction pressures for different relative humidities..............................50

B-1 Data for Ocala limestone after compaction ............................................ ............... 57

B-2 D ata for Ocala lim estone after curing ...................................................... .............. 58

B-3 Data for M iami limestone after compaction ..................................... ........ ............... 59

B-4 D ata for M iam i lim estone after curing........................................ ........................... 60

B-5 Data for Loxahatchee shell rock after compaction ................................. ................61

B-6 Data for Loxahatchee shell rock after curing.................................. ....................... 62

C-1 Summary of values used for calculating precipitated calcite ...........................................65









LIST OF FIGURES

Figure page

2-1 Schematic of pavement layers showing concept of structural numbers ............................9

2-2 General relationship between pore diameter and relative humidity ..................................9

2-3 General relationship between total suction and relative humidity................................. 10

3-1 Map of Florida showing approximate locations of aggregate source mines ...................19

3-2 Grain size distribution curves for limestone materials ............................................... 20

3-3 M ercury Porosim eter specim en set-up....................................................................... ...22

3-4 X-Ray diffraction plot for untreated Ocala limestone ................................................. 23

3-5 X-Ray diffraction plot for untreated Miami limestone .............. ...................................23

3-6 X-Ray diffraction plot for untreated Loxahatchee limestone ........................................24

4-1 Ocala lim estone stiffness gain versus tim e ............................................. ............... 33

4-2 M iami limestone stiffness gain versus time.................................................................... 33

4-3 Loxahatchee shell rock stiffness gain versus time ......................................................34

4-4 Ocala limestone stiffness gain versus decrease in initial moisture.............. .................34

4-5 Miami limestone stiffness gain versus decrease in initial moisture...............................35

4-6 Loxahatchee shell rock stiffness gain versus decrease in initial moisture.........................35

4-7 O cala lim stone typical im age 1 ............................................... ............................. 36

4-8 Ocala lim estone typical im age 2 ..................................................................... 36

4-9 M iam i lim estone typical im age 1............................................................ .....................37

4-10 M iam i lim estone typical im age 2 ............................................................ .....................37

4-11 Loxahatchee shell rock typical im age 1 ........................................ ......................... 38

4-12 Loxahatchee shell rock image 2 showing zone of possible calcite crystal growth............38

4-13 Loxahatchee shell rock close-up of highlighted region in Fig. 4-12 .............................39

4-14 G lades core typical im age 1 ...................................................................... ...................39









4-15 Glades core typical image 2 showing zone of calcite crystal growth ............................40

4-16 Glades core close-up of highlighted region in Fig. 4-15 ......................................40

4-17 Glades core typical image 3 showing zone of calcite crystal growth.............................41

4-18 Glades core close-up of highlighted region in Fig. 4-17 ......................................41

4-19 Relative humidity values and corresponding affected pore diameters ...........................43

4-20 Mercury Porosimeter results for 30-day specimens and Glades core.............................44

4-21 Pore diameter histogram from ImageJ analysis for Ocala limestone .............................45

4-22 Pore diameter histogram from ImageJ analysis for Miami limestone.............................45

4-23 Pore diameter histogram from ImageJ analysis for Loxahatchee shell rock ...................46

4-24 Pore diameter histogram from ImageJ analysis for Glades core ...................................46

4-25 Ocala limestone pore diameter distribution from ImageJ analysis...............................47

4-26 Miami limestone pore diameter distribution from ImageJ analysis..............................47

4-27 Loxahatchee shell rock pore diameter distribution from ImageJ analysis.......................48

4-28 Image processing steps with ImageJ software............................................................. 49

4-29 Theoretical relative humidity values and corresponding total suction ...........................50

A-i Ocala limestone Modified Proctor and LBR data..........................................................54

A-2 Miami limestone Modified Proctor and LBR data .................................... ...............55

A-3 Loxahatchee shell rock Modified Proctor and LBR data............................................56

B-l Example 1 of frequency measured in Free-Free Resonant Column test..........................63

B-2 Example 2 of frequency measured in Free-Free Resonant Column test........................64
















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

INVESTIGATION OF STIFFNESS GAIN
MECHANISM IN FLORIDA LIMESTONE
BASE COURSE MATERIAL


By

Luis Alfonso Campos

May 2008

Chair: Michael McVay
Major: Civil Engineering

The Florida Department of Transportation (FDOT) has observed stiffness increases

over time in limestone base course materials. It is a goal of the FDOT to understand the

mechanism involved so that it may implement design procedures to account for the

stiffness increase. Past studies have credited calcium carbonate cementation as providing

the stiffness increase. The objective of this study was to test the hypothesis that

cementation can occur if there are pressure gradients adjacent to grain contacts.

Laboratory investigation involved compacting three Florida limestones and curing in

chambers with high, medium and low relative humidities, which would induce various

degrees of such pressure gradients. Modulus values were obtained over time by

performing free-free resonant column tests on all materials. Compacted materials were

later looked at with a scanning electron microscope to search for crystal growth in the

materials.









It was found that no cementation had occurred during the 30-day test period and

that the observed stiffness gains were a result of capillary suction within the nano and

micro-pores. SEM imagery for an aged field core paired with porosity data suggests that

cementation occurs, but at a much slower rate than observed in the compacted laboratory

specimens. Image analysis of the field core showed the presence of calcite crystals and

much less fine void space than the compacted specimen of similar material. Porosity

measurements were compared between the three compacted materials and the field core

to help clarify what processes are involved with the stiffness increases.














CHAPTER 1
INTRODUCTION

1.1 Background

The state of Florida has over 90,000 miles of paved public roads that commuters

rely on a daily basis. These roadways are designed by highway engineers using the

highest quality of material available while at the same time maximizing the design for

economy. The engineer will try out different material and thickness configurations to deal

with anticipated traffic loads and pick the least expensive design. The highways are

typically designed to last for 25 years or more, but as pavements progress through their

design life, the need to repair or replace the pavement arises.

With routine maintenance, the asphalt surface is milled and made thicker upon

replacement. This asphalt surface layer is by far the most expensive material used for

roadway construction, so optimization is important. The State of Florida Department of

Transportation (FDOT) has studied limestones and has noted significant increases in the

stiffness of the limestone base course materials over time. With stronger base course

materials, less asphalt concrete can be used, saving taxpayer money. Likewise, if the

potential for an increase in stiffness is known before the initial design, the highway

engineers could use this information to further improve upon their designs.

Understanding the behavior and properties of these materials, both present and future, is

the key to better engineering.









1.2 Purpose and Scope

As mentioned, studies have been done that note an increase in stiffness over time in

limerock base course materials (Gartland, 1979; Graves, 1987; Zimpher, 1989). The

FDOT has made attempts to reevaluate design parameters associated with base course

materials to account for the stiffness increase. A problem is that there are many sources

from different geological deposits from which these base course materials are mined. The

need to characterize the engineering properties effectively for each of these sources is

required. Simple tests to characterize some of the properties (such as stiffness) have been

established and are performed on a routine basis by local testing consultants. While

stiffness increases in limestone base course materials have been observed, no test has

been successful in predicting what a generic stiffness increase will be because the

mechanism is not yet fully understood.

One proposed possibility of the stiffness increase is due to calcite crystal growth

and cementation in the micro-pore structure of the limestone. Limestone is mostly

CaCO3, calcium carbonate, which will dissociate and precipitate under various natural

environmental conditions. Calcite crystals will precipitate within what was previously a

void in the limestone. These crystals bond calcite particles together and also create more

contact points with which to resist deformation, resulting in a stiffness increase. The

purpose of this study was to try and create conditions which are favorable for the

precipitation of calcite crystals and observe different material properties which may

affect this phenomenon.

1.3 Methodology

Bricker (1971) noted that cementation in carbonate material occurs due to many

factors, one of which is local pressure gradients adjacent to grain contacts. It is proposed









that by controlling the relative humidity within a curing chamber such a pressure gradient

will be induced and accelerate the cementation process within compacted limestone base

course specimens. The limestone materials were compacted, cured under varying relative

humidities and tested over time for an increase in stiffness.

Three types of limestones representing different geologic formations were used in

this study. Physical and chemical properties were determined for each material. The main

tool used in determining the stiffness increase in the base course materials was the free-

free resonant column test to find modulus values. Scanning electron microscopy (SEM)

techniques and imaging software was used to find pore structure characteristics in the

three cured materials. Pore structure data for a field core sample was also measured for

comparison.














CHAPTER 2
LITERATURE REVIEW

2.1 Introduction

The purpose of this research project was to create conditions which are favorable

for the precipitation of calcite crystals and observe different material properties which

may affect this phenomenon. A review of the literature was conducted to find information

on base course materials, carbonate cementation and compaction issues for limestone

base course materials.

2.2 Base Course Materials

Highway pavements fall into three design categories: flexible, rigid or composite

pavements. The most commonly used pavement type in Florida is the flexible design.

This design consists of an asphalt surface course, a base course just below that, and the

subgrade which consists of the existing soil. The goal of a pavement system is to protect

the subgrade. Therefore, high quality materials are used for the surface and base courses.

Pavements layers are designed using the concept of structural numbers. In order to

prevent an anticipated amount of damage to the layer just below, a structural number

requirement should be met. The quality and stiffness of each layer of material is indicated

by a structural layer coefficient, a. The structural number for each layer can be calculated

by multiplying the structural layer coefficient by the layer thickness. A diagram of the

pavement system and design is shown in Fig. 2-1. Design procedures can be found in

many textbooks, including Huang (2004). In the state of Florida, limestone is the most

commonly used base course material. Before the pavements are designed by engineers,









the structural layer coefficient, a, is know for each material. Materials with higher a

values are desired since designers can use less of the stiffer material, which cuts costs.

Past studies on limestone base course materials have observed increase in stiffness

over time, and have credited these stiffness increases to calcite cementation. Gartland

(1979) used treatment methods which mimicked vadose and phreatic conditions, as well

as using different water sources to test their effect on stiffness increase. It was found that

the greatest stiffness increases occurred under phreatic conditions (no cycling) and when

using plain water. The time required for significant cementation to occur was not

generically identified. Graves (1987) continued on a similar study by testing mixtures

with varying ratios of calcite to quartz. Phreatic curing conditions were simulated in an

attempt to find the length of time required for a significant stiffness increase. It was found

that the highest stiffness increase in untreated materials occurred after 14 days. Materials

with higher carbonate to quartz ratios showed greater stiffness increases. Similar work

and field testing has caused the FDOT to reevaluate the structural coefficient for base

course materials (Smith and Lofroos, 1981). Structural layer coefficients were changed

from 0.15 to 0.18 as recommended to account for the future increases in stiffness, but the

authors felt that more testing should be completed.

2.2 Chemistry of Carbonate Cementation

The goal of this research was to create conditions which are favorable for carbonate

cementation, as past studies have shown that this is the mechanism responsible for

stiffness increases. Calcium carbonate is very common throughout the state of Florida.

Carbonate cements are responsible for a significant amount of the cements which hold

together sedimentary rocks. Calcium carbonate will also dissolve and reprecipitate as

under typical changes in environmental conditions.









Carbon dioxide, C02, plays a major role in the solubility of CaCO3. Various

sources of CO2 in water exist. Carbon dioxide from the atmosphere may dissolve in

falling rainwater or CO2 may be provided to groundwater by bacteria or other organisms

in soil. With increased CO2 levels in water, more CaCO3 can be dissolved. Miller (1952)

described the process that CO2 in the atmosphere combines with water to form carbonic

acid which in turn reacts with calcium carbonate to form the soluble bicarbonate:

H20 + CO2 H2CO3 H H + (HCO3)-

CaCO3 + H+ + (HCO3)- Ca2+ + 2(HCO3)

These reactions show that CO2 gas must be present in order for the calcium carbonate to

dissolve or precipitate. Bricker (1971) states that the emplacement of carbonate cements

require precipitation from solution. Also, one way that CaCO3 can be made

supersaturated (and thus more able to precipitate) is through pressure reduction, or by

having local pressure gradients adjacent to grain contacts.

Other work has been done on the pore filling material. Lindholm (1974) states that

aragonite, a polymorph of calcite, is instable at near-surface environmental conditions.

Aragonite is not expected to be present in the base course materials, therefore only

rhombohedral calcite crystals are expected to be found. Although calcite cements may

precipitate, Moore (1989) notes that much of the porosity in limestones is intraparticle,

which is unique to carbonates. The living chambers, or shells, of various organisms

provide this source of porosity. Although calcite cement may be present in such pores,

they would not contribute to any stiffness increase. Caution must be used when searching

for calcite crystals, as this may be the case.









2.3 Kelvin's Equation

The use of saturated salt solutions is a way to control the relative humidity in a

confined space. Saturated salt solutions are able to adsorb relatively large quantities of

water while maintaining a constant relative humidity (Lu and Likos, 2004). Also, the

resulting relative humidities from the use of saturated salt solutions will cause the

pressure gradients which will drive the calcium carbonate precipitation within the pore

spaces. Kelvin's equation governs the relationship between the pressure changes across a

curved air-liquid boundary to the vapor pressure above the boundary. One form of

Kelvin's equation can be written:

4Tsvw
ln(RH) =- (2.1)
dRT

where RH is the relative humidity, Ts is surface tension (N/m), vw is the partial molar

volume of water vapor (m3/mol), d is the pore diameter (m), R is the universal gas

constant (N-m/K-mol) and Tis temperature (K). The pore structure can be idealized as a

system of capillary tubes with diameter d. These capillaries will fill with liquid and form

a meniscus dependant on the above variables. In the presence of a given relative

humidity, the pores will either lose or gain water, causing the meniscus to change and the

resulting vapor pressure above the air-liquid boundary will cause a pressure gradient to

exist within the material pores. The effect of curvature on the vapor pressures explains

the ability of the vapors and solutions in the pores to supersaturate (Shaw, 1992). Figure

2-2 shows the relationship between relative humidity and the pore diameter which it will

effect.

The relative humidities exhibited by the saturated salt solutions effects the pore

water in specimens. The relative humidity of the saturated salt solutions will cause the









pore water to evaporate until equilibrium is reached between the vapor and liquid in the

pore spaces, which causes suction. Kelvin's equation can also be rewritten in terms of

total suction as:

RT
yVt ln(RH) (2.2)
VwOCOv

where Vt is the total soil suction (kPa), vwo is the specific volume of the liquid (m3/kg), coy

is the molecular mass of the liquid vapor (kg/kmol), and R and Tare defined as above.

Figure 2-3 shows the relationship between relative humidity and total suction.

2.4 Compaction Issues

It is proposed that the specimens be compacted at 1% wet of the optimum moisture

content even though for granular materials, this generally decreases initial stiffness

values. This was done for two reasons. First, the extra fluid will be able to contain more

calcium carbonate in solution. Second, laboratory compaction curves generally yield

somewhat lower optimum moisture contents than the actual field optimum (Lambe and

Whitman, 1969). It is hoped that this will mimic field results better and more calcite

cements will precipitate, resulting in higher stiffness increases.












al


SN1 = D, x a


BASE
D2 a2 SN2 = D2X a2



SUB-BASE
D3 a3 SN3 = D3X a3


Figure 2-1. Schematic of pavement layers showing concept of structural numbers.


1.E-09 1.E-08 1.E-07

Pore Diameter (meters)

General relationship between pore diameter and relative humidity.


AC


SN


1.0

0.8

0.6

0.4

0.2

0.0
1.E-10


Figure 2-2.


1.E-06


D,










1.E+07

1.E+06

a 1.E+05
a-

S1.E+04

1.E+03

o 1.E+02

1.E+01

1.E+00 -
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Relative Humidity


General relationship between total suction and relative humidity.


Figure 2-3.














CHAPTER 3
MATERIALS AND METHODS

3.1 Selection of Materials

For roadway construction projects, the State of Florida allows the contractor to

choose the base course material in accordance with standard specifications, although

many contractors favor local materials as transportation costs are the major deciding

factor. There are many acceptable aggregate sources from different geological formations

across the State of Florida. The stiffness of these limestone base course materials is based

on many factors. The gradation, mineralogy, particle shape, moisture content and

compactive effort will determine the initial stiffness of the base course material.

The objective of this research was to better understand the stiffness gain

mechanism in base course material. As stated earlier, the physical and mineralogical

properties of Florida limestones vary from one geologic formation to the other, as well as

within the formations themselves. Three commonly used limestones from across Florida

were chosen as representative aggregates. The base course materials chosen were Ocala

limestone, Miami limestone and Loxahatchee shell rock (mines 26002, 87090 and 93406,

respectively, Fig. 3-1). These aggregates come from the Ocala Group, Miami Oolite and

Anastasia Formation, respectively.

For comparison, a field core taken from Glades County, Florida will be examined.

The base course material in the Glades core appears to be Miami limestone based on

physical characteristics and specific gravity, although it is uncertain what mine the

material originated from as attempts at verification have been unsuccessful.









3.2 Material Preparation

Aggregate was obtained from each of the three quarries in Florida. The material

was then dried and sieved to obtain grain size distribution curves as shown in Fig. 3-2.

Sieve analysis shows that the Miami limestone is the coarsest material, followed by the

Loxahatchee shell rock then the Ocala limestone. The Ocala Limestone had the highest

percentage of material passing the #200 sieve, followed by the Miami limestone and then

the Loxahatchee shell rock. Materials were separated by the #4 sieve in order to separate

the coarse and fine aggregate. Prior to compaction, specimens were remixed according to

the overall proportions in an attempt to maximize uniformity for the multiple specimens.

Material greater than 34" was omitted because there is a maximum allowable aggregate

size for both the resonant column (ASTM D 4015) and Limerock Bearing Ratio (LBR)

testing (FM 5-515).

