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Fracture Toughening Mechanisms in Nanoparticle And Micro-Particle Reinforced Epoxy Systems Using Multi-scale Analysis

Permanent Link: http://ufdc.ufl.edu/UFE0024281/00001

Material Information

Title: Fracture Toughening Mechanisms in Nanoparticle And Micro-Particle Reinforced Epoxy Systems Using Multi-scale Analysis
Physical Description: 1 online resource (85 p.)
Language: english
Creator: Boesl, Benjamin
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2009

Subjects

Subjects / Keywords: dispersion, fib, fracture, nanocomposite, optimization, tribology
Mechanical and Aerospace Engineering -- Dissertations, Academic -- UF
Genre: Aerospace Engineering thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Fracture toughness results from multi-scale experimentation and modeling of a polymer system reinforced with ZnO particles of two nominal diameters (53 nanometers and 75 microns) are presented within this work. The composites were fabricated using an orbital shear-mixing device. Fracture toughness measurements were completed using a four point bend apparatus following ASTM standard E1820, resulting in an increase of 80 percent in critical stress intensity factor for epoxy filled with 4 volume percent nanoparticles. Studies using a focused ion beam were conducted to investigate the toughening mechanisms of particle reinforcement at the micro-scale. Cantilever beams were created over two different length scales (approximately 1 mm and 10 microns) and loaded using an Omniprobe device in-situ in the focused ion beam. Using this method, both the nanoparticles and the crack were imaged simultaneously and the results were compared with common assumptions regarding crack propagation within particulate composites. Experimental results were compared to three hypotheses using both experimental results and modeling techniques in an attempt to explain the increase in toughness that can be observed in a typical nanocomposite system. Results showed strong correlations to mechanisms that reduce the apparent stress intensity factor in the crack tip region thus preventing unstable crack growth.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Benjamin Boesl.
Thesis: Thesis (Ph.D.)--University of Florida, 2009.
Local: Adviser: Sankar, Bhavani V.
Local: Co-adviser: Sawyer, Wallace G.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2009
System ID: UFE0024281:00001

Permanent Link: http://ufdc.ufl.edu/UFE0024281/00001

Material Information

Title: Fracture Toughening Mechanisms in Nanoparticle And Micro-Particle Reinforced Epoxy Systems Using Multi-scale Analysis
Physical Description: 1 online resource (85 p.)
Language: english
Creator: Boesl, Benjamin
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2009

Subjects

Subjects / Keywords: dispersion, fib, fracture, nanocomposite, optimization, tribology
Mechanical and Aerospace Engineering -- Dissertations, Academic -- UF
Genre: Aerospace Engineering thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Fracture toughness results from multi-scale experimentation and modeling of a polymer system reinforced with ZnO particles of two nominal diameters (53 nanometers and 75 microns) are presented within this work. The composites were fabricated using an orbital shear-mixing device. Fracture toughness measurements were completed using a four point bend apparatus following ASTM standard E1820, resulting in an increase of 80 percent in critical stress intensity factor for epoxy filled with 4 volume percent nanoparticles. Studies using a focused ion beam were conducted to investigate the toughening mechanisms of particle reinforcement at the micro-scale. Cantilever beams were created over two different length scales (approximately 1 mm and 10 microns) and loaded using an Omniprobe device in-situ in the focused ion beam. Using this method, both the nanoparticles and the crack were imaged simultaneously and the results were compared with common assumptions regarding crack propagation within particulate composites. Experimental results were compared to three hypotheses using both experimental results and modeling techniques in an attempt to explain the increase in toughness that can be observed in a typical nanocomposite system. Results showed strong correlations to mechanisms that reduce the apparent stress intensity factor in the crack tip region thus preventing unstable crack growth.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Benjamin Boesl.
Thesis: Thesis (Ph.D.)--University of Florida, 2009.
Local: Adviser: Sankar, Bhavani V.
Local: Co-adviser: Sawyer, Wallace G.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2009
System ID: UFE0024281:00001


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1 FRACTURE TOUGHENING MECHANISMS IN NANOPARTICLE AND MICRO PARTICLE REINFORCED EPOXY SYSTEMS USING MULTI SCALE ANALYSIS By BENJAMIN BOESL A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTI AL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2009

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2 2009 Benjamin Boesl

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3 To my wife and mother

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4 ACKNOWLEDGMENTS I would first like to thank my wife, L indsey, for being there throughout this long journey with love and support ; through any frustration I knew I could always count on her to help me relax and ease my mind. I would also like to thank my mother and brother, Sharon and Adam, for the encouragem ent to do something that I truly enjoyed and the unwavering support throughout my life. I would like to thank my advisor, Bhavani Sankar, for being incredibly thoughtful throughout this entire process, always putting the needs of me, the student, ahead of everything, which is something that I truly admire. His guidance both academically and intellectually have had a major impact on me both in the present and for the future. I would also like to thank Jerry Bourne for sharing his infinite wisdom and patience, it seems that no problem was too large or small to discuss and no matter the situation he was always there with a sympathetic ear. I would like to thank Greg Sawyer for allowing me into his lab as one of his own students and his many useful insights pertaining to this work. I would also like to thank Youping Chen for her guidance and our many helpful discussions. I would also like to thank all of the members of both the Center of Advanced Composite and the Tribology Lab for providing such a thought pr ovoking, unique, and entertaining atmosphere, especially the friendships of Ryan Karkkainen, Jason Bares, and Jeff Bardt. Finally, I would like to thank the contributions of the Ebaugh Professorship for funding this research.

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5 TABLE OF CONTENTS ACKNOWLEDGMENTS .................................................................................................................... 4 page LIST OF TABLES ................................................................................................................................ 7 LIST OF FIGURES .............................................................................................................................. 8 ABSTRACT ........................................................................................................................................ 11 CHAPTER 1 INTRODUCTION ....................................................................................................................... 12 2 BACKGROUND WORK AND MOTIVATION ..................................................................... 15 Background .................................................................................................................................. 15 Composite Preparation and Optimization .................................................................................. 16 Experimental Procedure .............................................................................................................. 18 Results and Motivation for Future Work ................................................................................... 19 3 IDENTIFICATION OF INFLUENCES IN NANOCOMPOSITE DESIGN ......................... 27 Particle Dispersion and Alignment ............................................................................................ 27 Survey of Dispersion Data .................................................................................................. 27 Dispersion Imaging Techniques ......................................................................................... 28 Two -d imensional t echniques: m icrotome and t ransmission e lectron m icroscopy ................................................................................................................ 28 Three d imensional t echniques: focused i on b eam ..................................................... 29 Quantification of Dispersion State ...................................................................................... 30 4 INITIAL FRACTURE TOUGHNESS EXPERIMENTATION .............................................. 38 Materials ...................................................................................................................................... 38 Fabrication Procedure ................................................................................................................. 38 Testing Procedure ........................................................................................................................ 39 Initial Observations ..................................................................................................................... 40 Analysis of Fracture Surfaces ..................................................................................................... 41 5 FRACTURE TOUGHENING MECHANISMS ....................................................................... 44 Hypothesis: Crack Area Increase ............................................................................................... 44 Hypothesis: Crack Shielding ...................................................................................................... 46 Hypothesis: Microcrack For mation and Crack Pinning ........................................................... 49 Insitu FIB micro -scale fracture tests (~ 1 mm cantilever length) .................................... 49 Insitu FIB micro -scale fracture tests (~ 10 m cantilever length) ................................... 50

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6 6 MODELING MATERIAL BEHAVIOR ................................................................................... 59 Stiffness Matrix Determination .................................................................................................. 60 Covalent Length Element (CL) ........................................................................................... 60 Covalent Angular Element (CA) ........................................................................................ 62 Leonard Jones Element (L J) ............................................................................................... 63 Force Calculations ....................................................................................................................... 64 Covalent Length Element (CL) ........................................................................................... 64 Cova lent Angular Element (CA) ........................................................................................ 65 Leonard Jones Element (LJ) ............................................................................................... 66 Creation of a Polymer Field Using a Random Walk Process ................................................... 66 Assembly of the Global Stiffness Matrix .................................................................................. 67 Polymer Field Relaxation ........................................................................................................... 67 7 S UMMARY AND CONCLUSION ........................................................................................... 73 APPENDIX A DDITIONAL MODELING IMAGES .................................................................................... 75 LIST OF REFERENCES ................................................................................................................... 82 BIOGRAPHICAL SKETCH ............................................................................................................. 85

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7 LIST OF TABLES Table page 2 1 Volume concentration of matrix material, epoxy, and filler materials, Zn O and PTFE along with the tabulated average values for steady state wear rate and friction coefficient. .............................................................................................................................. 26 6 1 List of constants used for AFEM polymer analysis ............................................................. 72

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8 LIST OF FIGURES Figure page 2 1 Plot of the volume percent correlating to optimum tribological properties according to the literature versus particle size in micrometers for v arious fillers in an epoxy matrix. ..................................................................................................................................... 21 2 2 Images obtained though electron microscopy of nanoparticles. ......................................... 21 2 3 Ternary diagram wi th the matrix material, epoxy, at the pinnacle and the filler materials, ZnO and PTFE, at the bottom corners. ................................................................ 22 2 4 Steady state wear data for the epoxy nanocomposite samples in this study. ..................... 23 2 5 Average steady state friction coefficient data for the epoxy nanocomposite samples in this study. ............................................................................................................................ 24 2 6 Three dimensional visualization of wear rate and friction coefficient resutls of EpoxyZnO -PTFE system ..................................................................................................... 25 3 1 A survey of TEM images throughout the literature ............................................................. 33 3 2 TEM images of a single domain within a 44 nm delta -gamma alumina filled epoxy at 2 vol. %. .................................................................................................................................. 34 3 3 Illustration of the slice and view procedure. ......................................................................... 34 3 4 Orthogonal views from three planes of the imaged volume. ............................................... 35 3 5 A three dimensional reconstruction of the imaged volume. The sample is a 1 vol. % Z nO filled Epoxy. ................................................................................................................... 35 3 6 Three dimensional particle views obtained using the slice and view technique. ............... 36 3 7 Application of the Monte Carlo analysis method to quantify a typical particle dispersion. ............................................................................................................................... 37 3 8 Multiple images obtained from 75m nominal diameter particle sample showing the existence of particles on the scal e of nanometers. ............................................................... 37 4 1 Typical load displacement curves of particulate epoxy composites ................................... 42 4 2 Fracture toughness of particulat e epoxy composites ........................................................... 42 4 3 Representative images of the fracture surfaces of an unfilled system and a 4 vol. % filled system ........................................................................................................................... 43

