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Polymer silicate and magnetic polymer nanocomposites: processing and characterization

University of Florida Institutional Repository

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POLYMER SILICATE AND MAGNETIC POLYMER NANOCOMPOSITES: PROCESSING AND CHARACTERIZATION By AJIT BHASKAR A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2003

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Copyright 2003 by Ajit Bhaskar

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This document is dedicated to Professor Beatty, my parents and my sister.

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ACKNOWLEDGMENTS First of all, I would like to express my heartfelt gratitude to Professor Beatty, my committee chair and mentor. He not only taught me the fundamentals of polymers, but also provided me financial support, and showed me the meaning of the word research. I would like to thank my committee members Professor Abbas A Zaman and Professor Hassan El-Shall for their invaluable guidance and support. I would also like to thank Professor Beattys graduate students Nathan Tortorella, Woo-Hyuk Jung and Xiaosang Huang, not only for helping me with my research but also for making research a pleasant and memorable experience. I am also very thankful to my parents and younger sister who have encouraged me for all these years. Finally I would like to thank all the funding agencies. iv

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TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iv LIST OF TABLES...........................................................................................................viii LIST OF FIGURES.............................................................................................................x ABSTRACT.......................................................................................................................xv CHAPTER 1 INTRODUCTION........................................................................................................1 1.1 Polymer Nanocomposites.......................................................................................2 1.1.1 Effect of Compatibilizer Concentration on the Mechanical Properties of Polypropylene-Montmorillonite Nanocomposites........................................2 1.1.2 Improving Impact Properties of Polypropylene/Clay Nanocomposites.......4 1.1.3 PMMA/Laponite Nanocomposites...............................................................5 1.1.4 Polycarbonate-Ferrite Nanocomposites........................................................5 1.1.5 Future Research............................................................................................6 1.2 A Word on Processing and Characterization of Nanocomposites..........................6 2 EFFECT OF COMPATIBILIZER CONCENTRATION ON MECHANICAL PROPERTIES OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES..................................................................................................8 2.1 Introduction.............................................................................................................8 2.2 Polypropylene Clay Nanocomposites...................................................................11 2.3 Research Objectives and Strategy........................................................................13 2.4 Materials...............................................................................................................13 2.5 Processing.............................................................................................................15 2.6 Characterization....................................................................................................18 2.6.1 Specimen Preparation.................................................................................19 2.6.2 Tensile Testing...........................................................................................23 2.6.3 X-Ray Diffraction.......................................................................................29 2.6.4 Differential Scanning Calorimetry (DSC)..................................................35 2.6.5 Transmission Electron Microscopy (TEM)................................................45 2.7 Discussion of Results............................................................................................50 2.7.1 Tensile Testing...........................................................................................50 v

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2.7.2 X-Ray Diffraction.......................................................................................52 2.7.3 DSC............................................................................................................53 2.7.4 TEM............................................................................................................55 2.8 Conclusions...........................................................................................................56 3 IMPACT MODIFICATION OF POLYPROPYLENE/MONTMORILONITE CLAY NANOCOMPOSITES....................................................................................57 3.1 Introduction...........................................................................................................57 3.2 Research Strategies...............................................................................................62 3.3 Materials...............................................................................................................63 3.4 Processing.............................................................................................................67 3.5 Characterization....................................................................................................70 3.5.1 Specimen Preparation.................................................................................71 3.5.2 Tensile Testing...........................................................................................73 3.5.3 X-Ray Diffraction.......................................................................................75 3.5.4 Izod Impact Testing....................................................................................77 3.5.5 Differential Scanning Calorimetry.............................................................79 3.5.6 Transmission Electron Microscopy............................................................79 3.6 Discussion of Results............................................................................................85 3.6.1 Tensile Testing...........................................................................................85 3.6.2 X-Ray Diffraction.......................................................................................86 3.6.3 Differential Scanning Calorimetry.............................................................87 3.6.4 Izod Impact Testing....................................................................................89 3.6.5 TEM............................................................................................................90 3.7 Conclusions...........................................................................................................90 4 PMMA / LAPONITE NANOCOMPOSITES............................................................91 4.1 Introduction...........................................................................................................91 4.2 Research Objectives and Strategy........................................................................91 4.3 Materials...............................................................................................................92 4.4 Processing.............................................................................................................95 4.5 Characterization....................................................................................................97 4.5.1 Sample preparation.....................................................................................98 4.5.2 Tensile Testing...........................................................................................99 4.5.3 X-Ray Diffraction.....................................................................................100 4.5.4 Differential Scanning Calorimetry (DSC)................................................103 4.5.5 Transmission Electron Microscopy (TEM)..............................................103 4.5.6 Nanoindentation.......................................................................................109 4.6 Discussion of Results..........................................................................................115 4.6.1 Tensile Testing.........................................................................................115 4.6.2 X-Ray Diffraction.....................................................................................115 4.6.3 DSC..........................................................................................................116 4.6.4 TEM..........................................................................................................117 4.6.5 Nanoindentation.......................................................................................118 4.7 Conclusions.........................................................................................................121 vi

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5 POLYCARBONATE-FERITE MAGNETIC NANOCOMPOSITES.....................122 5.1 Introduction.........................................................................................................122 5.2 Research Objectives and Strategy......................................................................122 5.3 Materials.............................................................................................................123 5.4 Processing of nanocomposites............................................................................126 5.5 Characterization..................................................................................................129 5.5.1 Specimen preparation...............................................................................130 5.5.2 Tensile Testing.........................................................................................132 5.5.3 X-Ray Diffraction.....................................................................................133 5.5.4 Differential Scanning Calorimetry (DSC)................................................134 5.5.5 Transmission Electron Microscopy (TEM)..............................................136 5.6 Discussion of Results..........................................................................................137 5.6.1 Tensile Testing.........................................................................................137 5.6.2 XRD..........................................................................................................139 5.6.3 DSC..........................................................................................................139 5.6.4 TEM..........................................................................................................144 5.6.5 SQUID Magnetometer..............................................................................145 5.7 Conclusions.........................................................................................................146 6 FUTURE RESEARCH.............................................................................................147 6.1 Introduction.........................................................................................................147 6.2 Polypropylene/Clay Nanocomposites.................................................................147 6.3 Impact Modification of Nanocomposites...........................................................148 6.4 Polymer/Nanoclay Modified Cement.................................................................148 6.5 Impact Modified Glass Fibers............................................................................149 6.6 Recycling of Ground Fiberglass.........................................................................149 6.7 Characterization of Nanocomposites..................................................................150 6.8 Conclusions.........................................................................................................151 APPENDIX A REPRESENTATIVE DATA FROM WINTEST SOFTWARE............................152 B REPRESENTATIVE DATA FROM DSC SOFTWARE........................................155 C REPRESENTATIVE DATA FROM XRD SOFTWARE.......................................160 LIST OF REFERENCES.................................................................................................179 BIOGRAPHICAL SKETCH...........................................................................................193 vii

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LIST OF TABLES Table page 2.1. Properties of Polypropylene used for the research.....................................................14 2.2. Physical properties of Nanomer I.34 TCN...............................................................14 2.3. Properties of Epolene G-3003...................................................................................15 2.4. Different temperature Zones of the twin screw extruder............................................17 2.5. Designation of different PPCNs..................................................................................18 2.6. Tensile moduli and tensile strengths of PP and PPCNs. Strain rate = 0.01 mm/sec., temperature of testing = 29oC..................................................................30 3.1. Properties of Basell Polypropylene used for the research..........................................65 3.2. Properties of Epolene G-3003...................................................................................65 3.3. Physical properties of Nanomer I.34 TCN...............................................................65 3.4. Properties of Engage 8842........................................................................................66 3.5. Properties of oligomeric, epoxy and hydroxyl end functionalized polybutadiene.....66 3.6. Properties of Glycidyl methacrylate...........................................................................67 3.7. Preparation of Impact modified nanocomposites.......................................................70 3.8. Percent compositions of different nanocomposites by weight (dry basis).................71 3.9. Tensile properties of impact modified PPCNs............................................................75 3.10. Impact strengths of impact modified PP/clay nanocomposites................................78 4.1. Chemical composition of Laponites...........................................................................94 4.2. Physical properties of Laponites.................................................................................95 4.3. Properties of PMMA...................................................................................................96 viii

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4.4. Nanoindentation results showing force and peak displacements for each specimen tested. Force was applied at 100nN/sec.................................................114 5.1. Properties of Lexan...................................................................................................124 5.2. Temperature settings in temperature zones of the twin-screw extruder...................129 5.3. Tensile modulus of PC and PC/Ferrite nanocomposite............................................132 ix