Modified Proctor (ASTM D 1557) and LBR testing was also completed on the

aggregates in order to verify that the materials meet the FDOT standards. Detailed

Modified Proctor and LBR data are presented in Appendix A. The LBR testing was

performed in accordance with FM 5-515 except for the fact that, as stated earlier, material

greater than 34" was discarded instead of crushed to 34" as required in the test. The FDOT

State Materials Office (SMO) completed Modified Proctor and LBR testing on the three

materials and descriptive data is given in Table 3-1. It should be noted that the material

from the Ocala quarry did not meet the minimum required LBR value of 100 as shown in

Table 3-1, but was used regardless since the increase in stiffness is of concern rather than

the initial stiffness values.









3.3 Compaction Procedures

Modified Proctor data gave the optimum moisture content required for compaction.

Materials were compacted at 1% wet of the optimum moisture content (See

LITERATURE REVIEW) into 4" diameter by 8" height plastic cylinders because

resonant column testing requires an aspect ratio of no less than 2:1. It should be noted

these dimensions are different from ASTM D 1557 which requires either a 4" or 6"

diameter by 4.584" height rigid metal mold. Plastic cylinders were chosen because

portions would later be sawed out for the destructive testing portion of this experiment.

Compaction procedures from ASTM D 1557 had to be modified to ensure that the

modified compactive effort of 56,000 ft-lbf/ft3 was still achieved. The specimens were

compacted in 9 layers with 25 blows per layer to achieve the Modified Proctor density.

The 10 pound hammer and 18" drop were still used. Materials were compacted using a

Rainhart automatic tamper at the FDOT SMO.

Two specimens were compacted for each testing variation and the resulting

modulus values and moisture content reductions were averaged. The testing variations

consisted of four different time periods and three different curing humidities. In total, 24

duplicate specimens were compacted for each of the three aggregate sources.

3.4 Curing Procedures

Curing periods of 2, 7, 15 and 30 days were used in this study to assess stiffness

increase over time. After compaction, the cylinders were placed in curing chambers for

the allotted time periods. Desiccator cabinets of approximately 0.75 ft3 were used as

curing chambers. The seals were previously tested to ensure no leakage. To maintain a

constant relative humidity in each of the chambers, different saturated salt solutions were









used. It was desired to use solutions which exhibited high, medium and low relative

humidities.

Saturated salt solutions were prepared by mixing a quantity of lithium chloride (RH

S11%), magnesium nitrate (RH z 53%) or potassium sulfate (RH Z 97%) with gently

heated, distilled water. Once the solution cools, excess solids will precipitate if the

solution is beyond saturation. This allows moisture from the compacted specimens to be

absorbed by the saturated salt solutions until excess solids are no longer present.

Approximately 250 mL of solution were used in each of the curing chambers and either

replaced or remixed as necessary to ensure that solids were present. Conditions inside

curing chambers were monitored with the use of temperature and humidity gages. The

temperature dependencies of the saturated salt solutions according to ASTM E 104 are

presented in Table 3-2. The temperature remained at a constant 250 C within the

chambers throughout the test period.

3.5 Resonant Column Testing

Testing for an increase in stiffness for each of the materials was the main concern

of this research. The testing program was designed to investigate the stiffness increase as

a function of relative humidity and time. It was important that the modulus test be non-

destructive as the later tests that would characterize different properties of the materials

are destructive.

The free-free resonant-column modulus test is a small strain (less than 10-4 in/in)

test which consists of applying a vibration excitation at one end of the specimen and

measuring the resulting vibration patterns from the applied compression wave at the other

end. Fifteen tests were conducted and averaged to obtain the resonant frequency of each

specimen. The resonant frequency was then used along with and geometric properties and









the compression wave speed to calculate Young's modulus values. Initial measurements

were taken immediately after compaction and final measurements were taken after the

allotted curing time for each specimen. After testing was completed, cylinders were

capped to ensure no further loss in moisture.

3.6 Scanning Electron Microscopy

3.6.1 Sample Preparation

In order to view specimens in the SEM, portions of the compacted specimens had

to be cut in order to be mounted and fit in the SEM. A major problem which must be

overcome is the brittleness of the compacted materials. Upon cutting the material from

the cylinders to the size required to fit in the SEM (approximately 1 in3), most of the

material will break apart from the vibration caused by the cutting saw which prevents the

examination of coherent pieces. In order to prepare samples for SEM analysis, large

slices measuring approximately 1.5" thick and 4" diameter were cut from the plastic

cylinders dried in an oven. The pieces were further broken by hand into the 1 in3 size

required to fit in the SEM mounting chamber. These samples were impregnated with a

low viscosity epoxy in order to fill as many voids as possible. Epoxied samples were then

cut and sanded until polished. When viewed in the SEM, the density of the epoxy makes

it appears black, allowing for easy identification of voids.

3.6.2 Scanning Electron Microscopy Analysis

SEM examinations of the three compacted materials and the field core were

conducted in order to search for the presence of calcite crystals. Specimens measured

approximately 3.0 cm by 2.5 cm and were flat. Fourteen random points were selected on

each specimen and images were taken. Any calcite crystals visible at this scale were

further investigated. As stated earlier, samples were polished so that the SEM settings









would not need to be reconfigured while investigating each sample and also in order to

run Energy Dispersive Spectrometer (EDS). The spectrometer identified and mapped the

chemicals present for selected images.

SEM examinations were conducted using a Hitachi S-3000 N Scanning Electron

Microscope with an EDS x-ray analyzer at the UF Department of Civil and Coastal

Engineering.

3.6.3 Imaging Software

ImageJ is an image processing program made available to the public. It was used to

characterize the number and size of voids in each of the SEM images. The SEM images

used for pore size analysis were taken at 90X magnification which limited the minimum

void size that the imaging software could discern as it only counts pixels. In the images, 1

mm is equal to 880 pixels and so the software will be able to recognize pore sizes greater

than 2 im. It was desired to count voids in this range as weight-volume relationships

were used to calculate bulk porosity and mercury porosimeter measurements were used to

describe pores smaller than 100 nm. If a higher magnification was used, it was felt that

the 14 images for each sample would not be a large enough sample population to describe

the pore structure.

A subroutine in ImageJ converted the SEM images from grayscale to binary. The

voids appeared black and were counted and sorted by total area. The software allows the

user to set the minimum pore size that the software will recognize.

3.7 Porosity Measurements

Porosity measurements were completed on 30-day samples cured under low

relative humidity. Specimens must be completely dry as any moisture will be turned into

compressible water vapor. This test is ran in two stages which cover a pore range









between approximately 150 [m and 1.8 nm. The specimen for this apparatus must fit

inside a glass sample cell as shown in Figure 3-3. Representative samples were difficult

to obtain since the compacted material is approximately 1650 cm3 and the mercury

porosimeter device accepts specimens of approximately 1.5 cm3. In an attempt to test

representative samples, aggregate pieces were taken with finer particles attached (no

"clean" aggregate).

All materials were tested in accordance with ASTM D 4404 using a Quantachrome

Autoscan 60 Mercury Porosimeter at the UF Particle Engineering Research Center

(PERC). Testing was completed by PERC personnel.

3.8 X-Ray Diffraction

X-Ray Diffraction (XRD) measurements were taken on the three virgin aggregate

sources. Approximately 5 grams of each aggregate was ground up with a mortar and

pestle and passed through the #200 sieve. From this, chemical and crystallographic

composition was obtained. The resulting plots are shown in Figs. 3-4, 3-5 and 3-6. These

plot show various intensities coupled with 2*0 angles. Each 2*0 angle pattern

corresponds to a unique crystalline structure, thereby making it possible not only to detect

quartz and calcite, but also to distinguish calcite from its polymorph aragonite. The

intensities at each angle, along with other data that may be obtained from the geometry of

these plots, represent the relative quantity of each mineral present. Minerals were

identified by matching the observed patterns to a mineralogical powder diffraction

database maintained by the Univ. of Arizona. From this database, quartz is known to

diffract with a major peak at 20 between 26.60 and 26.70, calcite with a major peak

(subsequent peaks exist and are present) at 20 between 29.40 and 29.50 and aragonite

with a major peak at 20 between 26.20 and 26.3.






18


As illustrated, calcite is the main component of each aggregate source. The Ocala

limestone is almost exclusively comprised of calcite while the Miami limestone and

Loxahatchee shell rock are comprised of calcite and quartz. It should also be noted that

aragonite was not present in any of the aggregate sources.

All materials were tested using a Philips APD 3720 powder diffractometer at the

UF Major Analytical Instrumentation Center (MAIC). Testing was completed by MAIC

personnel.




















26002


93406


87090


^p
+ P*~ -ra


Figure 3-1. Map of Florida showing approximate locations of aggregate source mines.














































/

cU II 0


0 0 0 0 0 0 0 0 0
m) co r- (D 10 'T co N N -


6U!SSed ZU03JOd


E



cn
N



CD
















Table 3-1. Descriptive data for three limestone base course materials.
Maximum Dry Optimum Water
Carbonate Density Content
Material Mine No. Content (pcf) (%) LBR
Ocala 26-002 99.2 111.8 13.4 92
Miami 87-090 77.5 129.6 7.8 175
Loxahatchee 93-406 53.8 127.2 7.9 131


Table 3-2. Equilibrium relative humidity values for saturated aqueous salt solutions.


Temperature
(C)
20
25
30


Lithium Chloride,
LiCl H20
11.3 + 0.3
11.3 + 0.3
11.3 + 0.2


Magnesium Nitrate,
Mg(NO3)2 6H20
54.4 + 0.2
52.9 + 0.2
51.4 + 0.2


Potassium Sulfate,
K2SO4
97.6 + 0.5
97.3 + 0.5
97.0 + 0.4


























SAMPLE CELL


1.0 cm
i_


SAMPLE


Figure 3-3. Mercury Porosimeter specimen set-up. Mercury is intruded from right
side. Approximate specimen size is 1 cm x 2 cm.


i









5000

4000

, 3000

" 2000

1000

0
25


30


n _
40
Angle (2*0)


Figure 3-4. X-Ray diffraction plot for untreated Ocala limestone.





5000

4000

S3000

r 2000

1000

0
25 30 35 40 45 50 55
Angle (2*0)


Figure 3-5. X-Ray diffraction plot for untreated Miami limestone.


h ~nn


'= ,-
























5000

4000

, 3000

" 2000

1000

0-
25


30 35 40 45 50 55
Angle (2*0)


Figure 3-6. X-Ray diffraction plot for untreated Loxahatchee limestone.














CHAPTER 4
RESULTS AND DISCUSSION

4.1 Resonant Column Results

The main test to determine the increase in modulus of the conditioned limestones

was the free-free resonant column test. Modulus and moisture content data for the

different materials and curing conditions are given in Tables 4-1 through 4-3. The

Young's modulus is compared relative to the 8 averaged initial modulus values for the

different relative humidities and the different compacted base course materials. Modulus

values are plotted as a percent increase over this initial reference modulus. Values

reported are averages of duplicate molds tested for each base course material and curing

condition. The data was plotted in Figs. 4-1 through 4-3 in order to better illustrate the

increases in stiffness. Each material showed increases in stiffness for all three relative

humidity levels with the greatest increase occurring when cured under low relative

humidity conditions. The stiffness of the Ocala limestone increased by approximately

2100%, the Miami limestone by 1600% and the Loxahatchee shell rock by 940% when

cured under low relative humidity conditions. Modulus values for materials cured under

high relative humidity conditions appear to be near their maximum as values are only

slightly increasing after 7 days. The Loxahatchee shell rock showed the lowest overall

modulus increases for each curing relative humidity and in general, modulus values only

slightly increase after 15 days. The modulus values of the Ocala and Miami limestones

increase at an almost constant rate for both the medium and low relative humidities and it

is evident from the plots that the modulus values show no sign of reaching a maximum









value. However, it is expected that the increase in modulus will diminish just as the

modulus values for the high relative humidity tests have. Resonant Column Testing data

is reported in Appendix B.

The initial weights for each test cylinder were record and compared with the

weights after curing. This weight loss is due to the saturated salt solutions absorbing

moisture from the specimens. The percentage of initial moisture lost was plotted against

the percent increase over the reference modulus as shown in Figs. 4-4 through 4-6. Each

material showed an approximately linear relationship between the percent moisture lost

and the percent increase in modulus, regardless of curing conditions. The Ocala limestone

gained more stiffness per moisture lost followed by the Miami limestone and finally the

Loxahatchee shell rock. These trends show that over this testing period the increase in

stiffness is related to moisture loss.

4.2 Scanning Electron Microscope Analysis

Scanning electron microscopy techniques were used in order to see whether the

moisture loss resulted in calcite cement growth, which could be responsible for the

observed stiffness increase in the resonant column testing portion of the research.

Specimens from materials cured for 30 days under low relative humidity were prepared

and examined because it was felt that they had the highest potential for showing calcite

cement bonding. Also, a section from a field core from Glades County was examined for

comparison with the laboratory compacted specimens.

After modulus testing, the selected specimens were cut out of the cylinder molds

and prepared for SEM analysis as stated in Chapter 3. Fourteen random locations on each

specimen were examined for the presence of calcite crystal and patterns which would

suggest growth. Selected images from the analysis showing typical characteristics are









presented. Figures 4-7 through 4-11 are typical examples of the Ocala, Miami and

Loxahatchee images. The light aggregates are calcium carbonate, grey aggregates are

quartz and the black areas are the intruded epoxy. SEM exploration of the laboratory

compacted specimens did not reveal zones with calcite cement growth. Figure 4-12

reveals a zone in the Loxahatchee shell rock containing textures related to calcite crystals.

Figure 4-13 is a close-up of the area of interest in Fig. 4-12, but reveals that the crystals

are only intraparticle and therefore would not contribute to any stiffness increase from

aggregate-to-aggregate cementation.

Scanning electron micrographs of the Glades core were also taken. Typically, the

Glades core shows less void area than the compacted specimens. Also, many of the

Glades core images contained easy to spot, relatively large calcite crystals which are

appear to be growing between aggregates. Typical features of the Glades core are shown

in Figs. 4-14 through 4-18. Rhombohedral calcite crystals are shown filling in the pore

spaces in Figures 4-16 and 4-18.

Additionally, element maps were taken for selected SEM images. Element maps for

the Ocala limestone consist of calcium, carbon and oxygen which indicates that only

calcite is present. Element maps for the Miami limestone and Loxahatchee shell rock

consist of calcium, carbon, oxygen and silicon which indicate the presence of calcite and

quartz. These measurements are in agreement with the XRD analysis.

4.3 Porosity Measurements

The initial moisture content values were taken for each material during the modulus

testing portion of this research. The theoretical porosity was calculated using classic

weight-volume relationships. Descriptive properties are presented in Table 4-4. These

values represent the bulk porosity for the materials and are useful for comparing the









different methods for finding porosity. The calculations for the bulk specimens show that

the porosity for these materials ranges between 0.238 and 0.318.

Mercury Porosimeter testing gave further insight into the void structure of the

compacted limestone. Mercury porosimetry is able to give distributions of pore sizes

while bulk porosity measurements do not. The mercury porosimetry test is capable of

giving measurements accurate to diameters ranging between 3.6 nm and 100 inm. This

range of pore diameters corresponds with Kelvin's equation as stated in eq (2.1) which

shows the pore diameters that are affected by the relative humidities. Figure 4-19 shows a

plot of this equation for typical values of water of Ts = 0.072 N/m, vw = 1.8x105 m3/mol.

The temperature used was T= 298.15 K and the universal gas constant R = 8.314472

N-m/K-mol. Results in Figure 4-20 show that the Ocala limestone has the greatest amount

of fine pores of all the materials followed by the Miami limestone and finally the

Loxahatchee shell rock. The slope of each line indicates the number of pores at each

diameter. The flat portions of the plot ranging between 10-6 and 10-5 meters are due to

testing inaccuracies. As stated earlier, the test is run in two stages and it is between these

ranges that the transition between testing stages occurs.

The ImageJ software was used to analyze all the images from the SEM exploration.

Each image was made binary and the software counted and gave the area for each void.

Imaging analysis was used to describe the pore diameter data between 2x10-6 and 1x10-3

meters which covers the range of the transition measurements in the mercury

porosimetry. Data was reduced and summary statistics are shown in Table 4-5.

Histograms of the pore data ranging between 2x10-6 and 2x105 meters are presented in

Figs. 4-21 through 4-24, as this data accounts for over 97% of the pores found with the









software. Figures 4-25 through 4-27 presents the pore diameter distribution from ImageJ

analysis in relation to porosity and shows what portion of the total porosity the analysis

represents. The Glades core data was omitted because the bulk porosity was not known.

An example of the image processing steps is shown in Fig. 4-28.

The three different porosity measurements were compared in Table 4-6. The

porosity results show that for both the Ocala and Miami limestones, the Mercury

Porosimeter test reports higher porosity values than the SEM image analysis, but for the

Loxahatchee shell rock, the opposite is true. These results can lead one to the conclusion

that overall, the pores in the Ocala and Miami limestone are generally smaller and those

found in the Loxahatchee shell rock are generally larger.

4.4 Discussion

The resonant column test indicated stiffness increases for all materials. The Ocala

limestone showed the greatest rate for stiffness increase while Loxahatchee shell rock

showed the slowest rate of stiffness increase. Although solubility calculations show that

in the time frame for the experiment, only a small amount of calcite cement was able to

precipitate, SEM exploration did not reveal the presence of cementing calcite crystals in

any of the laboratory compacted specimens. The maximum volume of calcite able to

precipitate was 9.0x10-4 cm3 in the Ocala limestone cured under low relative humidity for

30 days, which was the best-case scenario. The cylinder volume was approximately 1650

cm3, so this equates to 0.00005% of new material precipitation. Calculations appear in

Appendix C. This amount of calcite precipitation would be very difficult to locate.