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9 4 4 Representative images of fracture surfaces of neat and filled epoxy systems far away from the crack tip. .................................................................................................................. 43 5 1 Typical load displacement curves for composites.. ............................................................. 52 5 2 Results of crack surface area simulations. ............................................................................ 52 5 3 Visualization of boundary conditions for finite element model exploring crack shielding. ................................................................................................................................. 53 5 4 Finite element mesh for unfilled epoxy sample. The simulation consists of about 5000 elements. ........................................................................................................................ 53 5 5 Close up view of the crack tip singularity region of the finite element mesh for unfilled epoxy sample.. .......................................................................................................... 54 5 6 Results of FEA experiments testing the crack shielding hypothesis. ................................. 54 5 7 Deformed shape and stress field of sample with 25 m diameter particles (perfect bonding) randomly dispersed in an epoxy matrix corresponding to 5 volume percent of reinforcement phase. .......................................................................................................... 55 5 8 Resutls for a random particle field dispersion of various particle diameters (without bonding, only contact) resulting in 5 volume percent of reinforcement phase. ................. 55 5 9 Deformed shape and stress field of sample with 25 m diameter particles (no bonding, only contact) randomly dispersed in an epoxy matrix corresponding to 5 volume percent of reinforcement phase. ............................................................................... 56 5 10 Results of electron microscopy on 1mm cantilevers. .......................................................... 56 5 11 FIB images of 5 vol. % ZnO/SC 15 10 m cantilever beam.. ............................................ 57 5 12 FIB images of unfilled 10m cantilever beam. .................................................................... 57 5 13 High magnification images of 10m cantilever with inverted color scheme.. ................... 58 6 1 Examples of element types .................................................................................................... 69 6 2 Example of a polymer field created using the random walk process. ................................. 69 6 3 Example of multiple polymer chain elements and the layout of each element type .......... 70 6 4 Example of polymer relaxation process ................................................................................ 71 6 5 Proposed AFEM simulations for future work ...................................................................... 72 A 1 Deformed shape and stress field of sample with neat epoxy sample. ................................. 75

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10 A 2 D eformed shape and stress field of sample with 25 m diameter particle placed 10 m from the crack tip. ............................................................................................................ 75 A 3 Deformed shape and stress field of sample with 25 m diameter particle placed 12.5 m from the crack tip. ............................................................................................................ 76 A 4 Deformed shape and stress field of sample with 25 m diameter particle placed 25 m from the crack tip. ............................................................................................................ 76 A 5 Deformed shape and stress field of sample with 25 m diameter particle placed 50 m from the crack tip. ............................................................................................................ 77 A 6 Deformed shape and stress field of sample with 50 m diameter parti cle placed 10 m from the crack tip. ............................................................................................................ 77 A 7 Deformed shape and stress field of sample with 50 m diameter particle placed 12.5 m from the crack tip. ............................................................................................................ 78 A 8 Deformed shape and stress field of sample with 50 m diameter particle placed 25 m from the crack tip. ............................................................................................................ 78 A 9 Deformed shape and stress field of sample with 50 m diameter particle placed 50 m from the crack tip. ............................................................................................................ 79 A 10 Deformed shape and stress field of sample with 75 m diameter particle placed 10 m from the crack tip. ............................................................................................................ 79 A 11 Deformed shape and stress field of sample with 75 m diameter particle placed 12.5 m from the crack tip. ............................................................................................................ 80 A 12 Deformed shape and stress field of sample with 75 m diameter particle placed 25 m from the crack tip. ............................................................................................................ 80 A 13 Deformed shape and stress field of sample with 75 m diameter particle placed 50 m from the crack tip. ............................................................................................................ 81

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11 Abstract of Dissertation Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy FRACTURE TOUGHENING MECHANISMS IN NANOPAR TICLE AND MICRO PARTICLE REINFORCED SYSTEMS USING MULTI-SCALE ANALYSIS By Benjamin Boesl May 2009 Chair: Bhavani Sankar Cochair: W. Gregory Sawyer Major: Aerospace Engineering Fracture toughness results from multi -scale experimentation and modeling of a polymer system reinforced with ZnO particles of two nominal diameters (53 n ano m eters and 75 microns ) are presented within this work T he composites were fabricated using an orbital shear -mixing device. Fracture toughness measurements were completed using a four point bend apparatus following ASTM standard E1820, resulting in an increase of 80 percent in critical stress intensity factor for epoxy filled with 4 vol ume percent nanoparticles. Studies using a focused ion beam were conducted to investigate the toughening mechanisms of particle reinforcement at the micro scale. Cantilever beams were created over two different length scales (approximately 1 mm and 10 microns ) and loaded using an Omniprobe device in -situ in the focused ion beam Using this method both the nanoparticles and the crack were imaged simultaneously and the results were compared with common assumptions regarding crack propagation within particulate composites. Experimental results were compared to three hypotheses using both experimenta l results and modeling techniques in an attempt to explain the increase in toughness that can be observed in a typical nanocomposite system. Results showed strong correlations to mechanisms that reduce the apparent stress intensity factor in the crack tip region thus preventing unstable crack growth.

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12 CHAPTER 1 INTRODUCTION Polymer matrix composites (PMCs) have set the standard in specific strength and toughness in the aerospace industry, but as the needs of aerospace structures become more stringent, fib er reinforced composites must be improved. One possible avenue for improvement began with the discovery of the single wall carbon nanotube by Iijima in the early nineties [1]. Iijimas publication in 1990 was credited with the introduction of carbon nanotubes to the more mainstream research communit y (though CNT origins may have predated this work [2]), which has led to the development of nanoparticles (particles with one or more characteristic lengths smaller th an 100 nm) as reinforcements in composite materials. Financial restrictions limit the use of CNTs and thus other lower cost particles including metal oxides, nanoclays, and nanofibers [3 5] have also been used as ad ditives to improve some of the properties of polymers. Nanocomposite systems have high potential as a reinforcement phase of PMCs. PMC reinforcement phases should not only be able to withstand large stresses, but also must interact with the matrix to tra nsfer the applied loading. The potential in nanocomposite systems is derived from their small size, which limits the number of defects in each particle. With fewer defects, the particles have higher strength compared to larger particles of the same materi al. Typically the force of bonding, and consequently the ability to transfer load, is a function of the amount of surface area between the particle and matrix. Nanocomposite systems have very large interfacial contact areas when properly dispersed (on the order of 500 m2/g for single wall carbon nanotubes) allowing for efficient load transfer. Although nanoparticles have potential as a sole reinforcement phase within a polymer matrix, cost and complications in manufacturing (particle agglomerations and al ignment of nonspherical particles for example) restrict the extent that nanoparticles can act as the only

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13 reinforcement phase. One possible method of incorporating nanoparticles into design of functional materials is to disperse them into traditional fib er composites, something that cannot occur with larger particles because they cannot infuse between the sub-micron gaps between fibers. The challenge of scale is a major issue in obtaining a working knowledge of the advanced mechanisms in nanometer size r einforcement of composite materials. Important phenomena in understanding and modeling the behavior of these systems happen over length scales that range ten orders of magnitude and no single analysis tool to date (be it experimental or computational) has been able to analyze this full range of scale. This work attempts to provide a working knowledge of the mechanisms of fracture of nanocomposites by using a multi -scale experimentation and modeling approach. At scales on the order of nanometers, material behavior and interactions can drastically change from those seen in macro -scale experimentation and modeling. The current state of the art in modeling nanocomposite systems attempts to account for these interactions using multi scale modeling, including finite element analysis and molecular dynamics simulations [6 8]. Multi -scale simulations attempt to piece together the mechanisms at varying scales into a single model that can explain the behavior of the entire system. This work will use this multi -sca le approach through experimentation, by varying the scale of testing using both conventional and newly developed techniques to piece together the varying stages of behavior of nanocomposite systems. Finally, the experimentation is compared to three differ ent hypotheses using modeling techniques to fill in some of the gaps that experimentation alone cannot predict. The goals of the research are to fabricate a composite using a typical engineering plastic reinforced with low cost metal oxide nanoparticles u sing vacuum assisted resin transfer molding (VARTM) compatible

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14 materials and techniques, characterize the composite, compare the results to a micro -particle reinforced system, investigate the mechanisms of fracture of the composite, and apply preliminary modeling techniques to begin to predict the behavior of the system.

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15 CHAPTER 2 BACKGROUND WORK AND MOTIVATION Background Epoxy alone has a high friction coefficient in most applications, as well as poor wear resistance compared to epoxy containing a filler component Fillers have been added to reduce both friction coefficient and wear rate. Studies with epoxy and micron-scale fillers by Burroughs et al. [6], Zhang et al. [7], and Chang et al. [8], show a monotonic reduction in wear rate with increased fill er loading up to 30 volume percent (vol %). Nanoscale fillers such as, TiO2 [7,8] SiO2 [9], Al2O3 [10,11] and Si3N4 [12] have also been shown to reduce friction and wear in epoxy m atrix composites. Chang et al. [8] used TiO2, PTFE, short carbon fiber, and graphite as fillers in a epoxy matrix, and was able to decrease the friction coefficient to =0.35 and decrease the wear rate 10x with 10 vol % TiO2 Shi et al. [10] saw a 0.4x decrease in friction coefficient, from =0.58 to =0.35, and 10x decrease in wear resistance with the addition of 2.0 vol % nanoscale Al2O3 to epoxy, and Wetzel et al. [11] saw a 2x decrease in wear resistance with the addition of small amounts of nano -Al2O3. Shi et al. [10] also saw decreases in friction coefficient, from =0.7 to =0.32 with the addition of up to 2.25 vol % of nano -Si3N4. The mechanical properties of par ticle filled composites are dependent upon the number and sizes of the particle defects in the matrix, and tend to be diminished with increased filler loading. Thus, it is desirable to optimize tribological properties at low particle loading. The filler volume fraction that resulted in the lowest wear rate of the composite (optimum loading) is plotted versus average reported filler diameter for the aforementioned studies in Figure 2 1. The optimum volume fraction is reduced with reduced particle size mot ivating the use of nanoparticles in this study.