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LIST OF FIGURES Figure page 1.1. Classification of research areas on the basis of filler employed...................................1 1.2. Structure of montmorillonite clay.................................................................................3 1.3. Different types of clay platelet dispersion by diffusion of polymer chains..................3 2.1. Schematic illustrations...............................................................................................10 2.2. A model for the torturous zigzag diffusion path in an exfoliated polymer clay nanocomposite when used as a gas barrier...............................................................11 2.3. Orientations of alkyl ammonium ions in the galleries of layered silicates with different layer charge densities................................................................................12 2.4. A Maleic anhydride group..........................................................................................15 2.5. Schematic of reactive twin-screw extruder.................................................................16 2.6. Block diagram of the extruder showing different zones.............................................17 2.7. Schematic diagram of Carver compression molding press.........................................20 2.8. Placement of mold between two metal plates covered with Teflon coated aluminum foil...........................................................................................................21 2.9. The EnduraTEC ELF 3200 series machine................................................................25 2.10. Specimen testing chamber........................................................................................26 2.11. Temperature control box and emergency stop buttons.............................................27 2.12. Control unit. This acts as an interface between the computer and software.............27 2.13. Stress versus strain plots for different PPCNs. Strain rate = 0.01 mm/sec., temperature of testing = 29 oC..................................................................................31 2.14. Dependence of tensile modulus on compatibilizer concentration. Strain rate = 0.01 mm/sec., temperature of testing = 29 oC....................................32 x

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2.15. Dependence of tensile strength on compatibilizer concentration. Strain rate = 0.01 mm/sec., temperature of testing = 29 oC....................................33 2.16. Fundamentals of X-ray Diffraction. Here, l= path difference, d= interplanar spacing and = semi-angle of diffraction................................................................34 2.17. Complete XRD patterns for PP and PPCNs in reflective mode, at 15 oC................36 2.18. Lower angle region of XRD patterns for PP and PPCNs in reflective mode, at 15 oC.........................................................................................................................37 2.19. Glass transition on a DSC thermogram....................................................................39 2.20. Crystallization transition on a DSC thermogram......................................................39 2.21. Melting transition on a DSC thermogram.................................................................40 2.22. DSC heating thermograms for PP and PPCNs. Heating rate = 10 oC/minute..........41 2.23. Tg region of DSC heating thermograms for PP and PPCNs. Heating rate = 10 oC/minute..................................................................................................................42 2.24. Tm transition for PP and PPCNs obtained from DSC heating thermogram. Heating rate = 10 o C/minute....................................................................................43 2.25. DSC cooling thermograms for PP and PPCNs. Cooling rate = 50 oC/minute..........44 2.26. Void formation between the folded silicate layers during the microtoming of the bulk nanocomposite..................................................................................................46 2.27. TEM micrographs of PP/CLAY (95:5).....................................................................47 2.28. TEM micrographs of PP/EP/CLAY (85.5:9.5:5)......................................................48 2.29. TEM micrographs of PP/EP/CLAY (85.5:9.5:5)......................................................49 3.1. Notched Izod impact strength of nylon 6 and 95/05 composites as a function of clay loading..............................................................................................................58 3.2. SEM observation: (a) Cavitated nanocomposite; (b) Fibrillated nanocomposite and polymer/clay interaction....................................................................................60 3.3. Notched Izod impact strength of nylon 6 and 95/05 composites as a function of temperature...............................................................................................................61 3.4. Effect of addition of elastomer on craze crack structure............................................62 3.5. Stress strain curves for different types of materials....................................................64 xi

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3.6. Schematic representation showing mixing of Epolene with oligomeric polybutadiene...........................................................................................................69 3.7. Synthesis of impact modified nanocomposites using a reactive twin-screw extruder.....................................................................................................................71 3.8. Tensile behavior of PP and impact modified PP/Clay nanocomposites at 0.01 mm/sec., 28 oC.........................................................................................................74 3.9. XRD patterns for PP and impact modified PP clay nanocomposites in reflective mode, at 15 oC..........................................................................................................76 3.10. Low angle region of XRD plot................................................................................77 3.11. Izod impact testing apparatus...................................................................................78 3.12. DSC heating thermogram for PP and impact modified PP/clay nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min...............................................80 3.13.Tg region of DSC heating thermograms....................................................................81 3.14. Tm region of DSC heating thermograms..................................................................82 3.15. DSC cooling thermogram for PP and impact modified PP/clay nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min...............................................83 3.16. TEM micrograph of PP/COMP/F-OLIG/CLAY......................................................84 3.17. TEM micrographs of PP/COMP/F-POE/CLAY.......................................................84 3.18. TEM micrographs of PP/COMP/F-POE/CLAY at a higher magnification..............85 3.19. Schematic showing that oligomeric elastomers may be more effective in aiding chain intercalation than polymeric elastomers.........................................................88 4.1. Structural formula of atactic PMMA..........................................................................91 4.2. Layered structure of Laponite.....................................................................................93 4.3. Idealized, average shape of laponite particles when dispersed in water.....................93 4.4. Synthesis of PMMA/Laponite JS nanocomposites using a reactive twin-screw extruder.....................................................................................................................97 4.5. Tensile testing results for PMMA and PMMA + 2 wt % Laponite JS at 0.05 mm/sec, 28 oC. All samples tested showed failure................................................101 xii

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4.6. Dependence of tensile modulus on clay loading. Modulus values were obtained from linear region of the curves in 4.5. Strain rate = 0.05 mm/sec, temperature = 28 oC................................................................................................102 4.7. XRD patterns (reflective mode) for PMMA and PMMA/Laponite nanocomposites. Reflective mode, temperature = 15 oC.......................................104 4.8. DSC thermograms for PMMA and PMMA/Laponite JS nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min.............................................105 4.9. TEM micrograph of PMMA/2 wt % Laponite JS at 60 kX......................................106 4.10. TEM micrograph of PMMA/2 wt % Laponite JS at 100 kX..................................106 4.11. TEM micrograph of PMMA/2 wt % Laponite JS at 200 kX..................................107 4.12. TEM micrograph of PMMA/5 wt % Laponite JS at 50 kX....................................107 4.13. TEM micrograph of PMMA/5 wt % Laponite JS at 100 kX..................................108 4.14. TEM micrograph of PMMA/5 wt % Laponite JS at 150 kX..................................108 4.15. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 250 N. Force was applied at 100 nN/sec..........................................................110 4.16. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 500 N. Force was applied at 100 nN/sec..........................................................111 4.17. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 1000 N. Force was applied at 100 nN/sec........................................................112 4.18. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 5000 N. Force was applied at 100 nN/sec........................................................113 4.19. Interpretation of nanoindentation data....................................................................119 4.20. Load versus maximum distance penetrated by the tip. The curves show that the nanocomposite containing 5-wt % clay is the hardest material. Force was applied at 100 nN/sec.............................................................................................120 5.1. Structure of Polycarbonate........................................................................................122 5.2. Results of particle size distribution of as-synthesized by particle size analyzer (UPA). It is measured after high power (650 W) ultrasonication for 10 min........127 5.3. XRD patterns of NiZnFe2O4 after drying at 60 oC for 3 hours in oven. Lattice parameter, a = 8.368 ...........................................................................................127 5.4. SEM image of Ni-Zn Ferrite after3 drying at 60 oC for 3 hours in oven..................128 xiii

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5.5. Proposed role of PVA in the formation of PC/ferrite nanocomposites....................128 5.6. Block diagram for the processing of PC/Ferrite nanocomposites............................130 5.7. Tensile test comparisons at 0.05 mm/sec., 30 oC......................................................133 5.8. XRD patterns for PC and PC/Ferrite nanocomposite using reflective mode at 15 oC.........................................................................................................134 5.9. DSC thermograms for PC and PC/PVA/ferrite nanocomposite. Heating rate =10 oC/min., cooling rate = 50 oC/min..........................................................................135 5.10. TEM images of PC/PVA/Ferrite nanocomposite...................................................136 5.11. Stress strain comparisons for PC/Ferrites with and without PVA, at 0.05 mm/sec., 30 oC. All samples tested showed failure...............................................138 5.12 High angle XRD region for various nanocomposites using reflective mode at 15 oC.......................................................................................................................140 5.13. Lower angle region for various nanocomposites using reflective mode at 15 oC.......................................................................................................................141 5.14. DSC Thermograms for PC and various nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min.....................................................................143 5.15. Dark Field TEM micrographs of PC/Ferrites, without PVA..................................144 5.16. Dark Field TEM micrographs of PC/Ferrites, without PVA at a lower magnification..........................................................................................................145 xiv

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Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science POLYMER-SILICATE AND MAGNETIC POLYMER NANOCOMPOSITES: PROCESSING AND CHARACTERIZATION By Ajit Bhaskar August 2003 Chair: Charles L Beatty Major Department: Materials Science and Engineering The research can be categorized with respect to the fillers used, namely clay and ferrite magnetic nanoparticles. Polymer layered silicate nanocomposites (PLSNs) are nanocomposites of polymers and clays. One of the investigations carried out was regarding the amount of compatibilizer necessary to get the optimum adhesion between the hydrophobic polymer and the hydrophilic clay. The matrix used was polypropylene (PP) and the clay used was an organically modified montmorillonite. It was found that beyond a certain concentration of the compatibilizer, the mechanical properties deteriorated. This was explained on the basis of the ways in which the compatibilizer, a maleic anhydride grafted polypropylene, influenced the nanocomposites. In another work, the impact properties of the nanocomposites processed above were attempted to be improved using different elastomeric species and using different processing protocols. It was observed that a low molecular weight oligomeric elastomer xv