However, images taken of the Glades core commonly show cementing calcite crystals

and filling most voids.









Even though calculations show that calcite cement was able to precipitate, it is

believed that it is not the source for the increase in stiffness. Instead, suction from the loss

of water in the pore spaces is reasonable. The potential for stiffness increase due to

suction is determined from the Kelvin's equation as stated in eq (2.2). Figure 4.29 shows

a plot of this equation for typical values for water of vo = 0.001 m3/kg, co, = 18.016

kg/kmol and T and R are previously defined. Table 4.7 shows this theoretical suction

pressure for each of the relative humidities used. The theoretical total suction values

differ by approximately an order of magnitude which provides an explanation for the

difference in stiffness increases for each curing condition. It is felt that the materials

cured under the medium and low relative humidities did not reach equilibrium with the

saturated salt solutions and therefore did not reach the potential moisture loss to show the

full effects of the stiffness increase due to the suction pressures. The materials cured

under high relative humidity reached near-constant moisture contents, so the effects of

the suction pressure are shown in the material stiffness.











Table 4-1. Summary of Ocala limestone under different curing conditions. Average
stiffness gain and reduction in moisture content versus time.
Average Time Average % Decrease Average % Increase
Curing Type (days) in Initial Moisture in Young's Modulus
Low RH 1.99 1.05% 142.0%
7.94 3.13% 573.5%
15.83 5.04% 959.7%
32.10 9.96% 2108.6%
Medium RH 1.99 0.76% 71.4%
7.95 2.52% 551.0%
15.83 3.35% 657.4%
32.04 8.03% 1513.3%
High RH 1.99 0.56% 58.2%
7.97 1.18% 466.1%
15.84 1.55% 475.1%
32.04 1.94% 536.8%











Table 4-2. Summary of Miami limestone under different curing conditions. Average
stiffness gain and reduction in moisture content versus time.
Average Time Average % Decrease Average % Increase
Curing Type (days) in Initial Moisture in Young's Modulus
Low RH 2.05 1.36% 42.0%
7.77 3.82% 457.9%
15.76 7.20% 971.8%
31.09 11.17% 1627.6%
Medium RH 2.05 1.03% 59.1%
7.79 3.39% 221.0%
15.77 4.86% 647.3%
31.07 9.35% 1118.8%
High RH 2.05 0.73% 22.6%
7.81 1.42% 28.0%
15.78 1.73% 73.0%
31.10 2.68% 149.4%


























Table 4-3. Summary of Loxahatchee shell rock under different curing conditions.
Average stiffness gain and reduction in moisture content versus time.
Average Time Average % Decrease Average % Increase
Curing Type (days) in Initial Moisture in Young's Modulus
Low RH 2.00 2.18% 170.4%
7.82 4.02% 354.6%
15.83 8.50% 798.8%
31.24 12.76% 940.0%
Medium RH 1.98 1.19% 121.0%
7.83 2.90% 265.9%
15.84 5.33% 596.9%
31.24 8.43% 637.9%
High RH 1.97 0.34% 52.4%
7.85 1.12% 187.2%
15.85 1.38% 277.1%
31.24 2.21% 307.7%










u 2400%
-5

0 2000%

S1600%
c
o 1200%
a-

a 800%

400%

0%


- Low
- Medium
-aHigh


0 5 10 15 20
Time (days)


25 30 35


Figure 4-1.






u 2400%

0 2000%

-1600%
c
o 1200%

a 800%
U,)

400%

0%


Ocala limestone stiffness gain versus time for different relative humidities.












Low
Medium
High


0 5 10 15 20 25 30 35
Time (days)


Figure 4-2. Miami limestone stiffness gain versus time for different relative
humidities.










2400%

2000%

1600%

1200%

800%

400%

0%


0 5 10 15 20
Time (days)


25 30 35


Figure 4-3. Loxahatchee shell rock stiffness gain versus time for different relative
humidities.




u, 2400%

0
| 2000% -

-S 1600%
-" -- Low
o 1200% Medium
.= +- High
S800%

o 400%

0%
0% 2% 4% 6% 8% 10% 12% 14%
% Decrease in Initial Moisture


Figure 4-4.


Ocala limestone stiffness gain versus decrease in initial moisture for
different relative humidities.


-- Low
- Medium
-aHigh










, 2400%

" 2000%

-, 1600%
00
o 1200%


800%

400%

0%
0% 2% 4% 6% 8% 10% 12% 14%
% Decrease in Initial Moisture


Figure 4-5.


-- Low
--Medium
-a-High


Miami limestone stiffness gain versus decrease in initial moisture for
different relative humidities.


u 2400%

" 2000%

-, 1600%
0 0
o 1200%


-- Low
- Medium
-- High


w 800%

- 400%

0% ,,-
0% 2% 4% 6% 8% 10% 12% 14%
% Decrease in Initial Moisture


Figure 4-6. Loxahatchee shell rock stiffness gain versus decrease in initial moisture
for different relative humidities.








































Ocala limestone typical image 1.


Ocala limestone typical image 2.


Figure 4-7.


Figure 4-8.


--.r r
.r
.i a rr~br
(I 'EL

a :II,'r: ~i~(t I

~?d~~:1

I: i
a9~ r. -



























Miami limestone typical image 1.


Figure 4-10. Miami limestone typical image 2.


Figure 4-9.


u

B






















Loxahatchee shell rock typical image 1.


Figure 4-12. Loxahatchee shell rock image 2 showing zone of possible calcite crystal
growth on left side.


Figure 4-11.


~4]4~88 ~~~j-
oa~C~"~:
'Q,"s!
~--cs~ L s1~slS 1











-4.
S VAR'


Figure 4-13. Loxahatchee shell rock close-up of highlighted region in Fig. 4-12.


Figure 4-14. Glades core typical image 1.































Figure 4-15.


Glades core typical image 2 showing zone of calcite crystal growth.


*' 1














.9
.4~ iia


Figure 4-16. Glades core close-up of highlighted region in Fig. 4-15.










L C

iJt


Figure 4-17.


Glades core typical image 3 showing zone of calcite crystal growth.


~4f L~et. .j


Figure 4-18. Glades core close-up of highlighted region in Fig. 4-17.












Table 4-4. Average bulk properties of base course materials.
Average Moisture
Specimen Specific Gravity Content (%) Porosity, n
Ocala Limestone 2.75 14.28 0.318
Miami Limestone 2.78 8.76 0.238
Loxahatchee Shell Rock 2.84 9.00 0.266


Glades Core


2.78


Table 4-5. Summary statistics for pore sizes from ImageJ analysis.


Specimen
Mean
Standard Error
Median
Mode
Standard Deviation
Sample Variance
Kurtosis
Skewness
Range
Minimum
Maximum
Sum
Count


Ocala
6.07E-06
8.59E-08
3.63E-06
2.57E-06
1.41E-05
1.99E-10
493.6809
18.9514
0.000522
2.57E-06
0.000524
0.163367
26917


Miami
5.55E-06
4.54E-08
3.63E-06
2.57E-06
9.28E-06
8.62E-11
701.3346
19.53987
0.000532
2.57E-06
0.000535
0.231454
41715


Loxahatchee
6.31E-06
1.37E-07
3.84E-06
2.56E-06
1.76E-05
3.1E-10
926.6147
24.77442
0.000932
2.56E-06
0.000934
0.104128
16497


Glades Core
5.39E-06
7.37E-08
3.63E-06
2.56E-06
1.09E-05
1.18E-10
1008.251
24.98864
0.000651
2.56E-06
0.000654
0.116765
21677


Table 4-6. Comparison of porosity values from different methods.
Bulk Mercury SEM Image
Specimen Measurements Porosimetry Analysis
Ocala Limestone 0.318 0.235 0.183
Miami Limestone 0.238 0.150 0.147
Loxahatchee Shell Rock 0.266 0.101 0.170


0.088


Glades Core


---


0.101
























1.0
0.973 ....................
0.9
0.8

0.7

0 0.6
0. 0.529 .. ... ......
0 0.5
I
S0.4D r
^ 0.3

0.2
0.113
0.1 ---------------------

0.0
1.E-10 1.E-09 1.E-08 1.E-07 1.E-06
Pore Diameter (meters)


Figure 4-19. Relative humidity values and corresponding affected pore diameters.
Horizontal lines represent targeted relative humidities.



























o

f =5
00





0




? o
E II
-E 0




oo
'-
0 -
E 0


o
0


0?

















10 0 10 0 0 o
S0 0

AI!soJod WlWOI|
i ^-^' // /:EE
J/^ ^ / : .




/^~~ ~ /// :Il
/ ~ ~~ / Q
/~~~~P / / T!r^r
















15300




5921


II2171


.0E-06


8.0E-06


1111 609 399

1.2E-05


280 185 134


1.6E-05


Pore Diameter (meters)


Figure 4-21. Pore diameter histogram from ImageJ analysis for Ocala limestone.
Values above bars are frequency.







100%
-0 100%


879 521 392 243 189


1.2E-05


1.6E-05


2.0E-05


Pore Diameter (meters)


Figure 4-22. Pore diameter histogram from ImageJ analysis for Miami limestone.
Values above bars are frequency.


100%


80%


60%


40%


20%


0%
4


2.0E-05
2.0E-05


80%

60%

40%

20%

0%


23664


9654


3505


1642


4.0E-06


8.0E-06
















8920



3900

1558

E-06 8. E-
OE-06 8.0E-06


351 230 158

1.2E-05 1.6E-05
1.2E-05 1.6E-05


121 65

2.OE-05
2.0E-05


Pore Diameter (meters)


Figure 4-23. Pore diameter histogram from ImageJ analysis for Loxahatchee shell rock.
Values above bars are frequency.




100%


80%


60%


40%


20%


13030


4678


1687


4.0E-06


8.0E-06


779 424 212 157 130 103


1.2E-05


1.6E-05


2.0E-05


Pore Diameter (meters)


Figure 4-24. Pore diameter histogram from ImageJ analysis for Glades core. Values
above bars are frequency.


100%


80%


60%


40%


20%


0%
4.











0.35
0
0.30
0.25
0.20
0.15
0.10
0.05
0.00
1.E-06


.318


1.E-05


1.E-04


1.E-03


Pore Diameter (meters)


Figure 4-25. Ocala limestone pore diameter distribution from ImageJ analysis in
relation to porosity. Horizontal line is the bulk porosity.


0.35
0.30
0.25 0.238
0.20
0.15
0.10
0.05
0.00
1.E-06


1.E-05


1.E-04


1.E-03


Pore Diameter (meters)


Figure 4-26. Miami limestone pore diameter distribution from ImageJ analysis in
relation to porosity. Horizontal line is the bulk porosity.



























0.35
0.30
^ 0.25
2 0.20
o
a-
- 0.15
0 0.10
0.05
0.00


0.266


1.E-06


1.E-05


1.E-04


1.E-03


Pore Diameter (meters)


Figure 4-27. Loxahatchee shell rock pore diameter distribution from ImageJ analysis in
relation to porosity. Horizontal line is the bulk porosity.







49



















-..^ ..






al l

**" ,*''-



',t f i ,t


A.4
**^*2wl.^ ^ -. 6 ,W. >Y-l' ;






















Figure 4-28. Image processing steps with ImageJ software. Example is from Ocala
specimen. A) Original SEM image taken in grayscale. B) Image converted
into binary. C) Binary image is converted into outlines and area data is
obtained.
"* .^ :.^ -^ -
Figre -2. Iageprcesingstps it Image sotwreExmlisfo ca
spcien A)Oiia E mg ae n rycl.B mg ovre
inobnr.C inr mg scnere nootiesadae aai
ob-taied











1.E+07

1.E+06

. 1.E+05
r-

g 1.E+04

" 1.E+03

5 1.E+02
I--


1.E+01

I C-i-nfl


I I


0.113 0.529 0.973


0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9


Relative Humidity


Figure 4-29.


Theoretical relative humidity values and corresponding total suction.
Vertical lines represent targeted relative humidities.


Table 4-7. Theoretical suction pressures for different relative humidities.
Suction Pressure Suction Pressure
Relative Humidity (kPa) (ksi)


Low
Medium
High


300,000
88,000
3800


43.6
12.8
0.55















CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS

5.1 Conclusions

1. Curing compacted specimens with different relative humidities resulted in

stiffness increases for each material type. Materials cured under low relative humidity

conditions showed the greatest increase in stiffness while materials cured under high

relative humidity conditions showed the lowest stiffness increase.

2. Materials cured under high relative humidity reached stable moisture contents

during the testing period. Materials cured under medium and low relative humidities did

not reach stable moisture contents in the allotted test period, but are likewise expected to

stabilize.

3. Stiffness increases in this experiment were due to increases in capillary suction

due to the removal of water from the system.

4. Materials with more fine pores in the sub-micron level and also more material

passing the #200 sieve resulted in greater stiffness increases. Ocala limestone showed the

greatest stiffness increase while Loxahatchee shell rock showed the lowest, which agrees

with this statement.

5. Materials showed a linear relationship between % increase in Young's modulus

and increased % reductions in moisture content. It is thought that the % increase in

Young's modulus will reach some maximum value, though the testing period was not

long enough to verify this.









6. Although all materials showed an increase in stiffness, calculations show the

potential crystal growth from calcite in solution was negligible. Expectantly, SEM

analysis did not reveal the presence of calcite crystals. It is concluded that the testing

period was not long enough to allow the materials to reach equilibrium with the saturated

salt solutions.

7. SEM imaging in the Glades core reveal the presence of relatively large calcite

crystals. The orientation of these crystals suggests that pores are being filled. Porosity

measurements in the Glades core also indicate that most of the pore volume has been

filled.

8. SEM analysis coupled with the ImageJ software provided excellent quantitative

analysis for describing voids.

5.2 Recommendations for Future Work

1. Roadway conditions of base course material should be studied. Sensors

recording the temperature, relative humidity, CO2 levels and moisture migration in pores

can be implemented during construction. Future test should be long term and mimic these

relevant field conditions rather than changing individual conditions that may be

irrelevant.

2. Doping the specimens with a know substance during compaction would be

beneficial when looking for new calcite growth. Due to the small quantities of calcite

crystals that precipitate and the heterogeneity of limestones, it is very difficult to

distinguish new crystal growth from crystals that may have formed hundreds or

thousands of years ago. Neoformed crystals would include the doped substance and

would be recognizable using EDS, XRD or cathodoluminescence techniques.






53


3. It may be coincidental that the materials with higher fines content resulted in

higher stiffness increases, but the effect of fines in regards to increases in stiffness should

be studied.

4. The effect of initial moisture content should be studied because contractors may

meet density requirements using moisture contents both wet and dry of the optimum. A

range of initial moisture contents and their effect on stiffness increase should be tested as

materials in this study were only compacted 1% wet of the optimum moisture content.















APPENDIX A
MODIFIED PROCTOR AND LBR RESULTS


e i
E s

0a

a a
ir

U,
Mrl


Ocala limestone Modified Proctor and LBR data


v9 tCO


MOISTURE (%)


_ ~


" -II I


Figure A-1.
























































S C


MOISTURE (%)

MOISTURE (%)


Miami limestone Modified Proctor and LBR data


C__


.. .1 .. A=


r u) (0 1-


CO 01


Figure A-2.























































0 I'- c C 0 C -


C3 S Co 0 -


MOISTURE(%)


Loxahatchee shell rock Modified Proctor and LBR data


_


yl II I


Figure A-3.
