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16 The epoxy used in this study is in the liquid phase prior to curing; this allows for easy particle dispersion as well as the ability to mold large and irregularly shaped parts. Nanoscale zinc oxide (ZnO) is thought to provide toughness and reduce wear by arresting cracks, promoting ductility, compartmentalizing damage, and reducing the effect of the third body debris. PTFE is a known solid lubricant and is used as filler in this study to form low shear strength transfer films. The interaction of these fillers is hypothesized to be synergistic, reducing traction stresses and the amount and size of third body debris which may destroy tribologically favorable transfer films. Composite Preparation and Optimization The ZnO used in this study was obtained from Nanophase is has an average particle size of 53 nm. The PTFE used in this study is 200 nm in diameter. The nanocomposites in this study consist of epoxy, zinc oxide, and PTFE. Both the zinc oxide particles and the PTFE particles are a gglomerated prior to sonication and dispersion into the epoxy resin. Scanning electron microscopy of the particles of zinc oxide and PTFE are shown in Figure 2 2 The PTFE particles are in agglomerations of around 20 m and the zinc oxide particles have some smaller agglomerations and some larger agglomerations up to 20 m in size. Similar to the process in Liao et al. [13] using acetone as a sol vent, epoxy resin was mixed with a 10:2 (resin to acetone) weight percent ratio and manually stirred for 5 minutes. Next, the zinc oxide and PTFE nanoparticles were mixed in slowly while stirring continuously. The mixture was then placed in a bath sonica tor for 6 hours to disperse the particles and reduce the amount and size of agglomerations of the PTFE and zinc oxide nanoparticles. Then, the mixture was placed in a vacuum oven at 75C for 2 hours to vaporize the acetone. A vacuum was slowly pulled on the oven to reduce porosity. The epoxy hardener was then added with a 10:2.5 (resin to hardener) weight percent ratio and the mixture was poured into a mold. The mixture was then cured at

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17 60C for 2 hours. Once cured the specimen was removed from the mo ld, post -cured at 170C for 50 minutes, and machined to the desired shape. Figure 2 2 shows a typical ZnO dispersion obtained from this processing. The tribological literature is full of binary composites that have been optimized in wt % or vol % for a particular property or behavior. There are numerous practical examples of ternary systems that have useful tribological properties. However, optimization of these systems has not been extensively reported in the tribology literature, nor have the methodologies to perform such experimental endeavors. The purpose of this study was to attempt an optimization of a nanocomposite to obtain the lowest wear rate and friction coefficient under a prescribed set of experimental conditions. One goal of this study is to see if there is an efficient experimental process that can be used to guide the materials development without exhaustively creating and evaluating a large sample population of nanocomposites. This is useful to reduce time, costs (due to the expensi ve nature of nanoparticles), and increase the number of constituents. The method that we are using is widely described as a Simplex Method following Nelder and Mead [14] which we have modified slightly to maintain reasonable increments in constituent loadings. For this optimization study, three initial samples were created at processable locatio ns on a ternary diagram. The initial three points were chosen at small volume percents of PTFE and zinc oxide nanoparticles to enable easy and robust processing. The ternary diagram shown in Figure 2 3 represents all three components of the composite mat erial with the matrix material, epoxy, at the top point and the fillers, zinc oxide and PTFE, on the side points. The lines on the ternary diagram are lines of constant volume percent of each constituent. Samples with less than fifty volume percent epoxy were not tested, (such high loadings inhibit epoxy curing). To find the next iteration in the search, a plane is fit to the three initial points based on the wear rates of the

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18 samples and a gradient of the plane is used to determine the search direction at a distance proportional to the gradient of the plane. Once the next point is tested, the samples wear rate along with the lowest two wear rates from the previous samples were used to create a new plane and find the next point. This process was repeat ed until the optimization scheme began pointing to previously tested sample compositions. It is important to note that the optimization process used can produce a local optimum, but for this study the only processable conditions pointed repeatedly to this optimum. Experimental Procedure Experiments for this study were conducted on a linear reciprocating pin -on-disk tribometer that has been extensively analyzed and discussed (see an uncertainty analysis of the friction coefficient and wear rate in Schmitz et al. [15,16] ). The counterfaces are lapped plates of AISI 304 stainless steel and are described in detail in Burris and Sawyer [17] Five measurements on a representative sample using scanning white light interferometry resulted in = 161 nm and = 35 nm. Composite samples are 6.35mm x 6.35mm x 12.7mm in size and are in contact with the counterface with a normal force of 250 N (6.3 MPa). The reciprocating length is 25.4mm and the average sliding speed is 50.8mm/s (1Hz). Samples and counterfa ces were cleaned with methanol prior to testing. Due to environmental uptake of the epoxy matrix, a gravimetric method could not be utilized to determine mass loss for samples that were very wear resistant. Thus, an LVDT was used to determine the change in height of the pin in-situ. In order to minimize the effects of creep, regressions of the wear slopes were conducted for the portion of the test determined to be at steady -state; this measurement is an upper bound on wear rate since the worn volume includes effects from both wear and creep. Because the wear rates of the samples vary by orders of

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19 magnitude, it was necessary to conduct tests for different distances of sliding. High wear rate materials are worn out quickly, while low wear rate samples must be run significantly longer sliding distances in order to detect statistically significant measures of wear volume. Results and Motivation for Future Work Epoxy is not inherently lubricious, with a coefficient of friction typically above =0.5. Epoxy is frequently used as a matrix for composites because of its strength and easy processing. For this study, the epoxy matrix was originally filled with small volume percents of zinc oxide to increase the wear resistance; the wear resistance increased by m ore than 10x with the addition of 1 vol % of zinc oxide nanoparticles (see Table 2 1). The sample with the lowest friction coefficient contained 3.5 vol % zinc oxide and 14.5 vol % PTFE. Figures 2 4 and 2 5 and Table 2 1 give all of the samples create d for the study and the corresponding wear rates and friction coefficient versus the vol % of each filler. The sample having the lowest wear rate, k=1.79x107mm3/Nm, contained 1 vol % zinc oxide and 14.5 vol % PTFE. The trend for wear rate pointed to having a composite with no zinc oxide filler and 15 vol % PTFE, but after testing a composite with no zinc oxide and 15 vol % PTFE it was proven that the addition of small amounts of zinc oxide nanoparticles were needed to obtain the lowest wear rate and friction coefficient. The wear rate and friction coefficient of the sample without zinc oxide and 15 vol % PTFE was k=3.70x107mm3/Nm and =0.193, respectively. Both of these values are higher than the values for the optimum samples wear rates and coef ficient of friction. There are a number of theories regarding the origins of wear resistance and friction coefficient reductions in polymeric nanocomposites. One constant observed in experimental tribology is that fine wear debris usually accompanies r educed wear rates, reduced friction coefficient, and uniform transfer films. The mechanics and physics underlying this debris generation is an open question. A hypothesis for the reduced friction coefficient and wear rate

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20 upon the inclusion of ZnO in epo xy is that the wear debris size was regulated though the control of particle dispersion (Figure 2 2). In summary an experimental process that utilized a simple optimization procedure was performed on a ternary nanocomposite. This process found and vali dated an optimum composition after creating under a dozen samples. The wear resistance of the epoxy nanocomposites was greatly increased with the addition of small volume percents of zinc oxide nanoparticles and nanoparticles of PTFE. The friction coeffic ient decreases with the addition of zinc oxide nanoparticles and was further decreased with the addition of PTFE nanoparticles.

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21 Figure 2 1 Plot of the volume percent correlating to optimum tribological properties according to th e literature versus particle size in micrometers for various fillers in an epoxy matrix. Figure 2 2 Images obtained though e lectron microscopy of nanoparticles. A ) Scanning electron microscopy of ZnO agglomerations and PTFE part icles. B ) T ransmission electron microscopy of ZnO dispersed in an epoxy matrix.

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22 Figure 2 3 Ternary diagram with the matrix material, epoxy, at the pinnacle and the filler materials, ZnO and PTFE, at the bottom corners. The lin es on the ternary diagram are line of constant volume percent. Filled circles represent tested samples and number circles represent the order of iterations. The fifth and third iteration lie on the same point indicating that the sample has been optimized.

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23 Figure 2 4 Steady state wear data for the epoxy nanocomposite samples in this study. These tests were run on a reciprocating tribometer under a 250N load and a 50.8mm/s sliding speed.

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24 Figure 2 5 Average steady state friction coefficient data for the epoxy nanocomposite samples in this study. These tests were run on a reciprocating tribometer under a 250N load and a 50.8mm/s sliding speed.

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25 Figure 2 6. Three dimensional visualization of wear rate and friction coefficient resutls of EpoxyZnO -PTFE system

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26 Table 2 1 Volume concentration of matrix material, epoxy, and filler materials, ZnO and PTFE along with the t abulated average values for steady state wear rate and fricti on coefficient. volume concentration Wear r ate x10 6 ( mm 3 /Nm) Coefficient of f riction Epoxy ZnO PTFE 85 5 10 0.658 0.163 85 10 5 8.130 0.185 90 5 5 2.290 0.177 85 2.75 12.25 0.281 0.123 82 3.5 14.5 0.607 0.113 84.5 1 14.5 0.179 0.135 85 0 15 0.37 0 0.193 100 0 0 8.350 x 10 1 0.704 99 1 0 6.100 0.273

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27 CHAPTER 3 IDENTIFICATION OF IN FLUENCES IN NANOCOMP OSITE DESIGN Particle Dispersion and Alignment Survey of Dispersion Data It is difficult to generalize the current state of particle dispersion in n anocomposite design. Many of the published nanocomposite studies focus on synthesis, characterization or mechanical property evaluation; broad ranging studies that include all three of these components are missing from the literature. Often, mechanical e ngineers lack the materials science background to conduct thorough nanocomposite characterization, and materials scientists lack the expertise required to conduct detailed investigations of their well -characterized nanocomposites. Together these disciplin es have the complimentary tools necessary to make large impacts in this area, but to the authors knowledge, this synergism has not yet been exploited to its full potential. Developing collaborations and sharing techniques between communities will facilit ate a more comprehensive understanding of the role of nanoparticles in composite design. A survey of the literature revealed the standard technique to verify the dispersion state of a nanocomposite consists of using Transmission Electron Microscopy (TEM) o n very small sample sizes. Figure 3 1 shows how the images obtained from TEM are presented in most journal papers. One can notice that the actual investigation size of a single TEM image insanely small compared to the bulk material. For a bulk sample wi th the dimensions of 10 mm x 10 mm x 20 mm the total volume is 2000 mm3, and the standard imaging volume using TEM in which it is possible to distinguish individual nanoparticles is about 1 m x 1 m x 200 nm giving a total volume of 2 x 1010 mm3. Theref ore the investigation size relating the dispersion state of the entire sample is thirteen orders of magnitude smaller than that of the bulk sample in a typical experiment. Adding to the complexity is the randomness of the chosen location of the volume