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produced the best results. It was also found that the sequence of addition of elastomer affected the mechanical and impact properties. Nanocomposites of PMMA and Laponite were prepared for enhanced abrasion and wear resistance, for window-based applications. However, the major challenge was to preserve the optical clarity of PMMA, a key emotive property that makes it a commodity plastic. A recent technique called nano-indentation was employed for assessing the hardness of these materials. Nanocomposites of polymers using magnetic nanoparticles offer an interesting research avenue. Nanocomposites using Polycarbonate (PC) and Ni-Zn based ferrite nanoparticles were prepared. They were found to be clear with a brown tinge, and were characterized for different properties. It was found that the melt viscosities of these nanocomposites were significantly lower than the pure polymer. This was explained on the basis of the different phases added to PC. Most of the processing for the research was carried out using a reactive twin-screw extruder, which simulates continuous, mass-production operations to a considerable extent. An insight into the microstructure was obtained using various techniques such as differential scanning calorimetry, X-Ray diffraction, transmission electron microscopy, and nanoindentation. Mechanical properties were evaluated using tensile tests and Izod impact testing. The results obtained from these analytical tools were interpreted and a coherent explanation of different phenomena occurring on a macroscopic as well as microscopic level was attempted. xvi

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CHAPTER 1 INTRODUCTION My research focuses on polymer nanocomposites. Nanocomposites of polymers with different fillers were processed and characterized. The entire research can be classified based on the nature of filler employed, namely clay and ferrite nanoparticles. Figure 1.1 shows a schematic describing the same. Figure 1.1. Classification of research areas on the basis of filler employed. 1

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2 Two different clays were used, montmorillonite and laponite. Chapters 2 and 3 describe research on polypropylene/montmorillonite nanocomposites. Chapter 4 deals with Poly (methyl methacrylate)/laponite nanocomposites. Finally, Chapter 5 describes Polycarbonate/ferrite nanocomposites. Chapter 6 discusses suggestions for future research. Here, many ideas and concepts from earlier research have been attempted to be applied to different avenues having different applications. The following section gives a summary of each of these chapters. 1.1 Polymer Nanocomposites 1.1.1 Effect of Compatibilizer Concentration on the Mechanical Properties of Polypropylene-Montmorillonite Nanocomposites One of the objectives of this research was to demonstrate that addition of clay to a polymeric matrix not only enhanced the properties of the pristine polymer, but it could also achieve the same with small loadings. This could be attributed to the large surface to mass ratio when compared to traditional fillers used for polymeric composites. However, the major difficulty in preparing these nanocomposites was exfoliation of clay. Exfoliation is one of the terms used to determine the extent of dispersion of clay in the polymer matrix. The clay used for this work was montmorillonite, a smectite clay. The clay structure comprised of tetrahedral layers of silica sandwiching octahedral layers of alumina. On a whole, the structure looked like nearly parallel layers of silica held by alumina pillars. Figure 1.2 shows the structure of montmorillonite clay. When these galleries (i.e, the clay interlayers) are split far apart by the application of high temperature and shear force generated due to the molten polymer and the extruder in which it is processed, this type of dispersion is called exfoliation.

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3 Figure 1.2. Structure of montmorillonite clay. Other type of clay platelet separation possible is intercalation. Figure 1.3 shows the different types of clay platelet separations. Several publications involving polymer clay nanocomposites have been published with polar polymers (such as Nylon 6, Nylon 6,6, Polyurethane) as the matrix material. In this work, a non-polar polymer, namely polypropylene was chosen. Intercalation Exfoliation Figure 1.3. Different types of clay platelet dispersion by diffusion of polymer chains. This is because PP is an inexpensive commercial plastic used for a variety of applications. Besides, it is difficult for the clay to bond to a non-polar polymer, which can be attributed to the hydrophilic nature of the clay and organophilic nature of the matrix.

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4 So, the clay used in this study was organically modified. However, it was found that the use of a compatibilizer between the polymer and the clay yielded better mechanical properties. The compatibilizer used in this work was a maleic anhydride modified polypropylene. It was also found out that when no compatibilizer was added, the mechanical properties were inferior in comparison to the pure polymer. Thus it could be deduced that in spite of the clay being modified to behave in an organophilic manner, the use of a compatibilizer was necessary. To acquire an in depth insight into the effect of the compatibilizer, its concentration in the nanocomposite was varied. It was observed that after a certain percentage of the compatibilizer, the mechanical properties started to degrade. It was concluded that compatibilizers were necessary components for good dispersion of clay, but beyond a certain concentration, they had deleterious effects on the mechanical properties of the nanocomposite. 1.1.2 Improving Impact Properties of Polypropylene/Clay Nanocomposites Several publications show property enhancement in polymers upon the addition of clay, but most of the publications do not address impact properties in detail. Hence, a study was done in order to investigate the impact behavior of polymer clay nanocomposites and schemes for improving their impact properties were proposed. In one scheme, a functionalized elastomer was added before and after processing the polymer clay nanocomposite in two different processing protocols. In another scheme, an oligomeric, end functionalized elastomer was melt blended with the compatibilizer, and the resulting modified compatibilizer was then used for processing the nanocomposite. It was found that the second scheme produced better mechanical properties. Thus, it was speculated that oligomeric elastomer was able to penetrate into the clay galleries

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5 more easily and because of functional groups present; it could also bond well to create a more stable composite with respect to interfacial behavior. In addition, other mechanical properties of the nanocomposite were not sacrificed significantly. The functionalization of the polymeric elastomer used was carried out in a reactive twin-screw extruder, so this work was a combination of nanotechnology and reactive extrusion. The functionalizing agent used was glycidyl methacrylate. 1.1.3 PMMA/Laponite Nanocomposites This research was focused on making wear/abrasion resistant PMMA for superior windows based applications. The clay used here was Laponite JS, a synthetic clay, which already existed as nanoparticles when dispersed in water. These particles were disc-shaped. Two different loadings of clay were chosen, namely 2-wt % and 5-wt %. The surface hardness was characterized using nanoindentation technique. It was found that the addition of clay significantly reduced the penetration of the probe and hence, these nanocomposites exhibited increased hardness. However, it was also observed that only the 2-wt % nanocomposite exhibited optical clarity close to pure PMMA. The nanocomposite containing 5-wt % clay was translucent. 1.1.4 Polycarbonate-Ferrite Nanocomposites The aim of this research was to obtain magnetic nanocomposite materials. Nano-sized ferrite particles prepared at the Department of Materials Science and Engineering, University of Florida with help from Junyeon Hwang (working for Professor Darryl P. Butt). These particles were prepared using a co-precipitation method, with carefully controlled parameters such as temperature and pH. The synthesized particles were dispersed in a polymer matrix. The matrix material chosen was polycarbonate (PC). This is a transparent polymer, and is completely

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6 amorphous. The ferrites were first coated with a low molecular weight PVA (Poly Vinyl Alcohol). The ferrites are known to bond with alcoholic groups by means of silanol reaction. After coating the ferrites with PVA, these were dispersed in molten polycarbonate. The resulting material was still optically clear, with a brown tinge to it. With respect to mechanical behavior, the nanocomposite was more brittle than the virgin polymer, and exhibited a higher tensile modulus than pure PC. Characterization using a SQUID magnetometer showed that the nanocomposite was magnetic in nature. 1.1.5 Future Research Several concepts applied in the above research may be extended to other avenues as well. Few of these include polymer/clay modified cement. It is suggested that this approach may produce cement with good tensile properties. Another area is that of glass fibers. Recycling of glass fibers is one of the interests. It is possible that by imparting appropriate chemical treatment to the waste, ground fiberglass, they could be used again with resins such as unsaturated polyesters, epoxy, etc. Impact modified glass fibers is another area of interest. It is again possible that by giving the appropriate chemical treatment, glass fibers when introduced into resins yield composites with better impact properties without significant loss in tensile properties. 1.2 A Word on Processing and Characterization of Nanocomposites The equipment used for processing the nanocomposites by melt blending was a 30mm APV reactive twin-screw extruder, with a co-rotating intermeshing configuration of the screws. The length to diameter ratio (also addressed as l/d) was 40. The extruder had eight temperature zones, including feed and die zones. Characterization of nanocomposites prepared was performed using the following techniques:

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7 1. Tensile testing: Helps in comparing the tensile behavior of different materials and their tensile moduli. This test also tells us about the relative stiffness of different materials. 2. X-Ray Diffraction: The shift in diffraction peaks shows the extent of exfoliation or intercalation that has taken place. This also helps in getting an overall picture of intercalation/exfoliation in bulk. 3. Transmission Electron Microscopy (TEM): Is very effective in studying a local region of the nanocomposite for exfoliation. The greater the number of individual platelets that could be counted in a TEM micrograph, greater the extent of intercalation/exfoliation. 4. Nanoindentation: A very novel and useful tool for probing hardness of nanocomposite materials, especially at the surface. Its details are described later in appropriate sections. 5. Izod Impact Testing: It gives the impact strength of a material. Here, a swinging hammer is made to impact a specimen and the energy lost by the hammer upon impact is a measure of the impact strength of the material. 6. Differential Scanning Calorimetry: This technique is used to evaluate the behavior of a material upon heating. Different transitions such as melting, glass transition and crystallization behavior can be studied with this technique.