APPENDIX B
RESONANT COLUMN TESTING DATA


Table B-1. Data for Ocala Limestone after Compaction
Quarry : Ocala Mold Wt: 0.242 Ibs
Pit Number : 26-002 Diameter: 4 in
Sample Number : 26-AII Height: 8 in
Testing Condition : Initial Volume: 100.531 in^3
_Volume: 0.0582 ft^3

Moisture Density,
Date, Time MIS Weight Freq. Vp E
Specimen Content p
(m/ddlyy hh:mm) (Ibs) () (Hz) (ftsec) (ksi)

26-L-02-1 9/1/07 23:40 8.05 14.44% 104 4.1714 139 0.56
26-L-02-2 9/4/07 23:40 8.07 14.14% 136 4.1821 181 0.95
26-L-07-1 8/18/07 20:55 7.99 14.31% 120 4.1393 160 0.74
26-L-07-2 8/18/07 21:05 7.97 14.49% 216 4.1286 288 2.38
26-L-14-1 7/15/07 19:50 8.03 14.00% 128 4.1607 171 0.84
26-L-14-2 8/7/07 19:55 7.99 14.37% 112 4.1393 149 0.64
26-L-30-1 7/15/07 19:30 8.03 14.36% 152 4.1607 203 1.19
26-L-30-2 7/15/07 19:35 8.04 14.35% 136 4.1660 181 0.95
26-M-02-1 9/1/07 23:45 8.03 14.55% 104 4.1607 139 0.56
26-M-02-2 9/4/07 23:45 8.06 14.32% 104 4.1767 139 0.56
26-M-07-1 8/18/07 20:45 8.00 14.35% 120 4.1447 160 0.74
26-M-07-2 8/18/07 20:50 8.06 14.18% 112 4.1767 149 0.65
26-M-14-1 7/15/07 19:50 8.00 14.19% 136 4.1447 181 0.95
26-M-14-2 8/7/07 19:45 8.00 14.19% 120 4.1447 160 0.74
26-M-30-1 7/15/07 19:20 8.09 14.02% 176 4.1927 235 1.60
26-M-30-2 7/15/07 19:25 8.08 14.14% 112 4.1874 149 0.65
26-H-02-1 9/1/07 23:50 8.05 14.35% 120 4.1714 160 0.74
26-H-02-2 9/4/07 23:50 8.01 14.33% 128 4.1500 171 0.84
26-H-07-1 8/18/07 20:30 7.96 14.45% 120 4.1233 160 0.73
26-H-07-2 8/18/07 20:40 8.01 14.43% 120 4.1500 160 0.74
26-H-14-1 7/15/07 19:40 8.02 14.07% 136 4.1553 181 0.95
26-H-14-2 8/7/07 19:40 7.97 14.30% 128 4.1286 171 0.84
26-H-30-1 7/15/07 19:10 8.04 14.04% 120 4.1660 160 0.74
26-H-30-2 7/15/07 19:15 8.03 14.24% 120 4.1607 160 0.74










Table B-2. Data for Ocala Limestone after Curing
Quarry : Ocala Mold Wt: 0.242 Ibs
Pit Number : 26-002 Diameter: 4 in
Sample Number : 26-All Height: 8 in
Testing Condition : Final Volume: 100.531 in^3
Volume: 0.0582 ft^3

M/S Moisture
Date, Time S Moistur eq. Density, p Vp E
Specimen Days Weight Content si)
(m/ddlyy hh:mm) (Hz) (Ibs/ft3) (ftsec) (ksi)
-__ (Ibs) (%) _
26-L-02-1 9/3/07 23:40 2.00 8.04 14.29% 152 4.1660 203 1.19
26-L-02-2 9/6/07 23:00 1.97 8.05 13.99% 224 4.1714 299 2.58
26-L-07-1 8/26/07 19:25 7.94 7.96 13.90% 376 4.1233 501 7.20
26-L-07-2 8/26/07 19:30 7.93 7.93 14.00% 416 4.1073 555 8.78
26-L-14-1 8/1/07 13:45 16.75 7.95 13.00% 416 4.1179 555 8.80
26-L-14-2 8/22/07 17:40 14.91 7.95 13.94% 368 4.1179 491 6.88
26-L-30-1 8/16/07 20:25 32.04 7.92 12.92% 696 4.1019 928 24.53
26-L-30-2 8/16/07 23:30 32.16 7.93 12.93% 664 4.1073 885 22.36
26-M-02-1 9/3/07 23:45 2.00 8.02 14.48% 144 4.1553 192 1.06
26-M-02-2 9/6/07 23:05 1.97 8.05 14.17% 128 4.1714 171 0.84
26-M-07-1 8/26/07 19:35 7.95 7.97 13.97% 336 4.1286 448 5.75
26-M-07-2 8/26/07 19:40 7.95 8.04 13.84% 256 4.1660 341 3.37
26-M-14-1 8/1/07 13:50 16.75 7.95 13.55% 360 4.1179 480 6.59
26-M-14-2 8/22/07 17:45 14.92 7.97 13.88% 344 4.1286 459 6.03
26-M-30-1 8/16/07 20:15 32.04 8.00 12.88% 568 4.1447 757 16.51
26-M-30-2 8/16/07 20:20 32.04 7.99 13.02% 528 4.1393 704 14.25
26-H-02-1 9/3/07 23:50 2.00 8.05 14.32% 152 4.1714 203 1.19
26-H-02-2 9/6/07 23:10 1.97 8.00 14.20% 160 4.1447 213 1.31
26-H-07-1 8/26/07 19:45 7.97 7.95 14.28% 306 4.1179 408 4.76
26-H-07-2 8/26/07 19:50 7.97 7.99 14.26% 264 4.1393 352 3.56
26-H-14-1 8/1/07 13:55 16.76 8.01 13.85% 360 4.1500 480 6.64
26-H-14-2 8/22/07 17:50 14.92 7.95 14.08% 272 4.1179 363 3.76
26-H-30-1 8/16/07 20:05 32.04 8.02 13.76% 344 4.1553 459 6.07
26-H-30-2 8/16/07 20:10 32.04 8.01 13.97% 256 4.1500 341 3.36





n~t~ for Mi;lmi T.ime8tnne ;Ifter C~nmn~ctinn


Table B-3


Quarry : Miami Mold Wt: 0.242 lbs
Pit Number : 87-090 Diameter: 4 in
Sample Number : 87-AII Height: 8 in
Testing Condition : Initial Volume: 100.531 in^3
Volume: 0.0582 ft^3

Moisture Density,
Date, Time MIS Weight Freq. Vp E
Specimen Content p
(m/ddlyy hh:mm) (Ibs) (Hz) (ft/sec) (ksi)
(%) (lbs/ft3
87-L-02-1 9/4/07 22:00 8.66 8.85% 184 4.4973 245 1.88
87-L-02-2 9/4/07 22:05 8.64 8.80% 144 4.4866 192 1.15
87-L-07-1 8/18/07 23:25 8.56 8.88% 224 4.4438 299 2.75
87-L-07-2 8/18/07 23:30 8.61 8.92% 136 4.4705 181 1.02
87-L-14-1 7/15/07 22:45 8.63 8.63% 152 4.4812 203 1.28
87-L-14-2 8/7/07 20:15 8.62 8.60% 208 4.4759 277 2.39
87-L-30-1 7/16/07 16:45 8.60 8.79% 152 4.4652 203 1.27
87-L-30-2 7/16/07 16:50 8.62 9.03% 160 4.4759 213 1.41
87-M-02-1 9/4/07 22:10 8.62 8.75% 144 4.4759 192 1.15
87-M-02-2 9/4/07 22:20 8.61 8.69% 160 4.4705 213 1.41
87-M-07-1 8/18/07 23:15 8.63 8.93% 184 4.4812 245 1.87
87-M-07-2 8/18/07 23:20 8.59 8.49% 136 4.4599 181 1.02
87-M-14-1 7/15/07 22:40 8.61 8.50% 144 4.4705 192 1.14
87-M-14-2 8/7/07 20:10 8.61 9.20% 216 4.4705 288 2.58
87-M-30-1 7/16/07 16:35 8.54 8.06% 152 4.4331 203 1.26
87-M-30-2 7/16/07 16:40 8.63 8.30% 136 4.4812 181 1.02
87-H-02-1 9/4/07 22:25 8.56 9.01% 112 4.4438 149 0.69
87-H-02-2 9/4/07 22:30 8.50 8.72% 112 4.4118 149 0.68
87-H-07-1 8/18/07 23:05 8.54 8.76% 152 4.4331 203 1.26
87-H-07-2 8/18/07 23:10 8.55 8.90% 152 4.4385 203 1.27
87-H-14-1 7/15/07 22:35 8.61 8.73% 192 4.4705 256 2.03
87-H-14-2 8/7/07 20:05 8.61 9.19% 160 4.4705 213 1.41
87-H-30-1 7/16/07 16:25 8.63 8.96% 152 4.4812 203 1.28
87-H-30-2 7/16/07 16:30 8.56 8.57% 184 4.4438 245 1.86





n~t~ for Mi;lmi T.ime8tnne ;Ifter C~llring


TableB-4


Quarry : Miami Mold Wt: 0.242 lbs
Pit Number 87-090 Diameter: 4 in
Sample Number : 87-All Height: 8 in
Testing Condition : Final Volume: 100.531 in^3
Volume: 0.0582 ft^3

SM/S Moisture
Date, Time Freq. Density, p Vp E
Specimen Days Weight Content si)
(m/ddlyy hh:mm) (Hz) (Ibs/ft3) (ft/sec) (ksi)
____ (Ibs) I(%) __
87-L-02-1 9/6/07 23:15 2.05 8.65 8.71% 224 4.4919 299 2.78
87-L-02-2 9/6/07 23:20 2.05 8.63 8.70% 168 4.4812 224 1.56
87-L-07-1 8/26/07 18:00 7.77 8.53 8.53% 304 4.4278 405 5.05
87-L-07-2 8/26/07 18:05 7.77 8.58 8.59% 416 4.4545 555 9.52
87-L-14-1 8/1/07 13:20 16.61 8.55 7.74% 584 4.4385 779 18.69
87-L-14-2 8/22/07 18:10 14.91 8.59 8.25% 544 4.4599 725 16.29
87-L-30-1 8/16/07 18:55 31.09 8.51 7.80% 688 4.4171 917 25.81
87-L-30-2 8/16/07 19:00 31.09 8.53 8.03% 608 4.4278 811 20.21
87-M-02-1 9/6/07 23:25 2.05 8.61 8.65% 176 4.4705 235 1.71
87-M-02-2 9/6/07 23:30 2.05 8.61 8.61% 208 4.4705 277 2.39
87-M-07-1 8/26/07 18:15 7.79 8.60 8.60% 240 4.4652 320 3.18
87-M-07-2 8/26/07 18:20 7.79 8.57 8.23% 296 4.4492 395 4.81
87-M-14-1 8/1/07 13:25 16.61 8.56 7.88% 496 4.4438 661 13.50
87-M-14-2 8/22/07 18:20 14.92 8.59 8.96% 384 4.4599 512 8.12
87-M-30-1 8/16/07 18:15 31.07 8.48 7.28% 432 4.4011 576 10.14
87-M-30-2 8/16/07 18:30 31.08 8.57 7.55% 552 4.4492 736 16.74
87-H-02-1 9/6/07 23:35 2.05 8.56 8.94% 128 4.4438 171 0.90
87-H-02-2 9/6/07 23:40 2.05 8.49 8.66% 120 4.4064 160 0.78
87-H-07-1 8/26/07 18:25 7.81 8.53 8.64% 176 4.4278 235 1.69
87-H-07-2 8/26/07 18:30 7.81 8.54 8.77% 168 4.4331 224 1.54
87-H-14-1 8/1/07 13:30 16.62 8.60 8.57% 224 4.4652 299 2.77
87-H-14-2 8/22/07 18:30 14.93 8.60 9.04% 232 4.4652 309 2.97
87-H-30-1 8/16/07 18:45 31.10 8.61 8.72% 176 4.4705 235 1.71
87-H-30-2 8/16/07 18:50 31.10 8.54 8.34% 352 4.4331 469 6.78





n~t~ for T.nx~h~tchee ~ihell Rnck;lfter C~nmn~ctinn


Table B-5


Quarry : Loxahatchee Mold Wt: 0.242 lbs
Pit Number : 93-406 Diameter: 4 in
Sample Number : 93-AII Height: 8 in
Testing Condition : Initial Volume: 100.531 in^3
Volume: 0.0582 ft^3

Moisture Density,
Date, Time MIS Weight Freq. Vp E
Specimen Content p
(m/ddlyy hh:mm) (Ibs) (Hz) (ft/sec) (ksi)
(%) (lbs/ft3
93-L-02-1 9/1/07 22:00 8.55 8.66% 240 4.4385 320 3.16
93-L-02-2 9/1/07 22:05 8.55 9.20% 264 4.4385 352 3.82
93-L-07-1 8/18/07 22:55 8.46 8.99% 288 4.3904 384 4.50
93-L-07-2 8/18/07 23:00 8.47 8.94% 232 4.3958 309 2.92
93-L-14-1 7/15/07 22:25 8.50 8.75% 216 4.4118 288 2.54
93-L-14-2 8/7/07 17:25 8.47 9.01% 168 4.3958 224 1.53
93-L-30-1 7/16/07 13:45 8.51 9.03% 208 4.4171 277 2.36
93-L-30-2 7/16/07 13:50 8.52 9.15% 216 4.4225 288 2.55
93-M-02-1 9/1/07 22:10 8.54 8.81% 256 4.4331 341 3.59
93-M-02-2 9/1/07 23:20 8.52 8.89% 272 4.4225 363 4.04
93-M-07-1 8/18/07 22:45 8.46 9.11% 192 4.3904 256 2.00
93-M-07-2 8/18/07 22:50 8.53 9.15% 248 4.4278 331 3.36
93-M-14-1 7/15/07 22:20 8.50 9.23% 192 4.4118 256 2.01
93-M-14-2 8/7/07 17:20 8.48 8.79% 192 4.4011 256 2.00
93-M-30-1 7/16/07 13:35 8.51 9.78% 280 4.4171 373 4.28
93-M-30-2 7/16/07 13:40 8.57 8.73% 208 4.4492 277 2.38
93-H-02-1 9/1/07 23:15 8.51 9.24% 272 4.4171 363 4.03
93-H-02-2 9/1/07 23:30 8.55 8.62% 300 4.4385 400 4.93
93-H-07-1 8/18/07 22:35 8.49 9.00% 160 4.4064 213 1.39
93-H-07-2 8/18/07 22:40 8.48 8.80% 184 4.4011 245 1.84
93-H-14-1 7/15/07 22:15 8.42 8.76% 208 4.3690 277 2.33
93-H-14-2 8/7/07 17:00 8.51 9.31% 216 4.4171 288 2.54
93-H-30-1 7/16/07 13:25 8.49 9.07% 144 4.4064 192 1.13
93-H-30-2 7/16/07 13:30 8.49 9.07% 192 4.4064 256 2.01





n~t~ for T.nx~h~tchee ~ihell Rnck;lfter C~llring


Table B-6


Quarry : Lox Mold Wt: 0.242 lbs
Pit Number : 93-406 Diameter: 4 in
Sample Number : 93-All Height: 8 in
Testing Condition : Final Volume: 100.531 in^3
Volume: 0.0582 ft^3

SM/S Moisture
Date, Time Freq. Density, p Vp E
Specimen Days Weight Content si)
(m/ddlyy hh:mm) (Hz) (Ibs/ft3) (ft/sec) (ksi)
____ (Ibs) I(%) __
93-L-02-1 9/3/07 22:00 2.00 8.54 8.51% 424 4.4331 565 9.84
93-L-02-2 9/3/07 22:05 2.00 8.53 8.96% 400 4.4278 533 8.75
93-L-07-1 8/26/07 18:35 7.82 8.43 8.63% 536 4.3744 715 15.52
93-L-07-2 8/26/07 18:40 7.82 8.44 8.58% 552 4.3797 736 16.48
93-L-14-1 8/1/07 13:00 16.61 8.42 7.73% 608 4.3690 811 19.94
93-L-14-2 8/22/07 18:40 15.05 8.43 8.52% 536 4.3744 715 15.52
93-L-30-1 8/16/07 19:35 31.24 8.42 7.84% 728 4.3690 971 28.59
93-L-30-2 8/16/07 19:40 31.24 8.43 8.02% 640 4.3744 853 22.12
93-M-02-1 9/3/07 22:10 2.00 8.54 8.73% 392 4.4331 523 8.41
93-M-02-2 9/3/07 22:20 1.96 8.51 8.76% 392 4.4171 523 8.38
93-M-07-1 8/26/07 18:45 7.83 8.44 8.82% 376 4.3797 501 7.64
93-M-07-2 8/26/07 18:50 7.83 8.51 8.91% 464 4.4171 619 11.74
93-M-14-1 8/1/07 13:05 16.61 8.45 8.60% 568 4.3851 757 17.47
93-M-14-2 8/22/07 18:45 15.06 8.46 8.46% 440 4.3904 587 10.49
93-M-30-1 8/16/07 19:25 31.24 8.45 8.95% 704 4.3851 939 26.83
93-M-30-2 8/16/07 19:30 31.24 8.51 8.00% 608 4.4171 811 20.16
93-H-02-1 9/3/07 22:30 1.97 8.50 9.20% 352 4.4118 469 6.75
93-H-02-2 9/3/07 22:40 1.97 8.54 8.60% 352 4.4331 469 6.78
93-H-07-1 8/26/07 18:55 7.85 8.49 8.90% 264 4.4064 352 3.79
93-H-07-2 8/26/07 19:00 7.85 8.47 8.70% 320 4.3958 427 5.56
93-H-14-1 8/1/07 13:15 16.63 8.41 8.63% 400 4.3637 533 8.62
93-H-14-2 8/22/07 18:50 15.08 8.50 9.19% 424 4.4118 565 9.79
93-H-30-1 8/16/07 19:15 31.24 8.47 8.81% 288 4.3958 384 4.50
93-H-30-2 8/16/07 19:20 31.24 8.48 8.93% 392 4.4011 523 8.35






























































III _____ I I I'-I
0 Ln Hz 3
X:188Hz Y:2.68517


Figure B-1. Example 1 of frequency measured in Free-Free Resonant Column test.
Initial value from specimen 93-L-14-2.

























































0 Un Hz 3
X:53-HI Y:2.52701


Figure B-2. Example 2 of frequency measured in Free-Free Resonant Column test.
Final value from specimen 93-L-14-2.















APPENDIX C
CALCULATIONS

From Faure (1998), the highest possible concentration of calcium ions in solution is:

[Ca2] = 4.86x 104 (mol/L)


Vcacite = 36.93 (cm3 mol)


Molar volume of calcite


36.93 (cm3/mol) x 4.86x 10-4 (mol/L) = 1.79x 10-2 cm3/L


1.79 x 102 cm3/L


Ocala volume of solution = 0.501 L

0.501 (L) x 79 x 10-2 (cm3/L) = 9. Ox 10-3 Cm3

Moisture loss = 10%


9.0x 0-l3x 0.10

9.0x 0-4 cm3


9.0x]0-4cm3


Amount of calcite able to precipitate

Initial volume of water in specimen

Volume of Calcite able to precipitate

Moisture loss observed for low RH
curing


Volume of calcite precipitated


Table C-1. Summary of values used for calculating precipitated calcite.
Volume of Maximum Maximum Vol. of
Amount of calcite able to Moisture Calcite able to
Solution precipitate Lost Precipitate for Test
Material (Liters) (cm3) (%) Conditions (cm3)
Ocala 0.501 9.0x10-3 10 9.0x10-4
Miami 0.330 5.9 x103 11 6.5 x10-4
Loxahatchee 0.336 6.0x 103 13 7.8x10-4














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Transportation.