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28 b eing imaged. Many sample preparation techniques, including using a cryo-microtome (the most common and widely used method), are somewhat restricted in the areas that the imaged volume can be taken. That, and the fact that in order to get the best looking image from the TEM it is necessary to search within the sample to find a section of material that is thin enough to be electron transparent, can cause the images to be of volumes that are not necessarily representative of the bulk composite. Additionally, while the many journal articles include these TEM images, few make an attempt to quantify the dispersion state in any repeatable manner so that each dispersion technique can be analyzed for its dispersive characteristics. It was the apparent that the di spersion state of the nanoparticles within the composite community is an influence on the final design that has been somewhat ignored in the current state of the art nanocomposite literature. This research will attempt to further clarify dispersion state first using traditional methods (microtome and TEM) and then by developing a new imaging technique to increase the imaged volume of each sample. Finally, the images will be compared using statistical techniques in an attempt to quantify the dispersion sta te. Dispersion Imaging Techniques Two d imensional techniques: m icrotome and transmission e lectron m icroscopy The plan of the research was to use traditional techniques, with an emphasis on imaging a random volume that was as large as possible, as an initia l step and then build up from there. The technique consist of fabricating a sample, in a method similar to the one outlined in Chapter 2, and casting that sample in a mold specifically for the microtome. Within the microtome the sample was then shaven do wn to a size of 1 mm2 on the face and about 5 mm long using a standard razor blade. The face of the sample was then planed using the microtome to a thickness of about 200 nm and placed on a TEM grid. The thinned samples are then coated with a thin

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29 layer of Au Pd for conductivity within the microscope. Figure 3 2 illustrates the optimum images obtained using this process. One can see that the clarity of the images is high but the microtoming process has left the sample with a high number of voids through out. What is also unclear is the depth each particle is within the imaged volume, because TEM is a procedure that uses transmission of electrons through the volume of the material, and that volume (about 200400 nm thick) is almost an order of magnitude l arger that the particles being imaged, the images can include multiple planes of particles which may distort any statistical analysis, although if these shortfalls are know n and accounted for the images can be useful in analyzing the dispersion state of th e composite. Three -d imensional techniques: focused i on b eam As previously stated, the samples imaged using TEM are of a significantly smaller size than that of the bulk, therefore it is hard to make any correlation to the bulk composite with a single image A new procedure was developed to increase the imaged volume of the sample using a DB235 focused i on b eam. In this method the samples are fabricated, cast in a mold and coated with a thin layer of Au -Pd. The instrument has a field emission electron gun for high resolution imaging mounted at a 52 angle from a galvanized lithium ion beam (used for precise milling of the sample ) An illustration of the imaging procedure is shown in Figure 3 3 To start, an area larger than 5 m x 5 m of the surface is d eposited with a thin layer of platinum as a protective layer. The platinum coating also helps to reduce edge effects from the ion beam milling Using the ion beam, a trench was then milled around the volume of interest this allows for even slicing of the material near the imaged surface. In a process known as slice and view, the ion mill then slice s the sample at 30 nm intervals while the top surface is imaged using the electron beam. T his process wa s continued until the volume of interest is consumed. 1 00 slices are imaged making the overall imaged volume 5x5x3 microns. The images can then be

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30 processed using advanced imaging software and combined in tomographic process to form a three dimensional view of the composite, as shown in Figure 3 5 By using the FIB and reconstructing the images into a three dimensional image, this procedure solves a few of the problems TEM imaging can encounter. For starters, the imaged volume is almost two orders of magnitude larger for this procedure, the images are also of a two dimensional plane within the solid and not of a transmitted beam through the sample. The contrast mechanisms of SEM imaging are also favorable conditions for nanoparticle viewing. The major source of contrast in this system deals with the differ ence in atomic number between the constituents. The polymer system, having a very low atomic number appears black in the images and the nanoparticles (with a much higher atomic number) appear white in the images. This promotes a stark contrast between pa rticle and matrix, making it easier to distinguish between the two phases within the image processing software. Finally a t h roughthe lens detector was used in the imaging procedure accepts the signal of backscatter electrons whos interaction volume i s very small restricting the contrast influences to those on the surface of the composite. Quantification of Dispersion State In general, nanoparticle dispersion is qualitatively assessed using TEM imaging and qualitative descriptors (random, good, well, uniform, homogeneous, etc) of the observed dispersion. In many cases a single imaged is used for characterization, but it is difficult to capture the overall character of a particular dispersion with any single two -dimensional image. The challenge is t o find an appropriate method to create and image the slices. After reconstruction, many commercial codes can calculate a breadth of statistics, but there is no clear metric to describe dispersion.

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31 In many systems with heterogeneous dispersion the homogenei ty varies with observation size. Thus, a number of researchers use sequential scans at increasing magnification to capture the character of the dispersion. In particular, the structure and characteristic size of the agglomerations is qualitatively define d. In many cases the highest magnification suggests the best dispersion, while the lowest magnifications reveal the micro -scale distribution of composition for the composite. Figure 3 2 shows a series of such images taken using TEM from a 2 vol. % alumin a/epoxy nanocomposite. Such a technique is very useful in ascertaining the structure of the nanocomposites across a number of length scales. There are several quantitative dispersion characterization techniques in the literature and most involve measuring inter particle spacing, number densities and particle distributions [18 20] The discrete nature of the particle distribution suggests that a discrete statistical treatment such as the Poisson distribution may be used to describe the spatial arrangement of nanoparticles. The Poisson distribution is used to compare random and discrete events occurring within a certain interval. In this case, the probability, P, of a random occurrence, x, as a function of area, 1. (;) !xe Px x (3 1) One tedious approach that w as employed wa s to discretize the central locations of particles using the intens ities of the digital images collected from transmission and scanning electron microscopy. Many of these images need to be manually discretized. The result of discretization is shown in Figure 3 7 where the lowest magnification image from Figure 3 -2 is co nverted into a two dimensional point c loud. A Monte Carlo technique wa s used to place ten thousand squares of a prescribed area randomly within the point cloud domain. The number o f particles within each square wa s measured and a histogram of particle nu m ber wa s created. By varying the area

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32 of the squares in the Monte Carlo simulation one can interrogate the dispersions. In Figure 3 7 the expected distributions from a truly random dispersion is shown to agree with the Poisson distribution; any dispersion that doesnt agree cant fairly be termed random. The presence of agglomeration is clear from the spread in the distribution for the largest areas. Another indicator is the most probable number of particles approaching 0 for the smallest areas, which i s commensurate with the most probable vacant area. Both are indicators of particle agglomeration and subsequently particle depleted domains. Additionally, the two peaks in the distribution that appear for the 4m x 4m simulation are likely due to the si mulation size coinciding with a characteristic agglomerate spacing. A method to characterize dispersion across length -scales is an area of much needed and continued development. Finally, characterization was done on the as received micro -particles, shown in Figure 3 8, in which the presence of nano-size inclusions was evident and therefore any of the hypotheses in the latter chapters may also apply to the micro -particles as well.

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33 Figure 3 1. A survey of TEM images throughout the literature

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34 Figure 3 2 T EM images of a single domain within a 44 nm delta -gamma alumina filled epoxy at 2 vol. %. T he images are increasing in magnification and are approximately 25m, 12.5m, and 6.25m in width. The alumina nanoparticles appear dark in the epoxy matrix due to atomic number contrast Figure 3 3. Illustration of the slice and view procedure. 1) The imaged area is loc ated at the top of the sample. 2) Platinum is dep osited to reduce edge effects. 3) Ion milling of a trench around the area of interest. 4) Ion milling of slices (100 total mills, each 30 nm thick), electron beam imaging of top surface. 5) Volume is milled and the slice and view is complete.

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35 Figure 3 4. Orthogonal views from three planes of the imaged volume. The plane labeled XY is an actual im age taken using the SEM, the XZ and YZ planes are reconstructed using visual analysis software. Figure 3 5. A three dimensional reconstruction of the imaged volume. The sample is a 1 vol % ZnO filled Epoxy.

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36 Figure 3 6. Three dimensional particle view s obtained using the slice and view technique A ) 1vol % ZnO B) 2 vol % ZnO (c) 3 vol % ZnO (d) 4 vol % ZnO. All imaged volumes are 5 m x 5 m x 3 m.

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37 Figure 3 7. A pplication of the Monte Carlo analysis method to quanti fy a typical particle dis persion. A) Actual particle dispersion field obtained from a micrograph and its statistical data. B) Random particle field, of the same volume fraction, obtained using a random number generator and its statistical data Figure 3 8. Multiple images obtain ed from 75m nominal diameter particle sample showing the existence of particles on the scale of nanometers.