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CHAPTER 2 EFFECT OF COMPATIBILIZER CONCENTRATION ON MECHANICAL PROPERTIES OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES 2.1 Introduction A nanocomposite is defined as a material in which the dispersing phase has at least one of its dimensions in the order of nano (10-9) meters. Polymer clay nanocomposites are a class of hybrid materials in which clays having a layered silicate structure are dispersed into a polymeric matrix. The spacing between these layers is of the order of few (2-3) nanometers prior to dispersion of polymer. Hence the hybrid is called a polymer clay nanocomposite [1-6]. The use of clays instead of traditional fillers is being encouraged for numerous reasons. First and foremost, due to high surface to mass ratio of clays, the same amount of property enhancement may be achieved with lesser quantity of clay than traditional fillers such as glass fibers. This is because increased surface/mass ratio means greater area available for adhesion. Thus, tremendous savings may be made with respect to weight of the end product. This may also make processing easier. Further, research at Toyota motor company has shown that for nylon-6/montmorillonite clay nanocomposites, at a loading of only 4.2 wt% clay, the modulus doubled, the tensile strength increased by more than 50%, and the heat distortion temperature increased by 80 oC compared to the pure polymer [7-8]. Researchers also demonstrated that organoclays exfoliated in nylon 6 matrix and greatly improved the dimensional stability, the barrier properties and even flame retardance [9-11]. 8

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9 However, the clay nanolayers are not easily dispersed in polymers due to their preferred face-to-face stacking tactoids. Dispersion of tactoids is further hindered by the fact that clays are hydrophilic in nature, and are therefore, incompatible with majority of polymers that are primarily hydrophobic. Hence, these clays are surface-modified (usually with an organic ammonium salt) in order to enhance compatibility between the matrix polymer and the clay. Such clays are termed as organoclays. This concept has been extended into various polymer systems including polyamides [12-17], epoxies [18-29], polyurethanes [30-38], polypropylene [39-62], polyesters [63-66], polystyrene [67-81], polyethylene [82], elastomers [83-87] and polysiloxanes [88] among others. Many liquid crystalline polymers have also been explored [89-92]. For true nanocomposites, the clay nanolayers must be uniformly dispersed (exfoliated) in the polymer matrix, as opposed to being aggregated (intercalated) into clusters of layers [1]. Figure 2.1 shows this. Dispersion and distribution of the filler is achieved when the hydrodynamic separation forces of the polymer melt overcome the agglomerating forces between the clay interlayers [12]. The exfoliation of clay in a polymer optimizes the number of reinforcing elements for carrying the applied load and deflecting cracks. The coupling between tremendous surface area of the clay (~760 m2/g) and the polymer matrix facilitates stress transfer to the reinforcement phase, allowing for such tensile improvements. High aspect ratio nanolayers also provide properties that are not possible for larger-scaled composites. The impermeable clay layers pose a tortuous pathway for a permeant to traverse the nanocomposite. Figure 2.2 demonstrates the same.

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10 Figure 2.1. Schematic illustrations of (A) a conventional; (B) an intercalated; (C) an ordered exfoliated; and (D) a disordered exfoliated polymer clay nanocomposite. The clay interlayer spacing is fixed in an intercalated nanocomposite. On the other hand, in an exfoliated nanocomposite, the average gallery height is determined by clay silicate loading. The difference between ordered and disordered exfoliated nanocomposites is that the former can be detected by X-ray diffraction and the latter is X-ray amorphous. The enhanced barrier characteristics, chemical resistance, reduced solvent uptake and flame retardance of polymer clay nanocomposites all benefit from the hindered diffusion pathways through the nanocomposite. The replacement of inorganic cations by organic onium ions on the gallery surfaces of smectite clays not only serves to match the clay surface polarity with the polarity of the polymer, but it also expands the clay galleries. Depending on the charge density of clay and the onium ion surfactant, different arrangements of the onium ions are possible. In general, longer the surfactant chain length, and the higher the charge density of the clay, further apart the clay layers will be forced.

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11 Figure 2.2. A model for the torturous zigzag diffusion path in an exfoliated polymer clay nanocomposite when used as a gas barrier. This is expected since both of these parameters contribute to increasing the volume occupied by the intragallery surfactant [1, 93]. Depending on the charge density of the clay, the onium ions may lie parallel to the clay surface as a monolayer, a lateral bilayer, a pseudo-trimolecular layer, or an inclined paraffin structure. At very high charge densities, large surfactant ions can adopt lipid bilayer orientations in the clay galleries. Figure 2.3 shows this. Polymer clay nanocomposites are being used in under the hood applications in automotive industry [1, 94]. 2.2 Polypropylene Clay Nanocomposites Polypropylene is a thermoplastic polymer, and is one of the most widely used polymers in the industry. It is inexpensive and is relatively easier to recycle and offers versatility in terms is properties and applications. The introduction of traditional fillers into PP requires special processing technologies involving prepreg preparation and fiber impregnation [39, 95-96]. This is the reason special emphasis is being laid on PP/clay nano-hybrids. These can be synthesized using a relatively easier approach of melt blending.

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12 Figure 2.3. Orientations of alkyl ammonium ions in the galleries of layered silicates with different layer charge densities. Researchers at Toyota and other laboratories [1, 46, 61, 97, 98, 99] have reported that it is possible to prepare PPclay hybrids by simple melt mixing of three components, i.e., PP, maleic anhydride-modified polypropylene oligomers (PP-MA), and clay intercalated with alkyl ammonium ions [51, 61, 97, 100-101]. Some of the common approaches adopted for preparing PP/Clay nanocomposites (PPCNs) are: 1. The clay is first blended with polar oligomeric species. Strong interactions result between the polar groups on the oligomeric species and the oxygen based groups on the clay. Examples of polar oligomers are maleic anhydride grafted PP and certain alcohol based oligomers. This system is then blended with PP for increasing the gallery spacing in the clay. 2. The clay is dispersed in a solvent, followed by the addition of a monomer. Then the monomer is polymerized to prepare a system compatible with PP. This clay-polymer hybrid is then blended with PP. From a processing perspective of nanocomposites, many methods have been reported. These include melt intercalation [12-14, 39-49, 51-58, 70, 80], solution blending [69, 74, 78] and in-situ polymerization [67, 71-73, 75, 77,79, 81].

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13 2.3 Research Objectives and Strategy In this research, the nanocomposites were prepared by combining the two above mentioned approaches. The clay was dispersed in a solvent. The low molecular weight compatibilizer was blended with PP instead of clay. The dispersed clay was then blended with the modified PP blend to give a nanocomposite. An attempt was made for studying the effects of the compatibilizer concentration on mechanical properties of PPCNs. Primary emphasis was laid on tensile properties. This is because the tensile properties are a very important criterion for materials selection for most of the applications. It has been reported in literature that using method #1 listed in the previous section for preparing PPCNs, a compatibilizer to clay ratio of 3:1 worked best. Kato et al. have observed that the density of the compatibilizer, a maleic anhydride modified PP, had a remarkable effect on the final morphology of the nanocomposite [61]. However, in their work, the authors did not make comments about the mechanical and thermal properties of the nanocomposites. Thus, it was shown that the ratio of 3:1 was best from an exfoliation/intercalation point of view. D. Garcia Lopez et al. [59] have also observed a similar ratio. However, it was seen from their work that the increase in tensile strength was not very significant. Hence, an attempt was made to study in depth, the role of the compatibilizer and the effect of its concentration on various mechanical properties of the nanocomposite. 2.4 Materials Montell (now Basell) supplied PP used for this research. The grade was Profax 6523. This was an extrusion grade plastic. Table 2.1 shows some of its properties.