University of Arizona, "The RRUFFTM Project." http://rruff.geo.arizona.edu/rruff/ (last
accessed October 2007)

Zimpfer, W.H. (1989) S. ength Gain and Cementation ofFlexible Pavement Bases. Final
Report for the Florida Department of Transportation. University of Florida,
Department of Civil Engineering.















BIOGRAPHICAL SKETCH

Luis Alfonso Campos was born in 1983 in Tampa, Florida. After

graduating from Sickles High School in 2001, he attended the University of

Florida where he received a Bachelor of Science degree in December 2005 with a

major in civil engineering.

During his undergraduate studies, he worked part time at a small

geotechnical engineering firm in Gainesville where he gained valuable experience

in geotechnical engineering. The experience that he gained led him to continue

with graduate studies at the University of Florida. He received a Master of

Engineering degree in May 2008 and plans to work at a geotechnical consulting

firm in North Carolina.





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INVESTIGATION OF STIFFNESS GAIN MECHANISM IN FLORIDA LIMESTONE BASE COURSE MATERIAL By LUIS ALFONSO CAMPOS 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 ENGINEERING UNIVERSITY OF FLORIDA 2008

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2008 Luis Alfonso Campos

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To my Parents and Sisters and to Carrie

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iv ACKNOWLEDGMENTS I would like to thank Dr. Bjorn Birgisson for giving m e the opportunity to work on this research project with wh ich most of the work was completed under. I would also like to thank Dr. Michael C. McVay for taking this research to completion and for his seemingly limitless knowledge and fascination in geotechnical engineering. I would also like to thank Dr. Philip S. Neuhoff of the De partment of Geology who helped shape this project and give it a new dir ection. I would also like to th ank Dr. Dennis R. Hiltunen and Dr. Reynaldo Roque for serving on my supervisory committee. I appreciate my former boss, the la te M. Fred Rwebyogo, and Dr. Frank C. Townsends guidance which steered me toward s my career in graduate school. I would also like to thank Dr. David Bloomquist for giving me the opportunity to work on a separate project which took me around the world to a place I would never have had a chance to see. I appreciate the patience and knowledge of Tanya Reidhammer with all of my chemistry and microscopy questions. I also appreciate the cooperation from the FDOT State Materials Office. Without their aid a nd experience th is research would not have been possible. Finally, I would like to thank my family for their support throughout the years. I also thank my friends for being such fantasti c distractions and entertainment in my life.

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v TABLE OF CONTENTS page ACKNOWLEDGMENTS............................................................................................................. iv LIST OF TABLES................................................................................................................. ....... vii LIST OF FIGURES..................................................................................................................... viii ABSTRACT.....................................................................................................................................x CHAP TER 1 INTRODUCTION....................................................................................................................1 1.1 Background ....................................................................................................................1 1.2 Purpose and Scope .........................................................................................................2 1.3 Methodology ..................................................................................................................2 2 LITERATURE REVIEW.........................................................................................................4 2.1 Introduction ................................................................................................................... .4 2.2 Base Course Materials ...................................................................................................4 2.2 Chemistry of Carbonate Cementation............................................................................ 5 2.3 Kelvins Equation ..........................................................................................................7 2.4 Compaction Issues......................................................................................................... 8 3 MATERIALS AND METHODS........................................................................................... 11 3.1 Selection of Materials ..................................................................................................11 3.2 Material Preparation.....................................................................................................12 3.3 Compaction Procedures............................................................................................... 13 3.4 Curing Procedures ........................................................................................................13 3.5 Resonant Colum n Testing............................................................................................ 14 3.6 Scanning Electron Microscopy ....................................................................................15 3.6.1 Sample Preparation............................................................................................15 3.6.2 Scanning Electron Microscopy Analysis ...........................................................15 3.6.3 Imaging Software............................................................................................... 16 3.7 Porosity Measurem ents................................................................................................ 16 3.8 X-Ray Diffr action........................................................................................................17 4 RESULTS AND DISCUSSION............................................................................................. 25 4.1 Resonant Colum n Results............................................................................................ 25 4.2 Scanning Electron Microscope Analysis .....................................................................26 4.3 Porosity Measurem ents................................................................................................ 27 4.4 Discussion ....................................................................................................................29

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vi 5 CONCLUSIONS AND RECOMME NDATIONS................................................................. 51 5.1 Conclusions ..................................................................................................................51 5.2 Recommendations for Future W ork.............................................................................52 APPENDIX A Modified Proctor and LBR Results........................................................................................ 54 B Resonant Column Testing Data.............................................................................................. 57 C Calculations............................................................................................................................65 LIST OF REFERENCES...............................................................................................................66 BIOGRAPHICAL SKETCH.........................................................................................................68

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vii LIST OF TABLES Table page 3-1 Descriptive data for three lim es tone base course materials............................................... 21 3-2 Equilib rium relative humidity values fo r saturated aqueous salt solutions....................... 21 4-1 Summ ary of Ocala limestone unde r different curing conditions....................................... 31 4-2 Summ ary of Miami limestone unde r different curing conditions...................................... 31 4-3 Summ ary of Loxahatchee shell rock under different curing conditions............................ 32 4-4 Average bulk properties of base course m aterials............................................................. 42 4-5 Summ ary statistics for pore sizes from ImageJ analysis................................................... 42 4-6 Comparison of porosity values from different methods.................................................... 42 4-7 Theoretical suction p ressures for different relative humidities.......................................... 50 B-1 Data for Ocala lim estone after compaction....................................................................... 57 B-2 Data for Ocala limestone after curing................................................................................ 58 B-3 Data for Miam i limest one after compaction...................................................................... 59 B-4 Data for Miam i limestone after curing............................................................................... 60 B-5 Data for Loxahatchee shell rock after com paction............................................................ 61 B-6 Data for Loxahatchee shell rock after curing ..................................................................... 62 C-1 Summary of values used fo r calculating precipitated calcite............................................. 65

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viii LIST OF FIGURES Figure page 2-1 Schem atic of pavement layers showing concept of structural numbers.............................. 9 2-2 General relationship between pore diam eter and relative humidity.................................... 9 2-3 General relationship between tota l suction and relative hum idity..................................... 10 3-1 Map of Florida showing approxim ate lo cations of aggregate source mines..................... 19 3-2 Grain size distribution curves for lim estone materials...................................................... 20 3-3 Mercury Porosim eter specimen set-up............................................................................... 22 3-4 X-Ray diffr action plot for untreated Ocala limestone.......................................................23 3-5 X-Ray diffr action plot for untreated Miami limestone...................................................... 23 3-6 X-Ray diffr action plot for untre ated Loxahatchee limestone............................................ 24 4-1 Ocala lim estone stiffness gain versus time........................................................................ 33 4-2 Miam i limestone stiffness gain versus time....................................................................... 33 4-3 Loxahatchee shell rock stiffness gain versus tim e............................................................. 34 4-4 Ocala lim estone stiffness gain vers us decrease in initial moisture.................................... 34 4-5 Miam i limestone stiffness gain versus decrease in initial moisture................................... 35 4-6 Loxahatchee shell rock stiffness gain versus decrease in initial m oisture......................... 35 4-7 Ocala lim estone typical image 1........................................................................................ 36 4-8 Ocala lim estone typical image 2........................................................................................ 36 4-9 Miam i limestone typical image 1....................................................................................... 37 4-10 Miam i limestone typical image 2....................................................................................... 37 4-11 Loxahatchee shell rock typical im age 1............................................................................. 38 4-12 Loxahatchee shell rock image 2 showing zone of possible calcite crystal growth ............ 38 4-13 Loxahatchee shell rock close-up of highlighted region in Fig. 4-12 ................................. 39 4-14 Glades core typical im age 1............................................................................................... 39

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ix 4-15 Glades core typical im age 2 showi ng zone of calcite crystal growth................................ 40 4-16 Glades core close-up of highlighted region in Fig. 4-15 ................................................... 40 4-17 Glades core typical im age 3 showi ng zone of calcite crystal growth................................ 41 4-18 Glades core close-up of highlighted region in Fig. 4-17 ................................................... 41 4-19 Relative hum idity values and corr esponding affected pore diameters.............................. 43 4-20 Mercury Porosim eter results for 30-day specimens and Glades core................................ 44 4-21 Pore diam eter histogram from Imag eJ analysis for Ocala limestone................................ 45 4-22 Pore diam eter histogram from ImageJ analysis for Miami limestone............................... 45 4-23 Pore diam eter histogram from ImageJ analysis for Loxahatchee shell rock..................... 46 4-24 Pore diam eter histogram from ImageJ analysis for Glades core....................................... 46 4-25 Ocala lim estone pore diameter dist ribution from ImageJ analysis.................................... 47 4-26 Miam i limestone pore diameter dist ribution from ImageJ analysis................................... 47 4-27 Loxahatchee shell rock pore diam eter distribution from ImageJ analysis......................... 48 4-28 Image processing steps w ith ImageJ software................................................................... 49 4-29 Theoretical relative hum idity values and corresponding total suction.............................. 50 A-1 Ocala lim estone Modified Proctor and LBR data.............................................................. 54 A-2 Miam i limestone Modified Proctor and LBR data............................................................ 55 A-3 Loxahatchee shell rock Modi fied Proctor and L BR data................................................... 56 B-1 Exam ple 1 of frequency measured in Free-Free Resonant Column test............................ 63 B-2 Exam ple 2 of frequency measured in Free-Free Resonant Column test............................ 64

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x Abstract of Thesis Presen ted to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Engineering INVESTIGATION OF STIFFNESS GAIN MECHANISM IN FLORIDA LIMESTONE BASE COURSE MATERIAL By Luis Alfonso Campos May 2008 Chair: Michael McVay Major: Civil Engineering The Florida Department of Transportation (FDOT) has observed stiffness increases over time in limestone base course materials. It is a goal of the FDOT to understand the mechanism involved so that it may implem ent design procedures to account for the stiffness increase. Past studi es have credited calcium car bonate cementation as providing the stiffness increase. The objective of th is study was to test the hypothesis that cementation can occur if there are pressure gradients adjacent to grain contacts. Laboratory investigation involved compacting three Florida limestones and curing in chambers with high, medium and low relative humidities, which would induce various degrees of such pressure gradients. M odulus values were obtained over time by performing free-free resonant column tests on all materials. Compacted materials were later looked at with a scanning electron microscope to search for crystal growth in the materials.

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xi It was found that no cementation had occu rred during the 30-day test period and that the observed stiffness gains were a resu lt of capillary sucti on within the nano and micro-pores. SEM imagery for an aged field co re paired with porosity data suggests that cementation occurs, but at a much slower rate than observed in the compacted laboratory specimens. Image analysis of the field core showed the presence of calcite crystals and much less fine void space than the compacted specimen of similar material. Porosity measurements were compared between the th ree compacted materials and the field core to help clarify what processes are in volved with the stiffness increases.

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1 CHAPTER 1 INTRODUCTION 1.1 Background The state of Florida has over 90,000 m iles of paved public roads that commuters rely on a daily basis. These roadways ar e designed by highway engineers using the highest quality of material available while at the same time maximizing the design for economy. The engineer will try out different mate rial and thickness conf igurations to deal with anticipated traffic loads and pick the least expensive design. The highways are typically designed to last for 25 years or more, but as pavements progress through their design life, the need to repair or replace the pavement arises. With routine maintenance, the asphal t surface is milled and made thicker upon replacement. This asphalt surface layer is by far the most expensive material used for roadway construction, so optimization is impor tant. The State of Florida Department of Transportation (FDOT) has studied limestones and has noted significant increases in the stiffness of the limestone base course materi als over time. With st ronger base course materials, less asphalt concrete can be us ed, saving taxpayer money. Likewise, if the potential for an increase in stiffness is known before the initia l design, the highway engineers could use this information to further improve upon their designs. Understanding the behavior and properties of these materials, both present and future, is the key to better engineering.

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2 1.2 Purpose and Scope As m entioned, studies have been done that no te an increase in stiffness over time in limerock base course materials (Gartla nd, 1979; Graves, 1987; Zimpher, 1989). The FDOT has made attempts to reevaluate desi gn parameters associated with base course materials to account for the stiffness increase. A problem is that there are many sources from different geological deposits from which these base course materials are mined. The need to characterize the engineering propertie s effectively for each of these sources is required. Simple tests to characte rize some of the properties (s uch as stiffness) have been established and are performed on a routine basis by local testing consultants. While stiffness increases in limestone base course materials have been observed, no test has been successful in predicting what a gene ric stiffness increase will be because the mechanism is not yet fully understood. One proposed possibility of the stiffness in crease is due to calc ite crystal growth and cementation in the micro-pore structur e of the limestone. Limestone is mostly CaCO3, calcium carbonate, which will dissociate and precipitate unde r various natural environmental conditions. Calcite crystals will precipitate within what was previously a void in the limestone. These crys tals bond calcite particles toge ther and also create more contact points with which to resist deforma tion, resulting in a stiffness increase. The purpose of this study was to try and create conditions which are favorable for the precipitation of calcite crystals and observ e different material properties which may affect this phenomenon. 1.3 Methodology Bricker (1971) noted that cem entation in carbonate mate rial occurs due to many factors, one of which is local pressure gradie nts adjacent to grain contacts. It is proposed

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3 that by controlling the relative humidity within a curing chamber such a pressure gradient will be induced and accelerate the cementation process within compacted limestone base course specimens. The limestone materials were compacted, cured under varying relative humidities and tested over time for an increase in stiffness. Three types of limestones representing diffe rent geologic formations were used in this study. Physical and chemical properties were determined for each material. The main tool used in determining the stiffness increase in the base course materials was the freefree resonant column test to find modulus values. Scanning electron microscopy (SEM) techniques and imaging software was used to find pore structure characteristics in the three cured materials. Pore structure data fo r a field core sample was also measured for comparison.

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4 CHAPTER 2 LITERATURE REVIEW 2.1 Introduction The purpose of this research project was to create conditions which are favorable for the precipitation of calcite crystals and observe different m ateri al properties which may affect this phenomenon. A review of the literature was conducted to find information on base course materials, carbonate cementation and compaction issues for limestone base course materials. 2.2 Base Course Materials Highway pavem ents fall into three design ca tegories: flexible, rigid or composite pavements. The most commonly used pavement type in Florida is the flexible design. This design consists of an asphalt surface cour se, a base course just below that, and the subgrade which consists of the existing soil. The goal of a pave ment system is to protect the subgrade. Therefore, high quality material s are used for the surface and base courses. Pavements layers are designed using the con cept of structural nu mbers. In order to prevent an anticipated amount of damage to the layer just below, a structural number requirement should be met. The quality and stiffn ess of each layer of material is indicated by a structural layer coefficient, a. The structural number for each layer can be calculated by multiplying the structural la yer coefficient by the layer thickness. A diagram of the pavement system and design is shown in Fi g. 2-1. Design procedur es can be found in many textbooks, including Huang (2004). In the st ate of Florida, limestone is the most commonly used base course material. Before the pavements are designed by engineers,

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5 the structural layer coefficient, a, is know for each materi al. Materials with higher a values are desired since designers can use less of the stiffer material, which cuts costs. Past studies on limestone base course mate rials have observed increase in stiffness over time, and have credited these stiffne ss increases to calcite cementation. Gartland (1979) used treatment methods which mimick ed vadose and phreatic conditions, as well as using different water sources to test their effect on stiffn ess increase. It was found that the greatest stiffness increases occurred under phreatic conditions ( no cycling) and when using plain water. The time required for significant cementation to occur was not generically identified. Graves (1987) conti nued on a similar study by testing mixtures with varying ratios of calcite to quartz. Phr eatic curing conditions were simulated in an attempt to find the length of time required fo r a significant stiffness increase. It was found that the highest stiffness increase in untreated materials occurred after 14 days. Materials with higher carbonate to quartz ratios showed greater st iffness increases. Similar work and field testing has caused the FDOT to reevaluate the structural coefficient for base course materials (Smith and Lofroos, 1981). St ructural layer coeffi cients were changed from 0.15 to 0.18 as recommended to account for th e future increases in stiffness, but the authors felt that more testing should be completed. 2.2 Chemistry of Carbonate Cementation The goal of this research was to create conditions which are fa vorable for carbonate cem entation, as past studies have shown th at this is the mechanism responsible for stiffness increases. Calcium carbonate is ve ry common throughout the state of Florida. Carbonate cements are responsible for a sign ificant amount of the cements which hold together sedimentary rocks. Calcium carbonate will also dissolve and reprecipitate as under typical changes in environmental conditions.

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6 Carbon dioxide, CO2, plays a major role in the solubility of CaCO3. Various sources of CO2 in water exist. Carbon dioxide from the atmosphere may dissolve in falling rainwater or CO2 may be provided to groundwater by bacteria or other organisms in soil. With increased CO2 levels in water, more CaCO3 can be dissolved Miller (1952) described the process that CO2 in the atmosphere combines with water to form carbonic acid which in turn reacts with calcium car bonate to form the soluble bicarbonate: H2O + CO2 H2CO3 H+ + (HCO3)CaCO3 + H+ + (HCO3)Ca2+ + 2(HCO3)These reactions show that CO2 gas must be present in orde r for the calcium carbonate to dissolve or precipitate. Bricker (1971) states that the emplacement of carbonate cements require precipitation from solu tion. Also, one way that CaCO3 can be made supersaturated (and thus more able to precipitate) is thr ough pressure reduction, or by having local pressure gradients adjacent to grain contacts. Other work has been done on the pore fill ing material. Lindholm (1974) states that aragonite, a polymorph of calcite, is instable at near-surface environmental conditions. Aragonite is not expected to be present in the base course materials, therefore only rhombohedral calcite crystals are expected to be found. Although calcite cements may precipitate, Moore (1989) notes that much of the porosity in limestones is intraparticle, which is unique to carbonates. The living ch ambers, or shells, of various organisms provide this source of porosit y. Although calcite cement may be present in such pores, they would not contribute to any stiffness increase. Caution must be used when searching for calcite crystals, as this may be the case.