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38 CHAPTER 4 INITIAL FRACTURE TOU GHNESS EXPERIMENTATI ON Materials The epoxy used in this study was SC 15 supplied by Applied Poleramic, Inc. It w as chosen as a typical, low -cost engineering plastic consisting of a two-part liquid system with a low viscosity of 300 cP at room temperature. The low viscosity allows the particles to be added to the system, dispersed, and cured without the use of solve nts which, when not completely evaporated, can change the properties of the polymer. The two phases of the epoxy are a resin mixture of diglycidylether of bisphenol -A with an aliphatic diglycidylether epoxy toughener and a hardener mixture of cycloaliphat ic amine and polyoxylalkylamine. SC 15 is also compatible with most composite manufacturing procedures including vacuum assisted resin transfer molding. Two sets of commercially available particles were acquired for use in this study. ZnO particles were chosen as a typical metal oxide particle used in nanocomposite studies, and the low cost and availability make it a viable option for large scale use. The particles were also available in varying sizes while maintaining the same phase. The manufacturer e stimated the diameter of each batch of particles as 53 nm (obtained from Nanophase) and 75 m (obtained from Alfa Aesar), respectively. Fabrication Procedure Various techniques have been used to disperse nanoparticles in polymers including one, or a co mbination of the following techniques: shear mixing, melt mixing, extrusion, sonication, solvent addition, and mechanical stirring. Yasmin et al. [21] compared ultrasonic techniques with shear mixing techniques and found that shear mixing provided the best dispersion of particles based on mechanical property calculations. Shear mixing also has the added benefit of being

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39 scalable, useful in large -scale manufacturing. As a result the samples for this study were created using a shear -mixing device. This mixture of epoxy and nanoparticles was also chosen for the future possibility of infusing through carbon fibers to create a hybrid nano particle filled carbon fiber reinforced composite. The composites were mixed using a Hauschild orbital shear -mixing device. The nanoparticles were first weighed and added to the resin and mixed at 3000 rpm for 4 minutes. Next, the hardener was added and mixed at 3000 rpm for 4 minutes. The solution was then cast in a mold and cured at 60C for 2 hours. Finally, a post cure was done at 150C for 50 minutes. Testing Procedure Previous studies on the fracture toughness of nanofiller reinforced composites have shown the ability to increase the fracture toughness of polymers by adding very small filler concentrations [3,11,2228] The fracture toughness of the particulate reinforced epoxy mixture was determined using a Mini Bionix II MTS testing machine following ASTM Standard E1820, modified to use a four -point bend fixture [29] A four point bend fixture was used to eliminate any alignment errors that may cause unwanted shear force within the sample. Samples are prepared for fracture testing after the curing process by machining the exposed surface to size (L a band saw. Following that, a razorblade is inserted into the starter crack and gently tapped with a rubber mall et. The crack was then measured using an optical microscope. The specimen was then loaded into the load frame and a pre -crack procedure was completed using a sinusoidal waveform with a frequency of 50 Hz at a load of less than 70% of Pmax. Fracture tests were completed using displacement control at a rate of 5 mm/min. To determine the critical stress intensity factor of each sample the following linear elastic fracture mechanics (LEFM) formulas were used [30] :

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40 2341.121.397.31314ICaaaa Ka WWWW (4 1) max 23 PD BW (4 2) where a, B, W are specimen dimensions defined above, D is the distance between the four point bend fixtures (D mm) and Pmax is the maximum load the sample sustains prior to failure. Initial Observations The results of the fracture testing are shown in Figure 4 1 and Figure 4 2 From the load deflection diagram, shown in Figure 4 1 one can notice that the material exhibits linear behavior until catastrophic failure. The nonlinearity at small loads can be attributed to local contact. For small loads the local indentation dominates the gl obal deflection of the beam, and the loadindentation behavior is nonlinear similar to Hertzian contact law. One can also note that the specimens fail in a brittle manner indicated by the sudden drop in load. This indicates that the crack propagation was i nstantaneous, at least in the macroscopic scale. The fracture toughness values calculated, using Equation 4 1, for various specimens are plotted in Figure 4 2 One can note that there is a monotonic increase in fracture toughness with the volume percentage of particles until 3%. The composite reinforced with nanoparticles seems to reach a plateau at about 4%. The samples reinforced with micron -size particles show a definite drop in fracture toughness beginning at 2% volume concent ration. The maximum increase in KIC compared to neat resin is about 80% for nanoparticles, whereas the micron -size particles show a maximum increase of about 55%. Another interesting observation form the load-displacement diagram is that the increase in fr acture toughness comes from the increase in load to fracture. There is no apparent inelastic

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41 behavior similar to yielding in ductile materials before failure. There is a possibility that the process zone ahead of the crack is very small compared to the cra ck length, and hence there is no significant load drop before failure of the specimen. In fact this behavior is confirmed by some of the observations discussed below. Analysis of Fracture S urfaces The SEM micrographs in Figure 4 3 are representative images of the area very near the initial pre -cracked region. The regions a, b and c in the pictures correspond to the regions of the fractured surface, the pre -crack region, and the band saw pre -crack region, respectively. The small cartoons in the images show the relative location and size of the imaged region in relation to the overall sample size. It is obvious that the morphology of the fracture surface in the filled system is much rougher and the path the crack travels is more to rtuous near the crack tip. This observation implies that at least a portion of the load is being transferred from the matrix to the particle and the toughening mechanism results in a more tortuous fracture path. In contrast, images at regions far away fr om the crack tip, shown in Figure 4 4 show that the fractures surfaces of the filled and unfilled systems are quite similar. These observations support the earlier theory of a small process zone in the crack tip region whose eff ects may not be apparent in a macro -scale fracture test. The results of experimentation and modeling were compared with three separate hypotheses to determine the most plausible toughening mechanism within the material, with the results presented in the fo llowing sections.

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42 Figure 4 1. Typical load displacement curves of particulate epoxy composites Figure 4 2. Fracture toughness of particulate epoxy composites

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43 Figure 4 3. Representative images of the fracture surfa ces of an unfilled system and a 4 vo l % filled system The highlighted region on the cartoon of each image is the relative location and size of the imaged region in relatio n to the specimen size. A) S hows the fractured surface. B) Shows the pre -crack region. C) Shows the b and saw pre -crack region. Figure 4 4. Representative images of fracture surfaces of neat and filled epoxy systems far away from the crack tip. The highlighted region on the cartoon of each image is the relative location and size of the imaged region in relatio n to the spe cimen size.

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44 CHAPTER 5 FRACTURE TOUGHENING MECHANISMS Hypothesis: Crack Area Increase One possible mechanism of toughening relates the increase in toughness to an increase in the area the crack travels during failure. The SEM images of the fracture surfa ces verify that, at least in the crack tip region, the morphology of the created surfaces are more tortuous than that of the unfilled system. This toughening mechanism is usually associated with systems reinforced with very large particles or stitches, an exampl e of which is shown in Figure 5 1 It is important to note that the path a crack travels is not determined until after the onset of propagation, therefore, for the crack area hypothesis to be valid for systems reinforced with much smaller particles there should be evidence of toughening of the composite after crack propagation begins. It is clear from Figure 4 1 that, if the increase in crack area were a dominant factor in the toughening of the material, the load displace ment graph would look similar to that of a stitched composite, where there is some initial onset of a crack followed by a period of continued energy dissipation. In contrast, the load displacement diagram shows that the toughening mechanism at work preven ts the crack from initially propagating, thus allowing for a higher maximum load and displacement. That is not to say that the crack cannot be diverted by the presence of the particles, in fact it can (shown both in the increased roughness of the fracture surface and in the later section involving microcracking), but merely that the energy required to create this surface is relatively small compared to other mechanisms. Further investigation of the crack area hypothesis was completed through a simple Mon te Carlo like simulation. As previously discussed, the energy required to fracture a material is proportional to the amount of new surface area the crack creates multiplied by the surface energy per unit area. Therefore, an ostensible model that fits this mechanism is to assume the particles

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45 are rigid and when the crack encounters a particle the crack path is diverted around the particle creating an increase in the new surface area created. To determine the possible increase in fracture surface area of a particulate filled composite a procedure was developed to randomly place a prescribed volume percent of rigid particles within a volume and determine the increase in area of a number of random planes that bisects that volume. The model simulates the possi ble increase in new surface area created by a random crack passing through the region and estimates the increase in energy needed for propagation. The limiting case, for maximum increase in surface area, assumes that the particles are rigid, as previously stated, the crack travels along the interface between the particle and matrix, and the surface energy per unit area of the interface region is the same as the matrix. A parametric study was completed wherein the particle diameter ranged from 50 nm to 5 m and the filler concentration ranged from 0 to 20 volume percent. The simulation averaged the area of 10,000 randomly placed cracks for each specific diameter and filler volume percent. The average area is then divided by the area of initial plane, in order to determine the increase in surface area. The average value at each specific volume percent and particle diameter are shown in Figure 5 2. The figure shows that even in the most ideal conditions the maximum increase in required energy is about .02% per volume percent of filler added, or about an order of magnitude lower than the overall increase shown in experimentation. It is important to note that the actual increase in fracture surface area would most li kely be much less than this ideal case further discrediting the theories validity as a toughening mechanism. Also, the crack area hypothesis would predict a large variance in the fracture toughness of composites reinforced with varying particle sizes. Exp erimental results show that the fracture toughness of the composites reinforced with 75 m particles and 50 nm particles are relatively the similar for the same volume percent

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46 of filler added. That being said, the analysis of crack propagation is very important, and cannot be ignored, in the crack tip region as shown in later sections. Hypothesis: Crack Shielding Macro -scale experimentation shows that the mechanism for improving toughness in particulate reinforced composites reduces the stress intensity f actor at the crack tip and prevents the crack from initial unstable propagation. Crack shielding is one possible mechanism that can explain the toughness increase. The hypothesis states that the load on the bulk material is transferred to the particles ar ound the crack tip, reducing the actual stress intensity factor at the crack tip. The externally applied load must then be increased for the material to fail, increasing the apparent toughness of the material. Analysis on a representative particulate re inforced polymer model was conducted using the ABAQUS software package [31] A 2D plane stress model was created for the purpose of comparing the stress intensity factor at t he tip of a crack in unfilled and multiple configurations of filled polymer systems. The stress intensity factor at the crack tip is measured using both J integral calculations and the stress matching approach, where applicable. The simulation used approximately 5,000, 8-node quadrilateral elements and the crack tip singularity was modeled using collapsed (triangular) elements with nodes at the quarter point. LEFM was used to determine the stress that should be applied along the boundaries of the model to simulate a specific loading state [30] The applied stresses are defined by: 3 cos1sinsin 222 2I xxK r (5 1) 3 cos1sinsin 222 2I yyK r (5 2)