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14 Table2.1. Properties of Polypropylene (Basell Profax 6523) used for the research. PROPERTY VALUE TEST METHOD PHYSICAL Specific Gravity 0.9 ASTM D792 Melt Flow Rate (230 C) 4.00 g/10 min ASTM D1238 MECHANICAL Tensile Strength @ Yield 4900 psi ASTM D638 Tensile Elongation @ Yield 12 % ASTM D638 Flexural Modulus (Procedure A) 1% Secant: 200000 psi ASTM D790 Notched Izod Impact (73 F) 0.7 ft-lb/in ASTM D256 Rockwell Hardness (R-Scale) 86 ASTM D785 THERMAL DTUL @66psi Unannealed 199 oF ASTM D648 Nanocor supplied the clay used for this study. The name of the product was Nanomer I.34TCN. It was specifically designed for extrusion compounding. Table 2.2 enlists some of its properties. However, it is worth mentioning that this clay was not designed for moisture barrier applications [102]. Table 2.2. Physical properties of Nanomer I.34 TCN. PROPERTY VALUE Appearance White Powder Mean Dry Particle Size (Microns) 16-22 + 325 Mesh Residue (%) 0.1 Specific Gravity 2.0 Moisture (%) 3.0 Bulk Density (gms/cc) 0.30-0.36 Purity (%) 98.5 The agent used for dispersing the clay was Xylene, supplied by Fisher Scientific. Eastman Chemical Company supplied the compatibilizer used for the research under the trade name Epolene G-3003. Table 2.3 describes some of its properties.

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15 Table 2.3. Properties of Epolene G-3003. PROPERTY VALUE Ring & Ball Softening Point C 158 Penetration Hardness <1 Density @ 25 C 0.912 Acid Number 8 Viscosity, cP (mPas) @ 190 C 60,000 Melt Index @ 190 C 12.7 Color (Gardner) 25 Molecular Weight 27,200 Epolene is a maleic anhydride grafted PP. It has a much lower molecular weight and consequently a lower softening point than PP. Thus, its chains exhibit greater mobility. Figure 2.4 shows the structure of a maleic anhydride group. Figure 2.4. A Maleic anhydride group. 2.5 Processing The nanocomposites were processed by melt compounding using a 30 mm APV co-rotating twin crew extruder, with 8-zone temperature settings ranging from 200 C (feed zone) to 234 C (die zone). The screw length to diameter ratio (L/D) was 40. Figures 2.5 shows a schematic representation of the extruder. Figure 2.6 shows the processing in the form of a block diagram. The Zenith pump is generally used for introducing the reactive species. However, upon preparing the clay dispersion, it was feared that the same might plug the pump. Hence, it was not used. The clay dispersion was introduced at the feed zone.

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16 Figure 2.5. Schematic of reactive twin-screw extruder. Table 2.4 shows the temperature profile along the different zones of the extruder. PP and Epolene were dried in an air-circulating oven prior to any melt compounding operation. The temperature was 80 oC. Drying was done to ensure removal of moisture. This was particularly important for Epolene, which had polar groups associated with it.

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17 Figure 2.6. Block diagram of the extruder showing different zones. The preparation of the sample containing 90-wt % PP, 5-wt % Epolene and 5-wt % clay is described. Nanocomposites with other compatibilizer concentrations were prepared in a similar fashion. Table 2.4. Different temperature Zones of the twin screw extruder. Zone Temperature ( oC) Zone 1 (Feed Zone) 200 Zone 2 204 Zone 3 208 Zone 4 214 Zone 5 218 Zone 6 223 Zone 7 227 Zone 8 (Die Zone) 234 PP was blended with Epolene in the weight ratio 90:5 in the extruder. The extruded strands were received in a flowing water bath, which formed a part of the extruder. These

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18 strands were pelletized and dried for 24 hrs. in a vacuum oven at 95 oC. These pellets were melt-compounded with the clay. The clay was dispersed in xylene (clay: xylene used was approximately 1:5 by weight). The dispersion was magnetically stirred for 10 minutes prior to addition to pellets at the feed zone of the extruder. The resulting strands were received in a flowing water bath, pelletized and vacuum dried for 24 hours under conditions described above. Table 2.5 summarizes the compositions (by weight, dry basis) of different nanocomposites thus prepared. A sample without any compatibilizer was also prepared in order to demonstrate the effect and necessity of Epolene. Pure PP was also run through the extruder under identical conditions in order to ensure uniform thermal history for all the materials compared for different properties. Table 2.5. Designation of different PPCNs. All compositions are in weight%. SAMPLE DESIGNATION % POLYPROPYLENE % EPOLENE % CLAY PP/Clay (95:5) 95 0 5 PP/EP/Clay (90:5:5) 90 5 5 PP/EP/Clay (85.5:9.5: 5) 85.5 9.5 5 PP/EP/Clay (76:19:5) 76 19 5 PP/EP/Clay (47.5:47.5:5) 47.5 47.5 5 2.6 Characterization Polymer characterization is considered to be a separate discipline of study in the field of polymers. It involves the investigation of the microstructure-property relationships of a polymeric material. Examination of microscopic details of the structure in order to understand the morphology, measurement of mechanical and thermal properties are all part of the characterization process. The following analytical tools were employed for characterizing the PPCNs:

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19 Tensile Testing X-Ray Diffraction Differential Scanning Calorimetry Transmission Electron Microscopy 2.6.1 Specimen Preparation Specimens for all the above mentioned techniques were prepared by compression molding. Compression molding is a process in which a polymer is made to take the shape of a mold by pressing it between two heated plates. The heat melts the polymer (if semi-crystalline) or takes the polymer chains well above the glass transition temperature (if amorphous). The machine used for compression molding was a Carver, model C-81000-141 press. Figure 2.7 shows the details of the press. Figure 2.8 shows the details of the compression molding process, and the placement of the mold containing polymer pellets between two metal plates. In order to prepare the specimens, the press was first heated to 420 oF. The mold used was square in shape, with dimensions of 70 mm X 70 mm X 0.8 mm. The mold was placed on a metal plate covered with Teflon coated aluminum foil. The mold was then filled with dried pellets. This plate with mold and the pellets was placed on the bottom plate of the press. Another Teflon coated aluminum foil covered metal plate was placed on top of the mold bearing plate, to give a sandwiched assembly. The bottom plate of the press was raised until the assembly just touched the top plate of the press. The pellets were then allowed to convert into a liquid state by heat transfer from the press. This took about 5-6 minutes. After that the pressure of the system was raised to 10, 000 psi. Initially, due to resistance offered by the liquid polymer as well relatively incomplete conversion to liquid, the pressure dropped below 10,000 psi. Under these circumstances, it was necessary again to raise the pressure to 10,000 psi.

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20 Figure 2.7. Schematic diagram of Carver compression molding press.

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21 Figure 2.8. Placement of mold between two metal plates covered with Teflon coated aluminum foil.

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22 INDEX: 1. Lever for raising bottom plate 2. Pressure gauge 3. Bottom plate 4. Top plate 5. Temperature dial 6. Temperature controller 7. Pressure release screw 8. Metal plate a covered with Teflon coated aluminum foil 9. Mold 10. Pellets 11. Metal plate b covered with Teflon coated aluminum foil. This was repeated until the pressure attained a steady value of 10,000 psi. The pressure could be measured using a gauge attached to the press. A pressure of 10, 000 psi. on the gauge corresponded to 9302 psi. on the sample. This was calculated using the formula: AgPgAsPs (Equation 2.1) Where, Ps = Pressure on the sample As = Cross sectional area of the sample Pg = Gauge pressure Ag = Cross sectional area of the piston of the press. As = 4900 mm2 Ag = 3.14. (32)/4 Pg = 10, 000 psi. After the gauge pressure became steady at 10, 000 psi., the mold was allowed to rest at the above mentioned temperature and pressure for 10 minutes. After that, the heat supply to the press was turned off. Immediately after this, the pressure-release screw was turned. The hot plate assembly containing the mold between the two metal plates was

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23 removed and was immersed in a cold-water reservoir and kept for 3 minutes. Then, the entire assembly was flipped over and was immersed in the reservoir for 3 more minutes. After the mold cooled down to ambient temperature, the solidified sheet was then taken out of the mold. Sheets were prepared in this way for pure PP, and the various nanocomposites. These sheets served as specimens for all the characterization techniques. 2.6.2 Tensile Testing The aim of tensile testing was to evaluate the mechanical response of the materials to a known strain or deformation rate. This gives a plot of stress versus strain from which a wealth of information may be obtained such as the brittle or ductile behavior, tensile modulus or an indication of stiffness of the material, tensile strength etc. The instrument used for performing tensile testing was an EnduraTEC ELF 3200 Series machine. The main parts of the system were: The linear motor assembly: Had a patented high-bandwidth, low-distortion actuator from Bose Corporation. Testing Chamber: Had facilities for introducing hot air, for increasing temperature as well as introducing liquid nitrogen. A bulb for viewing the test in case liquid nitrogen made the chamber cloudy was also provided. The door had a transparent section for viewing testing while in progress. There were two sets of grips. The bottom grip was stationary and was connected to the load cell. The upper grip was mobile and its motion was regulated by the Wintest software, and ultimately, the linear motor. Temperature Control: With the help of the software, temperature could be varied between oC to 150 oC. Controller box, which acted as an interface between the computer and the machine itself. Figure 2.9 shows the front view of the machine. Figure 2.10 describes the testing chamber. Figure 2.11 provides a rough description of the temperature controlling unit and

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24 the emergency stop button. Figure 2.12 shows the control unit. None of the parts were hydraulic, so maintenance was quite easy. It should be noted that the test was displacement controlled, i.e., the specimen was pulled by a pre-determined amount with each step of testing. The corresponding load exerted on the sample for pulling was recorded. The testing procedure can be described in steps as follows: The machine and the software were turned on. The specimen for tensile testing was a rectangular strip, which was cut from the compression-molded sheet using a penknife. Its width and thickness were measured using a micrometer. The specimen was placed between the grips and the grips were tightened. Over-tightening of the grips was avoided, especially for brittle materials, in order to avoid failure at grips. The linear motor was turned on using the locals button in the software. Load and displacement associated with the grips were tared. After that, the distance between the ends of the grips was measured. This was the gauge length. This value was usually 27 mm. The system was first tuned for a square wave of certain amplitude. The purpose of tuning was to make the command given to the machine by the software and the output generated by the machine match as closely as possible. Adjusting the PID control parameters during the time when the square wave was acting on the system did the required tuning. The tuning was double checked by re-tuning the system with a sinusoidal waveform. The waveform was set to ramp. This was the waveform used for tensile testing. Strain rate could be set according to requirements, by typing the value in the appropriate box. File names for saving the test data were specified using the data acquisition menu. This menu also allowed deciding the rate of scanning, number of scans and time between the scans for acquiring data.