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7 2.3 Kelvins Equation The use of saturated salt solutions is a wa y to control the relative humidity in a confined space. Saturated salt solutions are able to adsorb relatively large quantities of water while maintaining a constant relative humidity (Lu and Likos, 2004). Also, the resulting relative humidities from the use of saturated salt solutions will cause the pressure gradients which will drive the calci um carbonate precipitation within the pore spaces. Kelvins equation governs the relationship between the pressure changes across a curved air-liquid boundary to the vapor pr essure above the boundary. One form of Kelvins equation can be written: dRT vTws4 ln(RH) (2.1) where RH is the relative humidity, Ts is surface tension (N/m), vw is the partial molar volume of water vapor (m3/mol), d is the pore diameter (m), R is the universal gas constant (Nm/Kmol) and T is temperature (K). The pore st ructure can be idealized as a system of capillary tubes with diameter d. These capillaries will fill with liquid and form a meniscus dependant on the above variable s. In the presence of a given relative humidity, the pores will either lose or gain water, causing the meniscus to change and the resulting vapor pressure above the air-liquid boundary will ca use a pressure gradient to exist within the material pores. The effect of curvature on the vapor pressures explains the ability of the vapors and solutions in the pores to s upersaturate (Shaw, 1992). Figure 2-2 shows the relationship between relative hum idity and the pore diameter which it will effect. The relative humidities exhibited by the sa turated salt solutions effects the pore water in specimens. The relative humidity of the saturated salt solutions will cause the

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8 pore water to evaporate until equilibrium is reached between the vapor and liquid in the pore spaces, which causes suction. Kelvins eq uation can also be rewritten in terms of total suction as: ln(RH) 0 vw tv RT (2.2) where t is the total soil suction (kPa), vw 0 is the specific volume of the liquid (m3/kg), v is the molecular mass of the liquid vapor (kg/kmol), and R and T are defined as above. Figure 2-3 shows the relationship between relative humidity and total suction. 2.4 Compaction Issues It is proposed that the specimens be comp acted at 1% wet of the optimum moisture content even though for granular materials, this generally decreases initial stiffness values. This was done for two reasons. First, the extra fluid will be able to contain more calcium carbonate in solution. Second, labor atory compaction curves generally yield somewhat lower optimum moisture contents than the actual field optimum (Lambe and Whitman, 1969). It is hoped that this will mimic field results better and more calcite cements will precipitate, resulti ng in higher stiffness increases.

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9 BASE AC SUB-BASE D D D1 2 3a a a1 2 3SN = D x a111SN = D x a222SN = D x a333SN Figure 2-1. Schematic of pavement layers showing concept of structural numbers. 0.0 0.2 0.4 0.6 0.8 1.0 1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 Pore Diameter (meters)Relative Humidity, RH Figure 2-2. General relationship between pore diameter and relative humidity.

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10 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.00.10.20.30.40.50.60.70.80.91.0 Relative HumidityTotal Suction (kPa) Figure 2-3. General relationship between total suction and relative humidity.

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11 CHAPTER 3 MATERIALS AND METHODS 3.1 Selection of Materials For roadway construction projects, the Stat e of Florida allows the contractor to choose the base course material in accord ance with standard specifications, although many contractors favor local materials as transportation costs are the major deciding factor. There are many acceptable aggregate sour ces from different geological formations across the State of Florida. The stiffness of th ese limestone base course materials is based on many factors. The gradation, mineralogy, particle shape, moisture content and compactive effort will determine the initial stiffness of the base course material. The objective of this research was to better understand th e stiffness gain mechanism in base course material. As stat ed earlier, the physical and mineralogical properties of Florida limestones vary from one geologic formation to the other, as well as within the formations themselves. Three co mmonly used limestone s from across Florida were chosen as representative aggregates. Th e base course materials chosen were Ocala limestone, Miami limestone and Loxahatc hee shell rock (mines 26002, 87090 and 93406, respectively, Fig. 3-1). These aggregates come from the Ocala Group, Miami Oolite and Anastasia Formation, respectively. For comparison, a field core taken from Glades County, Florida will be examined. The base course material in the Glades co re appears to be Miami limestone based on physical characteristics and specific gravity, although it is uncertain what mine the material originated from as attempts at verification have been unsuccessful.

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12 3.2 Material Preparation Aggregate was obtained from each of the th ree quarries in Florida. The material was then dried and sieved to obtain grain size distribution curves as shown in Fig. 3-2. Sieve analysis shows that the Miami limestone is the coarsest material, followed by the Loxahatchee shell rock then the Ocala limestone. The Ocala Limestone had the highest percentage of material passing the #200 sieve, followed by the Miami limestone and then the Loxahatchee shell rock. Materials were se parated by the #4 sieve in order to separate the coarse and fine aggregate. Prior to co mpaction, specimens were remixed according to the overall proportions in an attempt to maximize uniformity for the multiple specimens. Material greater than was omitted because there is a maximum allowable aggregate size for both the resonant column (ASTM D 4015) and Limerock Bearing Ratio (LBR) testing (FM 5-515). Modified Proctor (ASTM D 1557) and LBR testing was also completed on the aggregates in order to verify that the ma terials meet the FDOT standards. Detailed Modified Proctor and LBR data are presen ted in Appendix A. The LBR testing was performed in accordance with FM 5-515 except for the fact that, as stated earlier, material greater than was discarded in stead of crushed to as required in the test. The FDOT State Materials Office (SMO) completed Modi fied Proctor and LBR testing on the three materials and descriptive data is given in Table 3-1. It should be noted that the material from the Ocala quarry did not meet the minimum required LBR value of 100 as shown in Table 3-1, but was used regardless since the incr ease in stiffness is of concern rather than the initial stiffness values.

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13 3.3 Compaction Procedures Modified Proctor data gave the optimum moisture content required for compaction. Materials were compacted at 1% wet of the optimum moisture content (See LITERATURE REVIEW) into 4 diameter by 8 height plastic cylinders because resonant column testing require s an aspect ratio of no less than 2:1. It should be noted these dimensions are different from ASTM D 1557 which requires either a 4 or 6 diameter by 4.584 height rigid metal mold. Plastic cylinders were chosen because portions would later be sawed out for the dest ructive testing portion of this experiment. Compaction procedures from ASTM D 1557 had to be modified to ensure that the modified compactive effort of 56,000 ft-lbf/ft3 was still achieved. The specimens were compacted in 9 layers with 25 blows per laye r to achieve the Modified Proctor density. The 10 pound hammer and 18 drop were still us ed. Materials were compacted using a Rainhart automatic tamper at the FDOT SMO. Two specimens were compacted for each testing variation and the resulting modulus values and moisture content reducti ons were averaged. The testing variations consisted of four different time periods and three different curing humidities. In total, 24 duplicate specimens were compacted for each of the three aggregate sources. 3.4 Curing Procedures Curing periods of 2, 7, 15 and 30 days were used in this study to assess stiffness increase over time. After compaction, the cyli nders were placed in curing chambers for the allotted time periods. Desiccato r cabinets of approximately 0.75 ft3 were used as curing chambers. The seals were previously tested to ensure no leak age. To maintain a constant relative humidity in each of the chambers, different saturated salt solutions were

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14 used. It was desired to use solutions whic h exhibited high, medium and low relative humidities. Saturated salt solutions were prepared by mixing a quantity of lithium chloride (RH 11%), magnesium nitrate (RH 53%) or potassium sulfate (RH 97%) with gently heated, distilled water. Once the solution c ools, excess solids will precipitate if the solution is beyond saturation. This allows moisture from the compacted specimens to be absorbed by the saturated salt solutions until excess solids are no longer present. Approximately 250 mL of solution were used in each of the curing chambers and either replaced or remixed as necessary to ensure that solids were present. Conditions inside curing chambers were monitored with the us e of temperature and humidity gages. The temperature dependencies of the saturated sa lt solutions according to ASTM E 104 are presented in Table 3-2. The temperature re mained at a constant 25 C within the chambers throughout the test period. 3.5 Resonant Column Testing Testing for an increase in stiffness for each of the materials was the main concern of this research. The testing program was desi gned to investigate the stiffness increase as a function of relative humidity and time. It was important that the modulus test be nondestructive as the later tests that would char acterize different properties of the materials are destructive. The free-free resonant-column modulus test is a small strain (less than 10-4 in/in) test which consists of applying a vibrati on excitation at one end of the specimen and measuring the resulting vibrati on patterns from the applied compression wave at the other end. Fifteen tests were conducted and averag ed to obtain the resonant frequency of each specimen. The resonant frequency was then used along with and geometric properties and

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15 the compression wave speed to calculate Young s modulus values. Initial measurements were taken immediately after compaction and final measurements were taken after the allotted curing time for each sp ecimen. After testing was completed, cylinders were capped to ensure no further loss in moisture. 3.6 Scanning Electron Microscopy 3.6.1 Sample Preparation In order to view specimens in the SEM, portions of the compacted specimens had to be cut in order to be mounted and fit in the SEM. A major problem which must be overcome is the brittleness of the compacted materials. Upon cutting the material from the cylinders to the size required to fit in the SEM (approximately 1 in3), most of the material will break apart from the vibrati on caused by the cutting saw which prevents the examination of coherent pieces. In order to prepare samples for SEM analysis, large slices measuring approximately 1.5 thick a nd 4 diameter were cut from the plastic cylinders dried in an oven. The pieces we re further broken by hand into the 1 in3 size required to fit in the SEM mounting chamber. These samples were impregnated with a low viscosity epoxy in order to fill as many voi ds as possible. Epoxied samples were then cut and sanded until polished. When viewed in the SEM, the dens ity of the epoxy makes it appears black, allowing for easy identification of voids. 3.6.2 Scanning Electron Microscopy Analysis SEM examinations of the three compacted materials and the field core were conducted in order to search for the presence of calcite crystals. Specimens measured approximately 3.0 cm by 2.5 cm and were fl at. Fourteen random point s were selected on each specimen and images were taken. Any cal cite crystals visible at this scale were further investigated. As stated earlier, samp les were polished so that the SEM settings

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16 would not need to be reconfi gured while investigating each sample and also in order to run Energy Dispersive Spectrometer (EDS). The spectrometer identified and mapped the chemicals present for selected images. SEM examinations were conducted usi ng a Hitachi S-3000 N Scanning Electron Microscope with an EDS x-ray analyzer at the UF Department of Civil and Coastal Engineering. 3.6.3 Imaging Software ImageJ is an image processing program made available to the public. It was used to characterize the number and size of voids in each of the SEM images. The SEM images used for pore size analysis were taken at 90X magnification which limited the minimum void size that the imaging software could disc ern as it only counts pixels. In the images, 1 mm is equal to 880 pixels and so the software will be able to recognize pore sizes greater than 2 m. It was desired to count voids in this range as weight -volume relationships were used to calculate bulk porosity and mercury porosimeter measurements were used to describe pores smaller than 100 m. If a hi gher magnification was used, it was felt that the 14 images for each sample would not be a large enough sample population to describe the pore structure. A subroutine in ImageJ converted the SEM images from grayscale to binary. The voids appeared black and were counted and so rted by total area. The software allows the user to set the minimum pore size that the software will recognize. 3.7 Porosity Measurements Porosity measurements were completed on 30-day samples cured under low relative humidity. Specimens must be completely dry as any moisture will be turned into compressible water vapor. This test is ran in two stages whic h cover a pore range

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17 between approximately 150 m and 1.8 nm. The specimen for this apparatus must fit inside a glass sample cell as shown in Figur e 3-3. Representative samples were difficult to obtain since the compacted material is approximately 1650 cm3 and the mercury porosimeter device accepts spec imens of approximately 1.5 cm3. In an attempt to test representative samples, aggregate pieces were taken with finer pa rticles attached (no clean aggregate). All materials were tested in accordance with ASTM D 4404 using a Quantachrome Autoscan 60 Mercury Porosimeter at the UF Particle Engineering Research Center (PERC). Testing was completed by PERC personnel. 3.8 X-Ray Diffraction X-Ray Diffraction (XRD) measurements were taken on the three virgin aggregate sources. Approximately 5 grams of each a ggregate was ground up with a mortar and pestle and passed through the #200 sieve. Fr om this, chemical and crystallographic composition was obtained. The resulting plots ar e shown in Figs. 3-4, 3-5 and 3-6. These plot show various inte nsities coupled with 2* angles. Each 2* angle pattern corresponds to a unique crystall ine structure, thereby making it possible not only to detect quartz and calcite, but also to distinguis h calcite from its polymorph aragonite. The intensities at each angle, along with other data that may be obtained from the geometry of these plots, represent the relative quantity of each mineral present. Minerals were identified by matching the observed patte rns to a mineralogical powder diffraction database maintained by the Univ. of Arizona. From this database, quartz is known to diffract with a major peak at 2 between 26.6 and 26.7, calcite with a major peak (subsequent peaks exist and are present) at 2 between 29.4 and 29.5 and aragonite with a major peak at 2 between 26.2 and 26.3.

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18 As illustrated, calcite is the main component of each aggregate source. The Ocala limestone is almost exclusively comprised of calcite while the Miami limestone and Loxahatchee shell rock are comprised of calcite and quartz. It shoul d also be noted that aragonite was not present in any of the aggregate sources. All materials were tested using a Ph ilips APD 3720 powder diffractometer at the UF Major Analytical Instrumentation Center (MAIC). Testing was completed by MAIC personnel.

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19 Figure 3-1. Map of Florida showing approxima te locations of aggregate source mines. 26002 93406 87090

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20 0 10 20 30 40 50 60 70 80 90 100 0.01 0.1 1 10 100 Grain Size (mm)Percent Passing a c b Figure 3-2. Grain size distribution curves for limestone materials. (a = Ocala limestone; b = Miami limes tone; c = Loxahatchee shell rock)

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21 Table 3-1. Descriptive data for th ree limestone base course materials. Material Mine No. Carbonate Content Maximum Dry Density (pcf) Optimum Water Content (%) LBR Ocala 26-002 99.2 111.8 13.4 92 Miami 87-090 77.5 129.6 7.8 175 Loxahatchee 93-406 53.8 127.2 7.9 131 Table 3-2. Equilibrium relative humidity va lues for saturated aqueous salt solutions. Temperature (C) Lithium Chloride, LiCl H2O Magnesium Nitrate, Mg(NO3)2 6H2O Potassium Sulfate, K2SO4 20 11.3 0.3 54.4 0.2 97.6 0.5 25 11.3 0.3 52.9 0.2 97.3 0.5 30 11.3 0.2 51.4 0.2 97.0 0.4

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22 1.0 cm SAMPLE SAMPLE CELL Figure 3-3. Mercury Porosimeter specimen set-up. Mercury is intruded from right side. Approximate specimen size is 1 cm x 2 cm.

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23 0 1000 2000 3000 4000 5000 25303540455055 Angle (2* )Intensity Figure 3-4. X-Ray diffraction plot for untreated Ocala limestone. 0 1000 2000 3000 4000 5000 25303540455055 Angle (2* )Intensity Figure 3-5. X-Ray di ffraction plot for untreated Miami limestone.

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24 0 1000 2000 3000 4000 5000 25303540455055 Angle (2* )Intensity Figure 3-6. X-Ray diffr action plot for untreated Loxahatchee limestone.