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47 3 cossinsin 222 2I xyK r (5 3) KI is the applied stress intensity factor, value of which is arbitrarily set to 1 MPam Figure 5 3 shows the applied boundary condition in the model Initially the model was verified by applying the boundary conditions that correspond to a given KI to an unfilled system, and comparing the calculated stress intensity factor to the applied value. At this poin t, a convergence study was performed on the unfilled system to insure that the number of elements and mesh refinement were adequate. The finite element mesh is shown in Figure 5 4 and Figure 55 for the unfilled case. Finally, the model was populated w ith multiple configurations of particles by creating sections within the model with the material properties of the nanoparticles (E = 50 GPa, = 0.3). The interface between the matrix and polymer was assumed to be perfect and all loads are restricted to be within the limits of the elastic region of deformation. After testing multiple particle configurations, two interesting cases stood out; a single particle of varying size placed at a varying distance from the crack tip, and a random configuration of p articles with constant volume percent and diameter. A parametric study was completed for both cases where the particle diameter varied from 25 to 75 m and the distance from the crack tip ranged from 10 to 50 m for the single particle simulations. Due to restrictions in the ability to fully model a three dimensional sample reinforced with varying particle dispersions and particle sizes the finite element results do not correlate one to one with the experimental data The results, shown in Figure 5 6 do indicate that a single particle placed directly in front of the crack path can drastically reduce the stress intensity factor at the crack tip, and the larger the particle and the closer to the crack tip the larger the decrease. While encouraging, there is no way to ensure that a single particle is in front of the crack tip in

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48 every experiment, meaning that the data should be widely varying for cases of the same volume percent of filler. As seen in the experimental data, this is not the case; the data is very repeatable for multiple data points. Figure 5 6 (with the stress field and deformed shape shown for an individual case shown in Figure 5 7) also shows the results for multiple random particle fields of a specific particle diameter at a single volume percent. These results are encouraging because the same average increase is seen for varying particle sizes, but the increase is much lower than that of the experimental data. Also interesting is the apparent larger spread in data points for larger part icle sizes, which was also seen in the experimental data. Finally, the bonding between particle and matrix was eliminated; leaving contact as the only form of load transfer, and the simulation of particle fields at a prescribed volume percent was re run. Results, shown in Figure 5 8 and Figure 59, show a slight drop in the ratio of actual to measured KIC, resulting in a lower predicted increase in fracture toughness. In this situation the complexity of the crack region many not be completely accurately represented in the simulation, and therefore further analysis should be completed to better understand the influence of particle and matrix interaction on the fracture toughness of this system. The results of the experimentation and finite element analysi s suggest that crack shielding can be a mechanism for toughening, but the method must be refined in order to explain the experimental results. As will be seen in some of the experiments discussed in the next section, inelastic behavior due to microcrack f ormation ahead of the crack tip should be included in modeling in order to explain the increase in fracture toughness. Future work should include a move away from linear elastic techniques, and look into other inelastic deformations of the polymer in the crack tip region.

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49 Hypothesis: Microcrack Formation and Crack Pinning The final hypothesis discussed involves the formation of microcracks within the region very near the crack tip. Cracks in a material generally create stress concentrations and reduce the toughness of a material, although the presence of very small cracks can actually increase the toughness in certain circumstances. This mechanism is dependent on the microcracks absorbing energy during their propagation and coalescing into a larger crack which ultimately leads to the catastrophic propagation of the parent crack. If unstable crack growth can be prevented, the load bearing capability of the material will increase, therefore increasing the critical stress intensity factor. Nanoparticles can be an effective barrier against crack growth assuming that there is a functional interface between the particle and matrix. In contrast to the crack area hypothesis, microcrack formation happens in a very small region in front of the crack tip. As a result, the formation of microcracks would not be noticeable in micro -scale experimentation, and the load displacement diagram would emulate Figure 5 1 for particulate reinforce composites. Insitu FIB micro -scale fracture tests (~ 1 mm cantilever length) One of the challenges of investigating composites with filler size on the order of nanometers is the inability to image the particles during the loading process. Lourie and Wagner [32] were able to fracture very thin, electron transparent polymer films reinforced with SWNT within the chamber of a transmission electron microscope (TEM) using thermal expansion by heating the polymer with the electron beam. In an effort to eliminate the thermal component of loading, a procedure was developed to observe mechanical deformation and crack growth within a scanning electron microscope. In these experiments the microscope is a FEI dual -beam focused ion beam A section of composite was shaped into a cantilever beam with a square cross section of 0.5mm 0.5mm with a razor blade. The length of the cantilever was approximately 1 mm. The composite is then coated with a thin layer of Au Pd for conductivity in the microscope. An

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50 Omniprobe micro -manipulator was used to deform the cantilever, producing a mode I crack. After deformation, the region in front of the crack was imaged at th e scale of the nanoparticles (65,000x magnification ), though the crack propagated too quickly to image crack growth at this scale. Experiments done using 1 mm cantilevers given in Figure 5 10, show the formation of microcracks within the nanocomposite. T he higher magnification image taken in the region directly in front of the crack shows the formation of the previously mentioned process zone in front of the crack tip. The cracks are uniformly distributed along the crack front and propagate in a region 3 to 4 microns in front of the crack tip. The cracks also appear to terminate at the particles in some instances, although it is uncertain that the propagation begins or ends at the particles since the crack in not being imaged dynamically. It is importan t to note that the process zone is not apparent in the 250x image and therefore it is safe to assume that the effect of the process zone were most likely not within the resolution of the load cell in the macro -scale experimentation. Insitu FIB micro -scale fracture tests (~ 10 m cantilever length) A smaller set of cantilevers were milled using the Ion Beam of the DB235 -FIB to reduce the length the crack propagates under deformation. The size of the cantilever was reduced to a cross section of approximately 5 m 5 m, and 10 m long. The cantilevers were again deformed using an Omniprobe, this time producing a mode III crack within the nanocomposite. The series of images in Figure 5 11 shows the results of an experiment on a sample with 5 vol% particles. The formation of microcracks is evident in the images, and through the progression of images the cracks are pinned in many places by particle formations. This is a stark contrast to the unfilled system shown in Figure 5 12 where the initial crack quickly propagates through the material and there is no apparent formation of any other cracks on the

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51 surface of the composite. Figure 5 13 shows the reinforced system on a larger scale and with the color scheme inverted, the images clearly show the presence of m icrocracks in the material as well as the pinning of cracks between particles. The findings in this experiment confirm the findings in the images of the fracture surfaces seen earlier in the paper. It is evident the presence of particle reinforcement res ults in a more tortuous fracture surface near the crack tip and the cracks tend to both form and terminate near particles. This process gives a qualitative look into fracture at the scale of both the nanoparticles and the formation and propagation of a cr ack, and while there is no apparent nonlinear behavior on the macro-scale, the material behavior in the crack tip region is very complex and further efforts should be made to characterize the material behavior using non -linear material properties.

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52 Fi gure 5 1. Typical load displacement curves f or composites. A ) Reinforced with stitches B) Reinforced with particles of diameter smaller than 500 m. Figure 5 2. Results of crack surface area simulations

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53 Figure 5 3. Visualization of boundary conditi ons for finite element model exploring crack shielding. Figure 5 4 Finite element mesh for unfilled epoxy sample. The simulation consists of about 5000 elements.

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54 Figure 5 5 Close up view of the crack tip singularity region of the finite element mes h for unfilled epoxy sample. The singularity is modeled using a collapsed, triangular element with nodes at the quarter point. Figure 5 6 Results of FEA experiments testing the c rack shielding hypothesis. A ) Results for a single parti cle in front of t he crack, each line corresponds to the distance the particle is placed in relation to the crack tip. B ) Resutls for a random particle field dispersion of various particle diameters resulting in 5 volume percent of reinforcement phase

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55 Figure 5 7 Deform ed shape and stress field of sample with 25 m diameter particles (perfect bonding) randomly dispersed in an epoxy matrix corresponding to 5 volume percent of reinforcement phase. Figure 5 8 Resutls for a random particle field dispersion of various part icle diameters (without bonding, only contact) resulting in 5 volume percent of reinforcement phase.

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56 Figure 5 9 Deformed shape and stress field of sample with 25 m diameter particles (no bonding, only contact) randomly dispersed in an epoxy matrix corresponding to 5 volume percent of reinforcement phase. Figure 5 10. Results of electron microscopy on 1mm cantilevers. A ) to C ) Schematic of bending the 1mm cantilever beams. D ) and E ) FIB images of fracture of 5 vol % ZnO/SC 15 nanocomposite.

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57 Figu re 5 1 1 FIB images of 5 vol % ZnO/SC 15 10 m cantilever beam. C) Image clearly illustrates microcracking and crack pinning in the composite. Figure 5 1 2 FIB images of unfilled 10m cantilever beam.

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58 Figure 5 1 3 High magnification images of 10m cantilever with inverted color scheme. The inverted color scheme allows for improved imaging of microcracks and crack pinning.

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59 CHAPTER 6 MODELING MATERIAL BE HAVIOR As mentioned previously, one of the largest challenges in working with nanocomposite mater ials is vastly varying scales at which crucial information must be input and measured. This is particularly challenging when trying to model the behavior of these systems, as interactions on the nanoscale can affect bulk mechanical properties on the macro -scale. The resolution of the model must be high enough to capture the very small local interactions, and large enough to simulate a large enough portion of the bulk material to make a connection to actual material behavior. A typical analysis tool for modeling bulk behavior is Finite Element Analysis (FEA), this analysis tool uses continuum mechanics and has been used for decades to model bulk material properties and interactions by interpolating the deformation of a material from a set of fixed points or nodes. The definition of the interpolation function can change based on the material and the property that is being investigated and is often lumped within a global definition of an element. FEA simulations are defined by the selection of the node s and elements and the simulation is limited by the limitations of the nodes and elements. A typical analysis tool for the modeling of nanoscale material interaction is Molecular Dynamics (MD) simulation. MD simulation is a relatively cutting edge simu lation technique in which the laws of quantum physics govern the interactions between atoms or molecules at a relative scale. As quantum events are random in nature, this simulation technique uses scale factors and a random number generator to assign a ve locity to an atom or molecule and then checks against know quantum rules to determine the feasibility of the assigned velocity and corrects the velocity if necessary. This technique allows for investigation of material interaction at a much smaller scale than that of FEA but the bulk size of the experiments are very limited at