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25 The machine stopped automatically after the specimen failed. In case the specimen did not fail, the machine stopped acquiring data beyond a critical extension of the specimen. This value was 7.082 mm. Figure 2.9. The EnduraTEC ELF 3200 series machine.

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26 Figure 2.10. Specimen testing chamber.

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27 Figure 2.11. Temperature control box and emergency stop buttons. Figure 2.12. Control unit. This acts as an interface between the computer and software.

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28 INDEX: 1) Linear motor assembly 2) Connection between linear motor assembly and grips 3) Testing chamber 4) Load cell 5) Door 6) Bulb 7) Liquid nitrogen inlet 8) Hot air blowing unit 9) Grip 10) Transparent portion of door for viewing testing 11) To load cell 12) Air flow warning button 13) Temperature control box 14) Emergency stop button 15) Heat enable button 16) Control unit (acts as an interface between the computer and the machine). The tensile testing data was obtained as a text file inforce versus displacement form. Knowing the width and thickness of the specimen, cross-sectional area of the specimen could be calculated using the formula: Thickness Width Area (Equation 2.2) The stress on the sample could be calculated by using the formula: Area Force Stress (Equation 2.3) Now, engineering strain is given by the formula: lo l (Equation 2.4) The displacement obtained from the testing data was l. l0, the initial separation between the grips (usually 27 mm) was already known. So strain could be calculated. Knowing stress and strain, stress versus strain curves could be plotted. temperature of testing was For the purpose of tensile testing, typical specimen width was between 4-5 mm and the thickness was between 0.6 to 0.9 mm. The strain rate used was 0.1 mm/sec. The 29 oC. 2-3 specimens were tested for each material.

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29 The scatter for modulus and tensile strength values were found to lie between 4-10 %. Figure 2.13 shows the stress strain plots for various materials. Figure 2.14 shows the variation of tensile modulus with compatibilizer concentration. The modulus values were obtained by calculating the slopes of the linear regions of the stress strain curves. Figure 2.15 shows the variation of tensile strength with compatibilizer concentration. Table 2.6 lists the tensile moduli and tensile strengths of PP and PPCNs. Representative data points generated by the Wintest software are provided in Appendix A. 2.6.3 X-Ray Diffraction When a beam of electron interacts with an atom, some of the incident electrons have sufficient energy to knock out an inner shell electron of that atom. As a result, an electron from one of the outer shells jumps in. In doing so, energy has to be emitted. Emitting X-rays can do this. These X-rays are characteristic of every atom and give information specifically about it. This is because each atom has its own excitation energies for its electron shells. Figure 2.16 illustrates the principles of XRD. When X-rays impinge on a crystalline material, atomic planes diffract them. The objective of performing XRD was to explore the possibility of any intercalation or exfoliation in the layered silicates due to possible penetration by the polymer into the clay layers. This is usually determined by the shifts in low angle peaks for the clay. According to Braggs law: sin2dN (Equation 2.5)

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30 Where N = order of diffraction = wavelength of X-rays used d = interplanar spacing and = semi-angle of diffraction. So, as the semi angle varies, the d spacing between the clay layers also varies. If the polymer is successful in penetrating the clay layers, then the d spacing of the clay layers increases, thereby reducing the angle corresponding to the peak observed. Braggs law quantifies this. Here, N, the order of diffraction is assumed to be one. X-Ray diffraction analysis was performed using a Philips APD 3720 instrument, using a Cu-K X-Ray source (Wavelength = 1.54 ). The range of angles scanned was 0-18 degrees. Reflective mode was used and the experiment was carried out at 15 oC. Table 2.6. Tensile moduli and tensile strengths of PP and PPCNs. Strain rate = 0.01 mm/sec., temperature of testing = 29 oC. MATERIAL TENSILE MODULUS N/mm2 TENSILE STRENGTH N/mm2 PP 1000 22.49 PP/Clay 95:5 968 18.9 PP/EP/Clay 90:5:5 2480 22.02 PP/EP/Clay 85.5:9.5:5 2891 23.6 PP/EP/Clay 76:19:5 1411 20.1 PP/EP/Clay 47.5:47.5:5 1144 18.9

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31 051015202500.050.10.150.20.250.3Strain (absolute)Stress (N/mm2) pp (didnt fail) pp/clay(95:5) (didnt fail) pp/ep/clay (90:5:5) (didnt fail) pp/ep/clay (85.5:9.5:5) (didnt fail) pp/ep/clay (47.5:47.5:47.5) ( f ai l ed) Figure 2.13. Stress versus strain plots for different PPCNs. Strain rate = 0.01 mm/sec., temperature of testing = 29 oC.

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32 050010001500200025003000350005101520253035404550Compatibilizer concentration (wt. %)Stress (N/mm2) Figure 2.14. Dependence of tensile modulus on compatibilizer concentration. Strain rate = 0.01 mm/sec., temperature of testing = 29 oC.

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33 1516171819202122232425010203040Compatibilizer concentration (wt%)Tensile Strength (N/mm2) 50 Figure 2.15. Dependence of tensile strength on compatibilizer concentration. Strain rate = 0.01 mm/sec., temperature of testing = 29 oC.

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34 Figure 2.16. Fundamentals of X-ray Diffraction. Here, l= path difference, d= interplanar spacing and = semi-angle of diffraction. The following stepwise procedure was followed: A 1 cm2 square was cut from the compression molded sheet of the sample, on which XRD analysis was to be done. This square was mounted on a glass slide using double-sided scotch tape. A dummy, with the same height as the sample, was mounted on the slide to go into the sample holder. Usually, the dummy was made out of cut pieces of glass slides and cover slips, which were then fastened together with double-sided tape. The purpose of the dummy was to ensure uniform level throughout the glass slide. The specimen was loaded on the spring clip with the glass slide extending towards the user. The slide was pushed back completely. The door was placed with its contact down. Depressing Blk Start button on X-ray checked water. 20 seconds were given for the operate light to turn on. The voltage was set to 40 kV. The current was set to 20 mA. The kV was reset to 40 kV.

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35 The shutter control was turned to Pressing the appropriate button opened shutter. On the software, using the APD menu and the sub menus within, system preparation and system parameters were defined. Under the Identify menu, program name, scan parameters and data collection parameters were set. F1 key was pressed to start testing. The instrument was shut down upon completion of test. Figure 2.17 shows the entire XRD pattern for each material. Figure 2.18 shows the low angle region of the XRD patterns shown in Figure 2.17. 2.6.4 Differential Scanning Calorimetry (DSC) This characterization technique is used to study the response of a polymer to thermal energy, or in other words, the behavior of a polymer is studied when it is heated [103]. Information regarding thermal transitions of polymers, such as melting, crystallization, and glass transition could be obtained. The basic set up of any DSC instrument consists of two symmetrically placed pans in a silver chamber. This chamber is heavily insulated from the atmosphere so that temperature can be controlled from the heaters and liquid nitrogen alone. Two pans are placed on each side of the chamber. One of them is blank, i.e., has nothing, whereas the other has the polymer sample in it. The amount of sample required ranges from 8-15 mg. After the pans have been placed, the chamber is closed and is taken to a starting temperature, from which it is started to heat. This starting point depends on the temperatures at which thermal transitions take place for the polymer. For example, if polypropylene, with a glass transition temperature between oC to 0 oC, is being used, the starting temperature should be about oC in order to cover the entire Tg transition. It is to be kept in mind

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36 Figure 2.17. Complete XRD patterns for PP and PPCNs in reflective mode, at 15 oC.

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37 Figure 2.18. Lower angle region of XRD patterns for PP and PPCNs in reflective mode, at 15 oC.