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25 CHAPTER 4 RESULTS AND DISCUSSION 4.1 Resonant Column Results The main test to determine the increase in modulus of the conditioned limestones was the free-free resonant column test. M odulus and moisture content data for the different materials and curi ng conditions are given in Tables 4-1 through 4-3. The Youngs modulus is compared relative to the 8 averaged initial m odulus values for the different relative humidities and the different compacted base course materials. Modulus values are plotted as a per cent increase over this initial reference modulus. Values reported are averages of duplicate molds tested for each base course material and curing condition. The data was plotted in Figs. 4-1 through 4-3 in order to better illustrate the increases in stiffness. Each material showed increases in stiffness for all three relative humidity levels with the greatest increas e occurring when cured under low relative humidity conditions. The stiffness of the Ocala limestone increased by approximately 2100%, the Miami limestone by 1600% and the Loxahatchee shell rock by 940% when cured under low relative humidity conditions. Modulus values for materials cured under high relative humidity conditions appear to be near their maximum as values are only slightly increasing afte r 7 days. The Loxahatchee shell ro ck showed the lowest overall modulus increases for each curing relative humid ity and in general, modulus values only slightly increase afte r 15 days. The modulus values of the Ocala and Miami limestones increase at an almost constant rate for both the medium and low relative humidities and it is evident from the plots that the modulus values show no sign of reaching a maximum

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26 value. However, it is expected that the in crease in modulus will diminish just as the modulus values for the high relative humidity tests have. Resonant Column Testing data is reported in Appendix B. The initial weights for each test cylinder were record and compared with the weights after curing. This weight loss is due to the saturated salt solutions absorbing moisture from the specimens. The percentage of initial moisture lost was plotted against the percent increase over the reference modulus as shown in Figs. 4-4 through 4-6. Each material showed an approximately linear relationship between the percent moisture lost and the percent increase in modulus, regardless of curing conditions. The Ocala limestone gained more stiffness per moisture lost followed by the Miami limestone and finally the Loxahatchee shell rock. These trends show th at over this testing period the increase in stiffness is related to moisture loss. 4.2 Scanning Electron Microscope Analysis Scanning electron microscopy techniques were used in order to see whether the moisture loss resulted in calcite cement growth, which could be responsible for the observed stiffness increase in the resonant column testing portion of the research. Specimens from materials cured for 30 days under low relative humidity were prepared and examined because it was felt that they had the highest potential for showing calcite cement bonding. Also, a section from a field core from Glades County was examined for comparison with the laboratory compacted specimens. After modulus testing, the selected specimens were cu t out of the cylinder molds and prepared for SEM analysis as stated in Chapter 3. Fourteen random locations on each specimen were examined for the presence of calcite crystal and patterns which would suggest growth. Selected images from the an alysis showing typical characteristics are

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27 presented. Figures 4-7 through 4-11 are typi cal examples of the Ocala, Miami and Loxahatchee images. The light aggregates are calcium carbonate, grey aggregates are quartz and the black areas are the intruded epoxy. SEM exploration of the laboratory compacted specimens did not reveal zone s with calcite cement growth. Figure 4-12 reveals a zone in the Loxahatchee shell rock co ntaining textures related to calcite crystals. Figure 4-13 is a close-up of the area of interest in Fig. 4-12, but reveals that the crystals are only intraparticle and theref ore would not contribute to any stiffness increase from aggregate-to-aggregate cementation. Scanning electron micrographs of the Glades core were also taken. Typically, the Glades core shows less void area than the compacted specimens. Also, many of the Glades core images contained easy to spot relatively large calcite crystals which are appear to be growing between aggregates. Typi cal features of the Glades core are shown in Figs. 4-14 through 4-18. Rhombohedral calci te crystals are show n filling in the pore spaces in Figures 4-16 and 4-18. Additionally, element maps were taken for selected SEM images. Element maps for the Ocala limestone consist of calcium, carbon and oxygen wh ich indicates that only calcite is present. Element maps for the Miami limestone and Loxahatchee shell rock consist of calcium, carbon, oxygen and silicon which indicate the pres ence of calcite and quartz. These measurements are in agreement with the XRD analysis. 4.3 Porosity Measurements The initial moisture content values were taken for each material during the modulus testing portion of this research. The theoretical porosity was calculated using classic weight-volume relationships. Descriptive prope rties are presented in Table 4-4. These values represent the bulk porosity for the ma terials and are useful for comparing the

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28 different methods for finding porosity. The calcu lations for the bulk specimens show that the porosity for these material s ranges between 0.238 and 0.318. Mercury Porosimeter testing gave further insight into the void structure of the compacted limestone. Mercury porosimetry is able to give distributions of pore sizes while bulk porosity measurements do not. The mercury porosimetry test is capable of giving measurements accurate to diameters ranging between 3.6 nm and 100 m. This range of pore diameters corres ponds with Kelvins equation as stated in eq (2.1) which shows the pore diameters that are affected by the relative humidities. Figure 4-19 shows a plot of this equation for t ypical values of water of Ts = 0.072 N/m, vw = 1.8x10-5 m3/mol. The temperature used was T = 298.15 K and the universal gas constant R = 8.314472 Nm/Kmol. Results in Figure 4-20 show that the Ocala limestone has the greatest amount of fine pores of all the materials followed by the Miami limestone and finally the Loxahatchee shell rock. The slope of each li ne indicates the number of pores at each diameter. The flat portions of the plot ranging between 10-6 and 10-5 meters are due to testing inaccuracies. As stated earlier, the test is run in two stages and it is between these ranges that the transition between testing stages occurs. The ImageJ software was used to analyze all the images from the SEM exploration. Each image was made binary and the software counted and gave the area for each void. Imaging analysis was used to describe the pore diameter data between 2x10-6 and 1x10-3 meters which covers the range of the transition measurements in the mercury porosimetry. Data was reduced and summar y statistics are shown in Table 4-5. Histograms of the pore data ranging between 2x10-6 and 2x10-5 meters are presented in Figs. 4-21 through 4-24, as this data account s for over 97% of the pores found with the

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29 software. Figures 4-25 through 427 presents the pore diameter distribution from ImageJ analysis in relation to poros ity and shows what portion of th e total porosity the analysis represents. The Glades core data was omitte d because the bulk porosity was not known. An example of the image processing steps is shown in Fig. 4-28. The three different porosity measurements were compared in Table 4-6. The porosity results show that for both the Ocala and Miami limestones, the Mercury Porosimeter test reports higher porosity values than the SEM image analysis, but for the Loxahatchee shell rock, the opposite is true. These results can lead one to the conclusion that overall, the pores in th e Ocala and Miami limestone ar e generally smaller and those found in the Loxahatchee shell rock are generally larger. 4.4 Discussion The resonant column test indicated stiffness increases for all materials. The Ocala limestone showed the greatest rate for sti ffness increase while Loxahatchee shell rock showed the slowest rate of s tiffness increase. Although solubili ty calculations show that in the time frame for the experiment, only a sm all amount of calcite cement was able to precipitate, SEM exploration did not reveal the presence of cementing calcite crystals in any of the laboratory compacted specimens. The maximum volume of calcite able to precipitate was 9.0x10-4 cm3 in the Ocala limestone cured under low relative humidity for 30 days, which was the best-case scenario The cylinder volume was approximately 1650 cm3, so this equates to 0.00005% of new material precipitation. Calc ulations appear in Appendix C. This amount of calcite precip itation would be very difficult to locate. However, images taken of the Glades core commonly show cementing calcite crystals and filling most voids.

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30 Even though calculations show that calcit e cement was able to precipitate, it is believed that it is not the source for the increas e in stiffness. Instead, suction from the loss of water in the pore spaces is reasonable. The potential for stiffness increase due to suction is determined from the Kelvins equati on as stated in eq (2.2). Figure 4.29 shows a plot of this equation for typical values for water of vw 0 = 0.001 m3/kg, v = 18.016 kg/kmol and T and R are previously defined. Table 4. 7 shows this theoretical suction pressure for each of the relative humidities used. The theoretical total suction values differ by approximately an order of magnit ude which provides an explanation for the difference in stiffness increases for each curi ng condition. It is felt that the materials cured under the medium and low relative humid ities did not reach equilibrium with the saturated salt solutions and therefore did not reach the potential moisture loss to show the full effects of the stiffness increase due to the suction pressures. The materials cured under high relative humidity reached near-consta nt moisture contents, so the effects of the suction pressure are shown in the material stiffness.

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31 Table 4-1. Summary of Ocala limestone under different curing conditions. Average stiffness gain and reduction in moisture content versus time. Curing Type Average Time (days) Average % Decrease in Initial Moisture Average % Increase in Youngs Modulus Low RH 1.99 1.05% 142.0% 7.94 3.13% 573.5% 15.83 5.04% 959.7% 32.10 9.96% 2108.6% Medium RH 1.99 0.76% 71.4% 7.95 2.52% 551.0% 15.83 3.35% 657.4% 32.04 8.03% 1513.3% High RH 1.99 0.56% 58.2% 7.97 1.18% 466.1% 15.84 1.55% 475.1% 32.04 1.94% 536.8% Table 4-2. Summary of Miami limestone under different curing conditions. Average stiffness gain and reduction in moisture content versus time. Curing Type Average Time (days) Average % Decrease in Initial Moisture Average % Increase in Youngs Modulus Low RH 2.05 1.36% 42.0% 7.77 3.82% 457.9% 15.76 7.20% 971.8% 31.09 11.17% 1627.6% Medium RH 2.05 1.03% 59.1% 7.79 3.39% 221.0% 15.77 4.86% 647.3% 31.07 9.35% 1118.8% High RH 2.05 0.73% 22.6% 7.81 1.42% 28.0% 15.78 1.73% 73.0% 31.10 2.68% 149.4%

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32 Table 4-3. Summary of Loxahatchee shel l rock under different curing conditions. Average stiffness gain and reduction in moisture content versus time. Curing Type Average Time (days) Average % Decrease in Initial Moisture Average % Increase in Youngs Modulus Low RH 2.00 2.18% 170.4% 7.82 4.02% 354.6% 15.83 8.50% 798.8% 31.24 12.76% 940.0% Medium RH 1.98 1.19% 121.0% 7.83 2.90% 265.9% 15.84 5.33% 596.9% 31.24 8.43% 637.9% High RH 1.97 0.34% 52.4% 7.85 1.12% 187.2% 15.85 1.38% 277.1% 31.24 2.21% 307.7%

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33 0% 400% 800% 1200% 1600% 2000% 2400% 05101520253035 Time (days)% Increase in Young's Modulus Low Medium High Figure 4-1. Ocala limestone stiffness gain versus time for different relative humidities. 0% 400% 800% 1200% 1600% 2000% 2400% 05101520253035 Time (days)% Increase in Young's Modulus Low Medium High Figure 4-2. Miami limestone stiffness ga in versus time for different relative humidities.

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34 0% 400% 800% 1200% 1600% 2000% 2400% 05101520253035 Time (days)% Increase in Young's Modulus Low Medium High Figure 4-3. Loxahatchee shell rock stiffness gain versus time for different relative humidities. 0% 400% 800% 1200% 1600% 2000% 2400% 0%2%4%6%8%10%12%14% % Decrease in Initial Moisture% Increase in Young's Modulus Low Medium High Figure 4-4. Ocala limestone stiffness gain versus decrease in initial moisture for different relative humidities.

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35 0% 400% 800% 1200% 1600% 2000% 2400% 0%2%4%6%8%10%12%14% % Decrease in Initial Moisture% Increase in Young's Modulus Low Medium High Figure 4-5. Miami limestone stiffness gain versus decrease in initial moisture for different relative humidities. 0% 400% 800% 1200% 1600% 2000% 2400% 0%2%4%6%8%10%12%14% % Decrease in Initial Moisture% Increase in Young's Modulus Low Medium High Figure 4-6. Loxahatchee shell rock stiffness gain versus decrease in initial moisture for different relative humidities.

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36 Figure 4-7. Ocala limestone typical image 1. Figure 4-8. Ocala limestone typical image 2.

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37 Figure 4-9. Miami limestone typical image 1. Figure 4-10. Miami limestone typical image 2.

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38 Figure 4-11. Loxahatchee she ll rock typical image 1. Figure 4-12. Loxahatchee shell rock image 2 showing zone of possible calcite crystal growth on left side.

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39 Figure 4-13. Loxahatchee shell rock closeup of highlighted region in Fig. 4-12. Figure 4-14. Glades core typical image 1.

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40 Figure 4-15. Glades core typical image 2 showing zone of calci te crystal growth. Figure 4-16. Glades core close-up of highlighted region in Fig. 4-15.

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41 Figure 4-17. Glades core typical image 3 showing zone of calci te crystal growth. Figure 4-18. Glades core close-up of highlighted region in Fig. 4-17.

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42 Table 4-4. Average bulk propertie s of base course materials. Specimen Specific Gravity Average Moisture Content (%) Porosity, n Ocala Limestone 2.75 14.28 0.318 Miami Limestone 2.78 8.76 0.238 Loxahatchee Shell Rock 2.84 9.00 0.266 Glades Core 2.78 ----Table 4-5. Summary statistics for pore sizes from ImageJ analysis. Specimen Ocala Miami Loxahatchee Glades Core Mean 6.07E-065.55E-066.31E-06 5.39E-06 Standard Error 8.59E-084.54E-081.37E-07 7.37E-08 Median 3.63E-063.63E-063.84E-06 3.63E-06 Mode 2.57E-062.57E-062.56E-06 2.56E-06 Standard Deviation 1.41E-059.28E-061.76E-05 1.09E-05 Sample Variance 1.99E-108.62E-113.1E-10 1.18E-10 Kurtosis 493.6809701.3346926.6147 1008.251 Skewness 18.951419.5398724.77442 24.98864 Range 0.0005220.0005320.000932 0.000651 Minimum 2.57E-062.57E-062.56E-06 2.56E-06 Maximum 0.0005240.0005350.000934 0.000654 Sum 0.1633670.2314540.104128 0.116765 Count 269174171516497 21677 Table 4-6. Comparison of porosity values from different methods. Specimen Bulk Measurements Mercury Porosimetry SEM Image Analysis Ocala Limestone 0.318 0.235 0.183 Miami Limestone 0.238 0.150 0.147 Loxahatchee Shell Rock 0.266 0.101 0.170 Glades Core --0.088 0.101

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43 0.113 0.973 0.5290.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 Pore Diameter (meters)Relative Humidity, RH Figure 4-19. Relative humidity values and corresponding affected pore diameters. Horizontal lines represent targeted relative humidities.

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44 0.00 0.05 0.10 0.15 0.20 0.25 Pore Diameter (meters)Total Porosity b c a d Figure 4-20. Mercury Porosimeter results for 30-day specimens and Glades core. (a = Ocala limestone; b = Miami limestone; c = Loxahatchee shell rock; d = Glades core) 109 108 107 106 105 104 103

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45 15300 5921 1111 2171 609 399 280 185 1340% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-21. Pore diameter histogram from ImageJ analysis for Ocala limestone. Values above bars are frequency. 189 243 392 521 879 1642 3505 9654 236640% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-22. Pore diameter histogram from ImageJ analysis for Miami limestone. Values above bars are frequency.

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46 65 121 158 230 351 738 1558 8920 39000% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-23. Pore diameter histogram from ImageJ analysis for Loxahatchee shell rock. Values above bars are frequency. 103 130 157 212 424 779 1687 13030 46780% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-24. Pore diameter histogram from ImageJ analysis for Glades core. Values above bars are frequency.

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47 0.3180.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 1.E-06 1.E-05 1.E-04 1.E-03 Pore Diameter (meters)Total Porosity Figure 4-25. Ocala limestone pore diameter distribution from ImageJ analysis in relation to porosity. Horizontal line is the bulk porosity. 0.2380.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 1.E-06 1.E-05 1.E-04 1.E-03 Pore Diameter (meters)Total Porosity Figure 4-26. Miami limestone pore diameter distribution from ImageJ analysis in relation to porosity. Horizontal line is the bulk porosity.

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48 0.2660.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 1.E-061.E-051.E-041.E-03 Pore Diameter (meters)Total Porosity Figure 4-27. Loxahatchee shell rock pore diameter distribution from ImageJ analysis in relation to porosity. Horizontal line is the bulk porosity.

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49 A B C Figure 4-28. Image processing steps with ImageJ software. Example is from Ocala specimen. A) Original SEM image taken in grayscale. B) Image converted into binary. C) Binary image is converted into outlines and area data is obtained.

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50 0.529 0.113 0.9731.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.00.10.20.30.40.50.60.70.80.91.0 Relative HumidityTotal Suction (kPa) Figure 4-29. Theoretical relative humidity va lues and corresponding total suction. Vertical lines represent targeted relative humidities. Table 4-7. Theoretical suction pressures for different relative humidities. Relative Humidity Suction Pressure (kPa) Suction Pressure (ksi) Low 300,000 43.6 Medium 88,000 12.8 High 3800 0.55

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51 CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 5.1 Conclusions 1. Curing compacted specimens with diffe rent relative humidities resulted in stiffness increases for each material type. Materials cured under low relative humidity conditions showed the greatest increase in stiffness while materials cured under high relative humidity conditions showed the lowest stiffness increase. 2. Materials cured under high relative hum idity reached stable moisture contents during the testing period. Materials cured under medium and low relative humidities did not reach stable moisture contents in the allo tted test period, but are likewise expected to stabilize. 3. Stiffness increases in this experiment were due to increases in capillary suction due to the removal of water from the system. 4. Materials with more fine pores in th e sub-micron level and also more material passing the #200 sieve resulted in greater sti ffness increases. Ocala limestone showed the greatest stiffness increase while Loxahatchee sh ell rock showed the lowest, which agrees with this statement. 5. Materials showed a linear relations hip between % increase in Youngs modulus and increased % reductions in moisture conten t. It is thought th at the % increase in Youngs modulus will reach some maximum value, though the testing period was not long enough to verify this.

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52 6. Although all materials showed an increa se in stiffness, calculations show the potential crystal growth from calcite in solution was negligible. Expectantly, SEM analysis did not reveal the presence of calcite crystals. It is concluded that the testing period was not long enough to allow the material s to reach equilibrium with the saturated salt solutions. 7. SEM imaging in the Glades core reveal the presence of relatively large calcite crystals. The orientation of these crystals suggests that pores are being filled. Porosity measurements in the Glades core also indicate that most of the pore volume has been filled. 8. SEM analysis coupled with the ImageJ software provided ex cellent quantitative analysis for describing voids. 5.2 Recommendations for Future Work 1. Roadway conditions of base course material should be studied. Sensors recording the temperature, relative humidity, CO2 levels and moisture migration in pores can be implemented during construction. Future test should be long term and mimic these relevant field conditions rather than ch anging individual conditions that may be irrelevant. 2. Doping the specimens with a know substance during compaction would be beneficial when looking for ne w calcite growth. Due to the small quantities of calcite crystals that precipitate and the heterogeneity of limestones, it is very difficult to distinguish new crystal grow th from crystals that may have formed hundreds or thousands of years ago. Neoformed crysta ls would include the doped substance and would be recognizable using EDS, XRD or cathodoluminescence techniques.

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53 3. It may be coincidental that the mate rials with higher fines content resulted in higher stiffness increases, but the effect of fines in regards to increases in stiffness should be studied. 4. The effect of initial moisture conten t should be studied because contractors may meet density requirements using moisture co ntents both wet and dry of the optimum. A range of initial moisture contents and their e ffect on stiffness increase should be tested as materials in this study were only compacted 1% wet of the optimum moisture content.