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60 this time. Also, as implied in the name, MD simulations are dynamic and the time scale must be chosen to include atomic vibrations that occur in picoseconds, meaning for observable deformations the strain rate of deformation must be high. In many cases this strain rate is much higher that that of any comparable experimental data. Both FEA and MD simulations have an infinite set of problems that they can solve, but in the case of ma terial systems that require simulation of nanoscale interactions and observation of bulk material properties the limitations of each method outweigh the benefits of use. In this case, a combination of the two methods can provide more accurate information in less time than one method alone. One method to that has been developed is to formulate elements in FEA that are governed by the atomic potentials of MD simulations. This method can include iteractions at the nanoscale, larger simulation sizes than typ ical MD systems can produce, as well as the removal of the dynamic component of MD systems that restrict the range of strain rate. Wang et. al. and Theodoru et. al. have used this technique to simulate polymer fields and in this work the data is recreate d to verify the results and improve the element definitions that were used [33, 34] This method will be denoted as Atomic Finite Element Method (AFEM) throughout the rest of the document. Stiffness Matrix Determina tion The use of AFEM to model polymeric systems requires the definition of three element types; two elements that are defined by the radial atomic spacing using two nodes and one element defined by the center angle between three connecting nodes. Each ele ment is further defined in the following sections. Covalent Length Element (CL) The covalent bonding within chains of a polymer system (from mer to mer) can be defined in the simplest sense using the harmonic potential. The harmonic potential behaves like a linear

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61 s pring and is defined in Equation 6 1; where Vr is the potential energy, kr is a spring constant that is determined empirically for each material, ro is the equilibrium spacing of the potential, and r is the actual radial spacing between two node s. 21 2rroVkrr (6 1) Differentiating the potential energy equation gives the force function given in equation 6 2. r rrodV Fkrr dr (6 2) Looking at a typical element shown in F igure 6 1 rewriting the force equation in terms of nodal displacements in the local coordinate system gives : 1 1 1 1 2 2 2 21010 0000 1010 0000x y r x yf u f v k f u f v (6 3) Where f is the nodal force and u and v are the nodal displacements at the subscripted node. Converting from the local to the global coordinate system shown in F igure 6 1 gives: 22 1 1 22 1 1 22 2 2 22 2 2 x y r x yf u llmllm f v lmmlmm k f u llmllm f v lmmlmm (6 4) The variables l and m in Equation 6 4 refer to direction cosines. From Equation 6 4 the element stiffness matrix of a CL element is defined as: 22 22 22 22 CLrllmllm lmmlmm kk llmllm lmmlmm (6 5)

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6 2 Covalent Angular Eleme nt (CA) The covalent angular element shown in Figure 6 1, consists of three nodes and defined is any way such that local node 2 is connected to both local node 1 and local node 3. This relationship insures that the angle in question (shown as a green arc in Figure 6 1) always occurs at node 2. The angle in a CA element is always assumed to be less than 180. The potential energy function of a CA element is given as: 21 2oVk (6 6 ) Where V is the potential energy, k is a torsional spring constant that is determined empirically for each material, o is the equilibrium angle of the potential function, and is the actual angle at local node 2 of the element. Relating the change in angle in Equation 6 6 to the global nodal displacements shown in Figure 6 1 gives: 112233 T oBuvuvuv (6 7 ) B in Equation 6 7 is a 1 by 6 array that can be determined by geometry and is defined in Equation 6 8 through Equation 6 11. 11223321 TBuvuvuv (6 8 ) 2121211111 1 11vvvlumvlul LL (6 9 ) 3232322222 2 22vvvlumvlul LL (6 10) Equating Equations 6 8 with Equation 6 9 and Equation 6 10 gives: 11212122 11212122mlmmllml B LLLLLLLL (6 1 1 )

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63 The potential energy function can now be expressed in terms of the kn own functions B and q (global nodal displacements) by substituting Equation 6 7 into Equation 6 6 given as Equation 6 12: 2 21111 2222T T oVkkBqkBqBqkqBBq (6 12) From the potential energy function, the element stiffness matrix can be defined as: 1 2T CAkkBB (6 13) Leonard Jones Element (LJ) The Leonard Jones elements behavior is very similar to that of the CL element, with the exception that the spring constant kr is not constant throughout the simulation but is a function of the radial dista nce between nodes. The kr value for a given radial spacing can be determined by taking the second derivative of the Leonard Jones potential given in Equation 6 14. 1264LJV rr (6 14) The constants and are empirically determined consta nts that vary with material. Taking the second derivative of Equation 6 14 gives: 12 6 2 224 15642LJ rdV k drrrr (6 15) An additional condition is necessary as finite element method requires that all diagonal terms of a stiffness matrix be positive. The co ndition requires an if statement to determine if the second derivative of the Leonard Jones potential is negative, and if so, sets the value of kr of the element stiffness mat rix to a small value denoted as -15 changes to:

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64 12 6 22 22 2 2 24 15642, 0 0LJ LJ r LJdV dV k if drrrrdr dV if dr (6 16) Looking at a typi cal element shown in Figure 6 1 rewriting the force equation in terms of nodal displacements in the local coordinate system gives : 1 1 1 1 3 3 3 31010 0000 1010 0000x y r x yf u f v k f u f v (6 17) Converting to the global coordinate system in F igure 6 1 22 1 1 22 1 1 22 3 3 22 3 3 x y r x yf u llmllm f v lmmlmm k f u llmllm f v lmmlmm (6 18) Finally, the LJ element stiffness matrix is defined in Equation 6 19 using the kr value from Equation 6 16. 22 22 22 22 LJrllmllm lmmlmm kk llmllm lmmlmm (6 19) Force Calcula tions Covalent Length Element (CL) The element force for each CL element can be determined using Equation 6 -20. CLroFkrr (6 20) Converting to nodal force gives:

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65 1 1 2 2 x y CL x yf l f m F f l f m (6 21) Covalent Angular Element (CA) When not in equilibrium, CA elements create a moment on each of the two connecting members defined by: oMk (6 22) Where and o are defined as: 21 (6 23) 2oo o oooif if (6 24) Equation 6 24 is necess ary because of the definition of With being defined as it is in Equation 6 23, allowing for angles greater than 180, the definition of o was changed for simplicity, giving the same results as changing The resultant force of each of moment can b e decomposed into two couples at either end of the connecting member at the local nodes. The forces in global coordinates are defined generically in Equation 6 25 and the element forces are given in Equation 6 -26. ok M f LL (6 25)

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66 1 1 1 1 1 1 13 2 2 13 3 2 3 2 2 2 o o x y xx x y yy x o y omk r lk f r f ff f f ff f mk f r lk r (6 26) Leonard Jones Element (LJ) The element force for each LJ element can be determined using Equation 6 -27. 12 64 126LJF rrr (6 27) Converting to nodal force gives: 1 1 2 2 x y CL x yf l f m F f l f m (6 28) Creation of a Po lymer Field Using a Random Walk Process With the element stiffness matrices and forcing functions defined, the next step in the process is to create a polymer field using a random walk process. This procedure creates a defined number of chains of a defined length in a step wise manner. Initially a random starting point for the first chain is chosen, then the chain is built up by randomly assigning the next point on the chain using two stipulations; the following point should be randomly chosen to have a radial spacing of 1 20% of the radial equilibrium distance, and at a random angle. Each chain is built in a stepwise fashion until the assigned chain length is reached. The process is then

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67 repeated until the assigned number of chains has been reached. It is important that the chains do not overlap within chains and from chain to chain. An example of a polymer field created using this random walk process is shown in Figure 62; the constants used to create the field are given in Table 6 1 Assembly of the Global Stiffness Matrix The global stiffness matrix for a polymer filed using AFEM is assembled by including each of the element stiffness matrices for each element of all three element types. The number of CA and CL element is set by the number of ch ains and the length of each chain. The number of LJ elements is variable and is set by the cutoff distance of the Leonard Jones potential. Interaction between two non -covalently bonded chains can act over an infinite distance therefore it is prudent to d etermine a cutoff distance at which the potential effect is negligible. For the polymer field example this distance is chosen to be 1.866 and the radius is shown in Figure 6 2 It is important to note that the stiffness matrix must be recalculated after any significant deformation as the stiffness of each individual LJ element changes, the recalculation of CA and CL elements is not necessary and can be eliminated to reduce computational costs. Polymer Field Relaxation In order to create a more accurate depiction of a polymer field, once the polymer field has been created and the global stiffness matrix assembled, the polymer field must be relaxed. The relaxation process in done in a stepwise procedure in which the global stiffness matrix is assembled and the nodal forces present on each of the nodes are calculated. The present nodal forces are reversed and applied as part of the boundary condition of the model and nodal displacements are calculated. The nodal positions are moved according to the calcul ated displacements and the process repeats itself. The global stiffness matrix is re -calculated and the nodal forces present on each of the nodes are calculated and reversed and reapplied until the

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68 force on every node is below and arbitrarily chosen value Figure 6 4 shows many of the intermediate steps during the relaxation of the previously used example polymer field. At this point the field is relaxed and further simulation of material behavior is available. Figure 6 5 shows possible simulations avail able for simulation with the AFEM model.

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69 Figure 6 1. Examples of element types A) Covalent length elements B) Covalent angular elements C) Leonard Jones elements Figure 6 2. Example of a polymer field created using the random walk process. The circle denotes the cutoff radius of the LJ elements for the highlighted node

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70 Figure 6 3. Example of multiple polymer chain elements and the layout of each element type

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71 Figure 6 4 Example of polymer relaxation process

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72 Figure 6 5. Proposed AFEM simulations for future work Table 6 1. List of constants used for AFEM polymer analysis. The constants were obtained from Wang et. al. [33] Constant Value Units k r 2.78 aJ/ 2 /bond k 0.498 aJ/rad/bond 0.585 x 10 3 aJ/bond 3.53 R o_ CL 1.47 o_CA 1.88 rad r o_LJ 4.589

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73 CHAPTER 7 SUMMARY AND CONCLUSI ON The motivation for this work came from a tribological study in which the presence of ZnO nanoparticles in a composite of P TFE nanoparticles and SC 15 epoxy lowered the wear rate and friction coefficient over that of a system consisting of PTFE and epoxy alone. The wear rate of the three phase system was optimized using systematic stepwise process and confirmed using multiple samples. At this point it was clear that the ZnO nanoparticles provided some measure of added toughness to the composite and it was necessary to complete additional analysis to determine the mechanisms in which the nanoparticles interacted with the matri x to cause such an increase. The formation of nanoparticle reinforced epoxy was developed that is compatible with many of the composite manufacturing techniques used today, specifically vacuum assisted resin transfer molding (VARTM). The samples were crea ted using an orbital mixing device and a dispersion study was conducted to analyze the validity of the mixing method as well and determine a baseline against which future comparisons could be made. Particle dispersion was imaged using a focused ion beam e lectron microscope and the dispersion was quantified by comparison to the Poisson distribution for discrete events. While an exact match to the Poisson distribution was not achieved, the samples showed good repeatability of the dispersion state within the sample and from sample -to -sample. ASTM standard E1820 was used to measure the fracture toughness of both filled and unfilled systems. The fracture toughness of the samples increased by 20% per volume percent of filler added for varying particle size usin g low filler percentages. Smaller particles reduce the scatter in the fracture toughness resulting in a consistent increase in fracture toughness even at higher volume percentages. The increase in fracture toughness can be attributed to an increase in