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38 that a polymer generally does not undergo transitions at a well-defined temperature, but it does so over a range of temperatures. After taking the polymer to the starting point, it is heated. As mentioned earlier, one of the pans is blank while the other has extra material in it, which is the polymer. Hence, heat requirements would be different for the two sides of the chamber. It is this difference in heat versus temperature that we plot in order to study the thermal transitions. Specific heat versus temperature can also be plotted. Specific heat can be obtained by dividing the heat supplied by the temperature difference resulting from the supply of heat. Thus specific heat is nothing but the amount of heat required to produce a certain temperature difference, and this obviously depends on the characteristics of the material. Figure 2.19 shows Tg transition on a DSC thermogram. The Figure shows that the polymer is absorbing heat and this results in a dip. For measuring glass transition temperatures, there are different procedures, one of which is to take the average of the starting point and end point of the transition. After glass transition, the polymer chains have a lot of mobility. They try to get themselves ordered. Finally when they get ordered after acquiring sufficient energy, they give off heat. This corresponds to the crystallization transition. Figure 2.20 shows this. This peak can help distinguishing between a crystalline and an amorphous system. Amorphous polymers do not show this peak. If the polymer is heated beyond its crystallization temperature, eventually a stage is reached when the temperature of the polymer does not rise until heat is absorbed. This stage is called melting. In other words, crystallization is undone. Now, the furnace has to supply additional heat because the polymer is absorbing heat, and the furnace to keep

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39 the temperature of the chamber rising at a constant rate as well. This results in a large dip. Figure 2.21 shows the melting transition on a DSC thermogram. Figure 2.19. Glass transition on a DSC thermogram. Figure 2.20. Crystallization transition on a DSC thermogram.

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40 Figure 2.21. Melting transition on a DSC thermogram. The heat of melting can be obtained by measuring the area of the corresponding peak. One very important information that can be obtained from a DSC plot, often called a thermogram is % crystallinity of the sample. Knowing the total heat of melting Hm and the total heat of crystallization Hc, Hm Hc gives the heat released by the crystals in the polymer chains that were present before the sample was heated. Dividing this by the specific heat of melting, the grams of polymer that was crystalline before heating the sample can be obtained. So, dividing this number by total mass of the sample and then multiplying by 100 would yield % crystallinity. DSC for this research was performed using a ThermoHaake DSC 220C model instrument, whose basic make-up is just as described above. However, the procedure had a minor difference. The instrument had to be calibrated first. This was done by doing a blank run with alumina in the reference pan and blank in the sample pan. This was followed by the actual experimental run with alumina in the reference pan and polymer in the sample pan. Crimped pans were used for placing the samples. Heating rate used was 10 o C/min, whereas the samples were cooled at 50 oC / min. The starting temperature was 50 oC and the maximum temperature to which the samples were heated was 250 oC. Two cycles were performed. This was to ensure that during the first cycle, any

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41 thermal history effects due to processing would be removed. Figure 2.22 shows the entire heating thermogram. Figure 2.22. DSC heating thermograms for PP and PPCNs. Heating rate = 10 oC/minute. Figure 2.23 shows the Tg region of the heating thermogram for the sake of clarity. Figure 2.24 shows the melting region alone for the same reason. Figure 2.25 shows the cooling thermogram and the crystallization peaks.

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42 Figure 2.23. Tg region of DSC heating thermograms for PP and PPCNs. Heating rate = 10 oC/minute.

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43 Figure 2.24. Tm transition for PP and PPCNs obtained from DSC heating thermogram. Heating rate = 10 o C/minute.

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44 Figure 2.25. DSC cooling thermograms for PP and PPCNs. Cooling rate = 50 oC/minute.

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45 2.6.5 Transmission Electron Microscopy (TEM) TEM is an extremely valuable tool for characterizing polymer/clay nanocomposites. This is because with this technique, the clay galleries dispersed in the polymer can be actually seen. Greater the number of individual platelets that can be counted on a TEM micrograph, better the dispersion of the clay. However, TEM demands a very careful preparation of specimens. Polymers are charged when bombarded with electrons. So, polymer specimens are coated with carbon or gold/palladium coatings. Fundamentally, a TEM makes use of electron optics. A high-energy beam of electrons is directed towards a thin specimen (usually 100 nm thin slices). The electrons that are transmitted through the specimen are collected on a screen and these give information about the microstructure of the material. The TEM consists of an electron gun. This could be either thermionic or a field emission gun. The filament however, is mostly made of tungsten, and is V-shaped. LaB6 filaments can also be used, but they are quite expensive. Other components of the TEM are condenser lens assembly, specimen stage, objective lens assembly and the recording system. A very high quality vacuum should be maintained at all times in order to make maximum use of the electrons emitted by the gun. The contrast obtained in a TEM image is atomic contrast. In our case, polymers have elements like carbon, hydrogen and oxygen, whereas the clay has silicon, aluminum etc., that have a higher atomic number. Thus, they scatter more and transmit fewer electrons. So, they appear dark in the micrograph. For preparing specimens for TEM, a few thin slices were cut from the compression-molded sheet of the material. These were embedded in a two-part epoxy

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46 resin in a mold, and were cured in a vacuum oven at 40 oC. Next, 100 nm thin slices were cut using an Ultracut microtoming machine. It was found that the polymer embedded in epoxy was hard enough to be cut with a diamond knife without being cooled with liquid nitrogen (referred to as ultracryomicrotomy). The slices were obtained in a small pool of water that was present in a specially designed area surrounding the diamond knife. These were picked up using hair tipped brushes and were mounted on copper grids. Carbon coating of slices followed this. It is worthwhile mentioning that sample preparation can introduce voids in the specimen. Figure 2.22 shows this [104]. Figure 2.26. Void formation between the folded silicate layers during the microtoming of the bulk nanocomposite. The prepared specimens were viewed under a JEOL 2010F TEM. Figure 2.24 shows TEM images for PP/Clay (95:5). Figure 2.25 shows TEM images for PP/EP/Clay (85.5:9.5:5). Figure 2.26 shows TEM images for PP/EP/Clay (47.5:47.5:5).

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47 Figure 2.27. TEM micrographs of PP/CLAY (95:5).

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48 Figure 2.28. TEM micrographs of PP/EP/CLAY (85.5:9.5:5).

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49 Figure 2.29. TEM micrographs of PP/EP/CLAY (85.5:9.5:5).

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50 2.7 Discussion of Results In this section, the results obtained in the form of various plots, tables and curves from different characterization techniques are discussed and their implications are elaborated. 2.7.1 Tensile Testing It is evident from Figure 2.13 that with the addition of clay and compatibilizer, the tensile properties showed remarkable improvement. Both modulus and tensile strength for the materials designated PP/EP/CLAY (90:5:5) and PP/EP/CLAY (85.5:9.5:5) were much better than pure PP. However, the same were inferior for PP/Clay (95:5). This material did not have any compatibilizer. This showed the necessity for adding Epolene. Table 2.6 shows the variation in modulus and tensile strength with variation in compatibilizer concentration. Figure 2.14 conveys the same pictorially. It was seen that for PP/EP/CLAY (90:5:5), the modulus was 148% greater than pure polypropylene, whereas for PP/EP/CLAY (85.5:9.5:5), the increase was 189.1%. This means that for these materials, the tensile moduli were more than two times that of pure PP. Figure 2.15 shows the dependence of tensile strength on compatibilizer concentration. The trend observed is similar to that with tensile modulus. An interesting feature to note regarding the trends shown by Figure 2.14 and Figure 2.15 was that the properties reached a maximum at a certain compatibilizer concentration and then leveled off after showing a decreasing trend. However, the weight % of clay in all these materials was constant, which was 5%. A possible hypothesis was proposed for such a behavior. Two additional components were added to PP. First was a low molecular weight compatibilizer, whose molecular weight was significantly lower than PP. The other material was clay, which acts as reinforcing agent. It was seen from Figure 2.13 that

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51 when no compatibilizer was present (i.e., for PP/CLAY (95:5)), the material still exhibited ductile behavior. This is because the clay has been modified organically to exhibit some compatibility with hydrophobic polymeric systems. However, the extent of clay dispersion and distribution was not adequate at this stage to optimize the number of load bearing clay platelets per unit volume. Hence, the modulus and tensile strength were lower than PP. When some compatibilizer was added (i.e., PP/EP/CLAY (90:5:5)), it was seen that the modulus showed tremendous improvement, and the tensile strength increased as well. However, the increase in tensile strength was not proportionate to the increase in tensile modulus. This is because the introduction of clay tends to make PP brittle. However, at higher stress and strain values, the small, low molecular weight compatibilizer chains tend to flow more easily than PP. In other words, the clay increases the tensile modulus, but the compatibilizer tends to bring it down. Hence, there is a certain amount of compatibilizer that can be added for a given amount of clay (to be added with PP) in order to get the optimum mechanical properties. So, the addition of a low molecular material may adversely affect the tensile properties. But on the other hand, the compatibilizer may also increase the spacing between the clay galleries, thereby increasing the effective surface area available for bonding. This could mean enhanced adhesion between the polymer matrix and the clay. This could lead to better mechanical properties. This is supported by TEM images, which are discussed in a later section. So there are two effects of the compatibilizer on the system: Being a low molecular component, it tends to have detrimental effects on the mechanical properties of the nanocomposite.