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54 APPENDIX A MODIFIED PROCTOR AND LBR RESULTS Figure A-1. Ocala limestone Modified Proctor and LBR data

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55 Figure A-2. Miami limestone Modi fied Proctor and LBR data

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56 Figure A-3. Loxahatchee shell rock Modified Proctor and LBR data

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57 APPENDIX B RESONANT COLUMN TESTING DATA Table B-1. Data for Ocala Limestone after Compaction Ocala Mold Wt: 0.242lbs 26-002 Diameter: 4in 26-All Height: 8in Initial V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 26-L-02-19/1/07 23:408.0514.44%1044.17141390.56 26-L-02-29/4/07 23:408.0714.14%1364.18211810.95 26-L-07-18/18/07 20:557.9914.31%1204.13931600.74 26-L-07-28/18/07 21:057.9714.49%2164.12862882.38 26-L-14-17/15/07 19:508.0314.00%1284.16071710.84 26-L-14-28/7/07 19:557.9914.37%1124.13931490.64 26-L-30-17/15/07 19:308.0314.36%1524.16072031.19 26-L-30-27/15/07 19:358.0414.35%1364.16601810.95 26-M-02-19/1/07 23:458.0314.55%1044.16071390.56 26-M-02-29/4/07 23:458.0614.32%1044.17671390.56 26-M-07-18/18/07 20:458.0014.35%1204.14471600.74 26-M-07-28/18/07 20:508.0614.18%1124.17671490.65 26-M-14-17/15/07 19:508.0014.19%1364.14471810.95 26-M-14-28/7/07 19:458.0014.19%1204.14471600.74 26-M-30-17/15/07 19:208.0914.02%1764.19272351.60 26-M-30-27/15/07 19:258.0814.14%1124.18741490.65 26-H-02-19/1/07 23:508.0514.35%1204.17141600.74 26-H-02-29/4/07 23:508.0114.33%1284.15001710.84 26-H-07-18/18/07 20:307.9614.45%1204.12331600.73 26-H-07-28/18/07 20:408.0114.43%1204.15001600.74 26-H-14-17/15/07 19:408.0214.07%1364.15531810.95 26-H-14-28/7/07 19:407.9714.30%1284.12861710.84 26-H-30-17/15/07 19:108.0414.04%1204.16601600.74 26-H-30-27/15/07 19:158.0314.24%1204.16071600.74 Sample Number : Testing Condition : Quarry : Pit Number :

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58 Table B-2. Data for Ocala Limestone after Curing Ocala Mold Wt: 0.242lbs 26-002 Diameter: 4in 26-All Height: 8in Final V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) Days M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 26-L-02-19/3/07 23:402.008.0414.29%1524.16602031.19 26-L-02-29/6/07 23:001.978.0513.99%2244.17142992.58 26-L-07-18/26/07 19:257.947.9613.90%3764.12335017.20 26-L-07-28/26/07 19:307.937.9314.00%4164.10735558.78 26-L-14-18/1/07 13:4516.757.9513.00%4164.11795558.80 26-L-14-28/22/07 17:4014.917.9513.94%3684.11794916.88 26-L-30-18/16/07 20:2532.047.9212.92%6964.101992824.53 26-L-30-28/16/07 23:3032.167.9312.93%6644.107388522.36 26-M-02-19/3/07 23:452.008.0214.48%1444.15531921.06 26-M-02-29/6/07 23:051.978.0514.17%1284.17141710.84 26-M-07-18/26/07 19:357.957.9713.97%3364.12864485.75 26-M-07-28/26/07 19:407.958.0413.84%2564.16603413.37 26-M-14-18/1/07 13:5016.757.9513.55%3604.11794806.59 26-M-14-28/22/07 17:4514.927.9713.88%3444.12864596.03 26-M-30-18/16/07 20:1532.048.0012.88%5684.144775716.51 26-M-30-28/16/07 20:2032.047.9913.02%5284.139370414.25 26-H-02-19/3/07 23:502.008.0514.32%1524.17142031.19 26-H-02-29/6/07 23:101.978.0014.20%1604.14472131.31 26-H-07-18/26/07 19:457.977.9514.28%3064.11794084.76 26-H-07-28/26/07 19:507.977.9914.26%2644.13933523.56 26-H-14-18/1/07 13:5516.768.0113.85%3604.15004806.64 26-H-14-28/22/07 17:5014.927.9514.08%2724.11793633.76 26-H-30-18/16/07 20:0532.048.0213.76%3444.15534596.07 26-H-30-28/16/07 20:1032.048.0113.97%2564.15003413.36 Testing Condition : Quarry : Pit Number : Sample Number :

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59 Table B-3. Data for Miami Limestone after Compaction Miami Mold Wt: 0.242lbs 87-090 Diameter: 4in 87-All Height: 8in Initial V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 87-L-02-19/4/07 22:008.668.85%1844.49732451.88 87-L-02-29/4/07 22:058.648.80%1444.48661921.15 87-L-07-18/18/07 23:258.568.88%2244.44382992.75 87-L-07-28/18/07 23:308.618.92%1364.47051811.02 87-L-14-17/15/07 22:458.638.63%1524.48122031.28 87-L-14-28/7/07 20:158.628.60%2084.47592772.39 87-L-30-17/16/07 16:458.608.79%1524.46522031.27 87-L-30-27/16/07 16:508.629.03%1604.47592131.41 87-M-02-19/4/07 22:108.628.75%1444.47591921.15 87-M-02-29/4/07 22:208.618.69%1604.47052131.41 87-M-07-18/18/07 23:158.638.93%1844.48122451.87 87-M-07-28/18/07 23:208.598.49%1364.45991811.02 87-M-14-17/15/07 22:408.618.50%1444.47051921.14 87-M-14-28/7/07 20:108.619.20%2164.47052882.58 87-M-30-17/16/07 16:358.548.06%1524.43312031.26 87-M-30-27/16/07 16:408.638.30%1364.48121811.02 87-H-02-19/4/07 22:258.569.01%1124.44381490.69 87-H-02-29/4/07 22:308.508.72%1124.41181490.68 87-H-07-18/18/07 23:058.548.76%1524.43312031.26 87-H-07-28/18/07 23:108.558.90%1524.43852031.27 87-H-14-17/15/07 22:358.618.73%1924.47052562.03 87-H-14-28/7/07 20:058.619.19%1604.47052131.41 87-H-30-17/16/07 16:258.638.96%1524.48122031.28 87-H-30-27/16/07 16:308.568.57%1844.44382451.86 Testing Condition : Quarry : Pit Number : Sample Number :

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60 Table B-4. Data for Miami Limestone after Curing Miami Mold Wt: 0.242lbs 87-090 Diameter: 4in 87-All Height: 8in Final V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) Days M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 87-L-02-19/6/07 23:152.058.658.71%2244.49192992.78 87-L-02-29/6/07 23:202.058.638.70%1684.48122241.56 87-L-07-18/26/07 18:007.778.538.53%3044.42784055.05 87-L-07-28/26/07 18:057.778.588.59%4164.45455559.52 87-L-14-18/1/07 13:2016.618.557.74%5844.438577918.69 87-L-14-28/22/07 18:1014.918.598.25%5444.459972516.29 87-L-30-18/16/07 18:5531.098.517.80%6884.417191725.81 87-L-30-28/16/07 19:0031.098.538.03%6084.427881120.21 87-M-02-19/6/07 23:252.058.618.65%1764.47052351.71 87-M-02-29/6/07 23:302.058.618.61%2084.47052772.39 87-M-07-18/26/07 18:157.798.608.60%2404.46523203.18 87-M-07-28/26/07 18:207.798.578.23%2964.44923954.81 87-M-14-18/1/07 13:2516.618.567.88%4964.443866113.50 87-M-14-28/22/07 18:2014.928.598.96%3844.45995128.12 87-M-30-18/16/07 18:1531.078.487.28%4324.401157610.14 87-M-30-28/16/07 18:3031.088.577.55%5524.449273616.74 87-H-02-19/6/07 23:352.058.568.94%1284.44381710.90 87-H-02-29/6/07 23:402.058.498.66%1204.40641600.78 87-H-07-18/26/07 18:257.818.538.64%1764.42782351.69 87-H-07-28/26/07 18:307.818.548.77%1684.43312241.54 87-H-14-18/1/07 13:3016.628.608.57%2244.46522992.77 87-H-14-28/22/07 18:3014.938.609.04%2324.46523092.97 87-H-30-18/16/07 18:4531.108.618.72%1764.47052351.71 87-H-30-28/16/07 18:5031.108.548.34%3524.43314696.78 Testing Condition : Quarry : Pit Number : Sample Number :

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61 Table B-5. Data for Loxahatchee Shell Rock after Compaction Loxahatchee Mold Wt: 0.242lbs 93-406 Diameter: 4in 93-All Height: 8in Initial V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 93-L-02-19/1/07 22:008.558.66%2404.43853203.16 93-L-02-29/1/07 22:058.559.20%2644.43853523.82 93-L-07-18/18/07 22:558.468.99%2884.39043844.50 93-L-07-28/18/07 23:008.478.94%2324.39583092.92 93-L-14-17/15/07 22:258.508.75%2164.41182882.54 93-L-14-28/7/07 17:258.479.01%1684.39582241.53 93-L-30-17/16/07 13:458.519.03%2084.41712772.36 93-L-30-27/16/07 13:508.529.15%2164.42252882.55 93-M-02-19/1/07 22:108.548.81%2564.43313413.59 93-M-02-29/1/07 23:208.528.89%2724.42253634.04 93-M-07-18/18/07 22:458.469.11%1924.39042562.00 93-M-07-28/18/07 22:508.539.15%2484.42783313.36 93-M-14-17/15/07 22:208.509.23%1924.41182562.01 93-M-14-28/7/07 17:208.488.79%1924.40112562.00 93-M-30-17/16/07 13:358.519.78%2804.41713734.28 93-M-30-27/16/07 13:408.578.73%2084.44922772.38 93-H-02-19/1/07 23:158.519.24%2724.41713634.03 93-H-02-29/1/07 23:308.558.62%3004.43854004.93 93-H-07-18/18/07 22:358.499.00%1604.40642131.39 93-H-07-28/18/07 22:408.488.80%1844.40112451.84 93-H-14-17/15/07 22:158.428.76%2084.36902772.33 93-H-14-28/7/07 17:008.519.31%2164.41712882.54 93-H-30-17/16/07 13:258.499.07%1444.40641921.13 93-H-30-27/16/07 13:308.499.07%1924.40642562.01 Testing Condition : Quarry : Pit Number : Sample Number :

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62 Table B-6. Data for Loxahatchee Shell Rock after Curing Lox Mold Wt: 0.242lbs 93-406 Diameter: 4in 93-All Height: 8in Final V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) Days M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 93-L-02-19/3/07 22:002.008.548.51%4244.43315659.84 93-L-02-29/3/07 22:052.008.538.96%4004.42785338.75 93-L-07-18/26/07 18:357.828.438.63%5364.374471515.52 93-L-07-28/26/07 18:407.828.448.58%5524.379773616.48 93-L-14-18/1/07 13:0016.618.427.73%6084.369081119.94 93-L-14-28/22/07 18:4015.058.438.52%5364.374471515.52 93-L-30-18/16/07 19:3531.248.427.84%7284.369097128.59 93-L-30-28/16/07 19:4031.248.438.02%6404.374485322.12 93-M-02-19/3/07 22:102.008.548.73%3924.43315238.41 93-M-02-29/3/07 22:201.968.518.76%3924.41715238.38 93-M-07-18/26/07 18:457.838.448.82%3764.37975017.64 93-M-07-28/26/07 18:507.838.518.91%4644.417161911.74 93-M-14-18/1/07 13:0516.618.458.60%5684.385175717.47 93-M-14-28/22/07 18:4515.068.468.46%4404.390458710.49 93-M-30-18/16/07 19:2531.248.458.95%7044.385193926.83 93-M-30-28/16/07 19:3031.248.518.00%6084.417181120.16 93-H-02-19/3/07 22:301.978.509.20%3524.41184696.75 93-H-02-29/3/07 22:401.978.548.60%3524.43314696.78 93-H-07-18/26/07 18:557.858.498.90%2644.40643523.79 93-H-07-28/26/07 19:007.858.478.70%3204.39584275.56 93-H-14-18/1/07 13:1516.638.418.63%4004.36375338.62 93-H-14-28/22/07 18:5015.088.509.19%4244.41185659.79 93-H-30-18/16/07 19:1531.248.478.81%2884.39583844.50 93-H-30-28/16/07 19:2031.248.488.93%3924.40115238.35 Testing Condition : Quarry : Pit Number : Sample Number :

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63 Figure B-1. Example 1 of frequency measur ed in Free-Free Resonant Column test. Initial value from specimen 93-L-14-2.

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64 Figure B-2. Example 2 of frequency measur ed in Free-Free Resonant Column test. Final value from specimen 93-L-14-2.

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65 APPENDIX C CALC ULATIONS From Faure (1998), the highest possible concentration of cal cium ions in solution is: [Ca2+] = 4.86-4 (mol/L) Vcalcite = 36.93 (cm3/mol) Molar volume of calcite 36.93 (cm3/mol) 4.86-4 (mol/L) = 1.79-2 cm3/L 1.79-2 cm3/L Amount of calcit e able to precipitate Ocala volume of solution = 0.501 L Initial volume of water in specimen 0.501 (L) 1.79-2 (cm3/L) = 9.0-3 cm3 Volume of Calcite able to precipitate Moisture loss = 10% Moisture loss observed for low RH curing 9.0-3 0.10 = 9.0-4 cm3 9.0-4 cm3 Volume of calcite precipitated Table C-1. Summary of values used for calculating precipitated calcite. Material Amount of Solution (Liters) Volume of calcite able to precipitate (cm3) Maximum Moisture Lost (%) Maximum Vol. of Calcite able to Precipitate for Test Conditions (cm3) Ocala 0.501 9.0-3 10 9.0-4 Miami 0.330 5.9-3 11 6.5-4 Loxahatchee 0.336 6.0-3 13 7.8-4

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66 LIST OF REFERENCES Allen, R.F. [et al.] (2000) Annual Book of ASTM Standards Vol. 4.08. American Society for Testing and Materials, Pennsylvania. Bricker, O.P., ed. (1971) Carbonate Cements. The Johns Hopkins Press, Baltimore. Faure, G. (1998) Principles and Applicat ions of Geochemistry 2nd Ed. Prentice Hall, Inc., New Jersey. Florida Department of Transportation, (2007) City County Mileage Report, FDOT Homepage, http://www2.dot.state.fl.us /planning/m ileage/word/pdf /pdf_report_final_inet.asp (Accessed May 2007) Gartland, J.D. (1979) Experimental Dissolution-Repreci pitation Processes with Two Florida Limestones. Masters Thesis, Univ. of Florida. Goldstein, J.I. [et al.] (1992) Scanning Electron Microsc opy and X-Ray Microanalysis 2nd Ed. Plenum Press, New York. Graves, R.E. (1987) Strength Developed from Carbonate Cementation in Silica/Carbonate Systems as Influenc ed by Cement-Particle Mineralogy Masters Thesis, Univ. of Florida. Huang, Y.A. (2004) Pavement Analysis and Design 2nd Ed. Pearson Prentice Hall, New Jersey. Lambe, T.W. and R.V. Whitman. (1969) Soil Mechanics John Wiley and Sons, Inc., New York. Lindholm, R.C. (1974) Fabric and Chemistry of Pore Filling Calcite in Septarian Veins: Models for Limestone Cementation. In D.S. Gorsline, Ed. Journal of Sedimentary Petrology Vol. 44. Society of Economic Paleonto logists and Mineralogists, Oklahoma. Lu, N. and W.J. Likos. (2004) Unsaturated Soil Mechanics John Wiley and Sons, Inc., New Jersey. Menq, F. (2003) Dynamic Properties of Sandy and Gravelly Soils PhD Dissertation, Univ. of Texas at Austin.

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67 Miller, J.P. (1952) A Portion of the Syst em Calcium Carbonate-Carbon Dioxide-Water, with Geological Implications. In C.R. Longwell and J. Rodgers, Eds. American Journal of Science Vol. 250. Yale University, Connecticut. Moore, C.H. (1989) Carbonate Diagenesis and Porosity Elsevier Science Publishers B.V., Amsterdam. Rasband, W.S., ImageJ, U. S. National Instit utes of Health, Bethesda, Maryland, USA, http://rsb.info.nih.gov/ij/ (Accessed June 2007) Shaw, D.J. (1992) Introduction to Colloid and Surface Chemistry 4th Ed. ButterworthHeinemann Ltd, Oxford. Smith, L.L. and W.N. Lofroos. (1981) Pavement Design Coefficients: A Re-Evaluation of Florida Base Materials Research Report. State of Florida Department of Transportation. University of Arizona, The RRUFF Project. http://rruff.geo.arizona.edu/rruff/ (las t accessed October 2007) Zimpfer, W.H. (1989) Strength Gain and Cementation of Flexible Pavement Bases Final Report for the Florida Department of Tr ansportation. University of Florida, Department of Civil Engineering.

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68 BIOGRAPHICAL SKETCH Luis Alfonso Ca mpos was born in 1983 in Tampa, Florida. After graduating from Sickles High School in 2001, he attended the University of Florida where he received a Bachelor of Science degree in December 2005 with a major in civil engineering. During his undergraduate studies, he worked part time at a small geotechnical engineering firm in Gainesville where he gained valuable experience in geotechnical engineering. The experience that he gained led him to continue with graduate studies at the University of Florida. He received a Master of Engineering degree in May 2008 and plans to work at a geotechnical consulting firm in North Carolina.


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