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74 max imum load the material can sustain prior to failure, as well as a process zone near the crack tip that displays a more complex region of fracture than that of the neat resin. Multi -scale experimentation was done using an MTS load frame and a focused ion be am electron microscope and three hypotheses of the toughening mechanisms of particle addition were examined. The increase in crack area was not a dominant factor in the increase in fracture toughness of the material based on the load displacement graphs and a Monte Carlo type simulation. Finite Element Analysis determined that the stress intensity factor in the region very close to the crack tip can be reduced by the addition of particles in load cases corresponding to linear elastic loading. Microcracking appears, under the loading conditions defined, and the cracks are pinned in the material, by the nanoparticles, restricting the propagation of an unstable crack. Further analysis is needed to accurately quantify the effects of both crack shielding and mi crocracking within the composite and the analysis should include nonlinear behavior in the crack tip region. In conclusion, the results show that relatively cheap, hard, metal oxide nanoparticles can increase the fracture toughness of an epoxy system by u p to 80%. These results are useful for many applications in which the fracture toughness of the matrix material is the dominant failure mode. Real world applications include composite hydrogen storage tanks and vehicle armor protection systems, were the use of composite materials may be able to drastically reduce the weight of the current state of the art in the field.

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75 APPENDIX ADDITIONAL MODELING IMAGES Figure A 1. Deformed shape and stress field of sample with neat epoxy sample. Figure A 2. Defo rmed shape and stress field of sample with 25 m diameter particle placed 10 m from the crack tip.

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76 Figure A 3. Deformed shape and stress field of sample with 25 m diameter particle placed 12.5 m from the crack tip. Figure A 4. Deformed shape and stress field of sample with 25 m diameter particle placed 25 m from the crack tip.

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77 Figure A 5. Deformed shape and stress field of sample with 25 m diameter particle placed 50 m from the crack tip. Figure A 6. Deformed shape and stress field o f sample with 50 m diameter particle placed 10 m from the crack tip.

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78 Figure A 7. Deformed shape and stress field of sample with 50 m diameter particle placed 12.5 m from the crack tip. Figure A 8. Deformed shape and stress field of sample with 50 m diameter particle placed 25 m from the crack tip.

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79 Figure A 9. Deformed shape and stress field of sample with 50 m diameter particle placed 50 m from the crack tip. Figure A 10. Deformed shape and stress field of sample with 75 m diameter particle placed 10 m from the crack tip.

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80 Figure A 11. Deformed shape and stress field of sample with 75 m diameter particle placed 12.5 m from the crack tip. Figure A 12. Deformed shape and stress field of sample with 75 m diameter particle pl aced 25 m from the crack tip.

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81 Figure A 13. Deformed shape and stress field of sample with 75 m diameter particle placed 50 m from the crack tip.

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82 LIST OF REFERENCES [1] Iijima S. Helical microtubules of graphitic carbon. Natur e. 1991;354(6348):5658. [2] Monthioux M, Kuznetsov VL. Who should be given the credit for the discovery of carbon nanotubes? Carbon. 2006;44(9):16211623. [3] Thostenson ET, Chou T -W. Processing -structure -multi -functional property relationship in carbon nanotube/epoxy composites. Carbon. 2006;44(14):30223029. [4] Thostenson ET, Li C, Chou T -W. Nanocomposites in context. Composites Science and Technology. 2005;65(34):491516. [5] Tjong SC. Structural and mechanical properties of polymer nanocomposites Materials Science and Engineering: R: Reports. 2006;53(34):73197. [6] Burroughs B, Kim J, Blanchet T. Boric acid self -lubrication of B2O3 -filled polymer composites. Tribology Transactions. 1999;42(3):592600. [7] Zhang Z, Breidt C, Chang L, Haupert F Friedrich K. Enhancement of the wear resistance of epoxy: short carbon fibre, graphite, PTFE and nano TiO2. Composites Part A: Applied Science and Manufacturing. 2004;35(12):13851392. [8] Chang L, Zhang Z, Breidt C, Friedrich K. Tribological properties of epoxy nanocomposites I. Enhancement of the wear resistance by nano TiO2 particles. Wear. 2005;258(14):141148. [9] Xing X, Li R. Wear behavior of epoxy matrix composites filled with uniform sized sub micron spherical silica particles. Wear. 2004;256(1 2):2126. [10] Shi G, Zhang M, Rong M, Wetzel B, Friedrich K. Sliding wear behavior of epoxy containing nano -Al2O3 particles with different pretreatments. Wear. 2004;256(1112):10721081. [11] Wetzel B, Haupert F, Qiu Zhang M. Epoxy nanocomposites wi th high mechanical and tribological performance. Composites Science and Technology. 2003;63(14):20552067. [12] Shi G, Zhang M, Rong M, Wetzel B, Friedrich K. Friction and wear of low nanometer Si3N4 filled epoxy composites. Wear. 2003;254(78):784796. [13] Liao Y -H, Marietta Tondin O, Liang Z, Zhang C, Wang B. Investigation of the dispersion process of SWNTs/SC 15 epoxy resin nanocomposites. Materials Science and Engineering A. 2004;385(12):175181. [14] Nelder JA, Mead R. A Simplex Method for Functio n Minimization. The Computer Journal. 1965;7(4):308313.

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83 [15] Schmitz T, Action J, Burris D, Ziegert J, Sawyer W. Wear -rate uncertainty analysis. Journal of Tribology Transactions of the ASME. 2004;126(4):802808. [16] Schmitz T, Action J, Ziegert J, Saw yer W. The difficulty of measuring low friction: Uncertainty analysis for friction coefficient measurements. Journal of TribologyTransactions of the ASME. 2005;127(3):673678. [17] Burris D, Sawyer W. Tribological sensitivity of PTFE/alumina nanocomposites to a range of traditional surface finishes. Tribology Transactions. 2005;48(2):147153. [18] Dennis HR, Hunter DL, Chang D, Kim S, White JL, Cho JW, Paul DR. Effect of melt processing conditions on the extent of exfoliation in organoclaybased nanocomp osites. Polymer. 2001;42(23):95139522. [19] Eckel DF, Balogh MP, Fasulo PD, Rodgers WR. Assessing organo-clay dispersion in polymer nanocomposites. Journal of Applied Polymer Science. 2004;93(3):11101117. [20] Fornes TD, Yoon PJ, Keskkula H, Pau DR. Ny lon 6 nanocomposites: the effect of matrix molecular weight. Polymer. 2001;42(25):0992909940. [21] Yasmin A, Luo J J, Daniel IM. Processing of expanded graphite reinforced polymer nanocomposites. Composites Science and Technology. 2006;66(9):11821189. [22] Gojny FH, Wichmann MHG, Fiedler B, Schulte K. Influence of different carbon nanotubes on the mechanical properties of epoxy matrix composites A comparative study. Composites Science and Technology. 2005;65(1516):23002313. [23] Li G J, Huang X-X, Guo J -K. Fabrication, microstructure and mechanical properties of Al2O3/Ni nanocomposites by a chemical method. Materials Research Bulletin. 2003;38(1112):15911600. [24] Liu W, Hoa SV, Pugh M. Fracture toughness and water uptake of high -performance epox y/nanoclay nanocomposites. Composites Science and Technology. 2005;65(1516):23642373. [25] McCook NL, Boesl B, Burris DL, Sawyer WG. Epoxy, ZnO, and PTFE nanocomposite: friction and wear optimization. Tribology Letters. 2006;22(3):253257. [26] Qi B, Zhang QX, Bannister M, Mai YW. Investigation of the mechanical properties of DGEBA-based epoxy resin with nanoclay additives. Composite Structures. 2006;75(14):514519. [27] Ragosta G, Abbate M, Musto P, Scarinzi G, Mascia L. Epoxy -silica part iculate nanocomposites: Chemical interactions, reinforcement and fracture toughness. Polymer. 2005;46(23):1050610516.

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84 [28] Burris DL, Boesl BP, Bourne GR, Sawyer WG. Polymeric Nanocomposites for Tribological Applications. Macromolecular Materials and Eng ineering. 2007;292(4):387402. [29] ASTM E1820, "Standard Test Method for Measurement of Fracture Toughness". ASTM International. [30] Anderson TL. Fracture Mechanics Fundamentals and Applications. Boca Raton: CRC Press, 1995. [31] ABAQUS. Theory Manual and User Manual, version 6.5.1,. Pawtucket, RI, USA: Hibbit, Karlsson and Sorensen Inc.; 2006. [32] Lourie O, Wagner HD. Transmission electron microscopy observations of fracture of single wall carbon nanotubes under axial tension. Applied Physics Letter s. 1998;73(24):35273529. [33] Wang Y, Sun C, Sun X, Hinkley J, Odegard GM, Gates TS. 2 D nano -scale finite element analysis of a polymer field. Composites Science and Technology. 2003;63(11):15811590. [34] Theodorou DN, Suter UW. Atomistic modeling of mechanical properties of polymeric glasses. Macromolecules. 1986;19(1):139154.

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85 BIOGRAPHICAL SKETCH Benjamin was born in Libertyville, IL, a suburb of Chicago in 1982. He moved shortly thereafter to South Florida, where he remained until moving to Ga inesville, FL in 2000 to attend the University of Florida. Ben received his bachelor's degree in aerospace engineering in December 2004. He decided to remain at the University of Florida where he received his doctorate degree in a erospace e ngineering in 2009 on his work with composite materials at the Center for Advanced Composites and UFs Tribology Laboratory. His research focuses on mechanical and tribological properties, mainly fracture toughness, of nanoparticle reinforced composites.