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52 It tends to increase the spacing between the clay platelets. This tends to enhance the mechanical properties. Now, as the percentage of compatibilizer was increased beyond 5 wt% (i.e., PP/EP/CLAY (85.5:9.5:5)), it was seen that the tensile properties improve further. The modulus and tensile strength were enhanced even further. Thus, we see that factor (a) is still prevalent over factor (b). Upon increasing the concentration of the compatibilizer further (i.e., PP/EP/CLAY (76:19:5)), a drastic drop in both modulus and tensile strength was observed. This showed that the low molecular factor associated with Epolene overcame its reinforcing capability by increasing the clay interlayer spacing. When the concentration of Epolene was increased to 47.5 % by weight, the tensile properties not only got worse, but also the material failed when subjected to tensile testing. This was not observed with any other material, including pure PP. This indicated the there was excessive low molecular weight Epolene present, and its effect on tensile properties by increment of clay interlayer spacing was certainly overcame by its own mechanically weak character. This material not only failed but it also did so in a brittle fashion. This is possibly due to presence of excessive low molecular weight component, as well many load bearing clay platelets per unit volume, which also tend to make the nanocomposite brittle. 2.7.2 X-Ray Diffraction Figure 2.17 shows the entire range of angles covered, which is between 0 to 18 o, while Figure 2.18 shows the low angle region of the same plot. It is known that pure clay has a diffraction peak, which corresponds to Si 001 plane, between 2 to 4 degrees. It can be seen from the plots that some intercalation has taken place, but the shift in the peaks is not very significant. XRD gives an overall view of the extent of clay dispersion. For

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53 actually seeing the clay dispersion on a local scale, TEM is employed, and its results are discussed in a later section. 2.7.3 DSC The DSC heating thermogram is shown in Figure 2.22. It is noteworthy that the abscissa of the plot is heat supplied by the instrument, which is directly proportional to specific heat. Since it is hard to distinguish between individual thermograms, Tg and Tm regions are shown separately in Figure 2.23 and Figure 2.24 respectively. From Figure 2.23, it is seen that there is not a significant shift in the Tg transition for the nanocomposites. However, it can be said that at glass transition, the heat requirement for PP/CLAY (95:5) is the least. This could be because the clay has a lower specific heat capacity than the pure polymer, and hence, the heat capacity of the composite decreases. Upon adding Epolene (90:5:5), the heat capacity is slightly increased. However, the heat capacity of Epolene is lower than PP. Hence, some chain confinement has possibly taken place. The addition of Epolene facilitates the penetration of PP chains into clay galleries as well as bonding between the clay and the matrix PP, thereby increasing the heat requirement for Tg. Increment in thermal requirement is observed for PP/EP/Clay (85.5:9.5:5) also, for the same reason. Both the nanocomposites also show a slightly higher Tg than PP. But the heat capacity of the system PP/EP/Clay (47.5:47.5:5) is found to be lower than PP. This could be because the low molecular weight (and hence lower energy required to move the chains) factor associated with Epolene has overcome its ability to aid chain intercalation. Also, the weight fraction of PP has decreased drastically in this nanocomposite. From Figure 2.24, it is seen that there are considerable shifts in Tm values. The Tm of PP is 171.4 oC. The Tm of PP/Clay (95:5) is 166.5 oC, about 5 oC lower than PP. This

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54 could be because the clay may be acting as a nucleating agent. So, there are numerous sites for heterogeneous nucleation per unit volume of the material. As a result, unlike PP, where there are fewer, but larger crystals, in the nanocomposite, there are numerous, but smaller crystals. The Tm values for all the nanocomposites are lower than PP, due to the possible explanation provided above. Figure 2.23 shows the cooling thermogram. Here also, the abscissa of the plot is heat supplied by the instrument. The large peaks between ca. 100 oC and ca. 150 oC represent crystallization phenomena. The most striking feature of the plot is the significant shift in the Tc (crystallization temperature) for the nanocomposites, ranging from about 4-12 degrees. This means that crystallization phenomenon begins much earlier for the nanocomposites. This also indicates that the clay might be acting as a nucleating agent. It is also seen from the figure that crystallization begins earliest for PP/EP/CLAY (90:5:5), which is very close to the onset of crystallization of PP/EP/CLAY (85.5:9.5:5). However, for the material PP/EP/CLAY (47.5.47.5:5), crystallization temperature is lower than the other nanocomposites. This is an interesting result. This is because PP/EP/CLAY (47.5.47.5:5) is expected to disperse the clay best and hence, the number of nucleating sites available per unit volume of the material is expected to be the highest for this material. Then why does the onset of crystallization occur much later than PP/EP/CLAY (85.5:9.5:5)? In a work by Potzgay et al. [105] the authors have proposed that crystallization is actually caused by those clay-platelets that are least separated by the penetration of polymer chains. This could explain the results obtained in this research. It offers an explanation for the earlier crystallization of PP/EP/CLAY (90:5:5) than PP/EP/CLAY (85.5:9.5:5), and also that the crystallization temperature of PP/EP/CLAY

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55 (47.5:475:5) is the least among the nanocomposites containing Epolene, because Epolene facilitates increase in clay-interlayer spacing. However, PP/Clay (95:5) does not follow this trend. This is possibly due to excessive stacked tactoids with virtually no polymer are present. So the number of nucleation sites per unit volume is drastically lower than the other nanocomposites. In summary, the following things should be kept in mind, while addressing crystallization behavior of nanocomposites: Epolene is more compatible with clay than PP and plays an important role at the PP/Clay interface. Epolene melts and crystallizes at temperatures much lower than PP. The molecular weight of Epolene is much lower than PP, so it exhibits higher mobility than PP at any temperature above its glass transition. Increase in Epolene concentration means more liquid material at elevated temperatures, but also better dispersion of clay in the polymeric matrix. These reasons also help to explain as to why be the crystallization temperature of PP/CLAY (95:5) greater than PP/EP/CLAY (47.5:47.5:5), besides the explanation provided by Potzgay et al. 2.7.4 TEM TEM micrographs shown in Figures 2.25 through 2.27 enable us to view to dispersion of clay on a local scale. It can be seen that clay is poorly dispersed in PP/CLAY (95:5) (Figure 2.25). There are quite big and distinct stacks of platelets in this material. The marker for the image taken at 10 kX gives a rough estimate of the size of these domains. The domains are approximately 2-3 microns large. The image taken at a higher magnification, 100 kX, shows that there is a significant amount of tactoids formation with little or no penetration by the polymer. This is evident from the big dark region that can be seen in the image. This can be explained by the fact that the

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56 organophilic polymer is still not very compatible with the clay, which is even though modified with organic substances. However, there are numerous platelets that are expanded by the penetration of polymer chains. In other words there is some intercalation. For PP/EP/Clay (85.5:19:5) (Figure 2.26), we observe that the dispersion is much better than PP/CLAY (95:5), and that the stacks of platelets that contain very less polymer are smaller and fewer. For PP/CLAY (47.5:47.5:5) (Figure 2.27), we see that the dispersion is even better. Even at low magnifications, such as 30 kX, the size of the stacked tactoids does not exceed ~ 600 nm, as seen from the image. It should be noted however, that these images do not represent the entire sample, with respect to dispersion and distribution of the clay. But the images prove a fundamental concept, which is the necessity of a compatibilizer for enhanced dispersion and distribution of clay platelets. 2.8 Conclusions The following can be concluded from the following research: Compatibilizers are necessary ingredients for enhanced dispersion and adhesion of silicates in organophilic polymer systems, especially with non-polar polymers such as PP. Better dispersion and distribution of clay platelets gave rise to better mechanical properties of nanocomposites. This was explained by the increase in number of load bearing clay platelets per unit volume of the material and also the uniformity of distribution of the platelets. However, when added beyond a certain concentration, the compatibilizer had deleterious effects on the mechanical properties of the nanocomposites. Addition of compatibilizer, besides affecting the extent of clay dispersion and mechanical properties, also influenced the thermal behavior of the nanocomposites. Compatibilizer also played a role in crystallization of the nanocomposites.

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CHAPTER 3 IMPACT MODIFICATION OF POLYPROPYLENE/MONTMORILONITE CLAY NANOCOMPOSITES 3.1 Introduction Numerous papers have been published on polymer/clay nanocomposites, but very few address one of the key issues associated with them, which is their impact properties. In spite of the fact that tensile modulus, tensile strength, barrier properties etc. show a significant increase upon the addition of clay, the impact properties remain either close to the original polymer matrix or they are inferior. The aim of the present work was to investigate and improve the impact properties of polymer/montmorillonite clay nanocomposites. The proposed strategy was to add elastomeric species. This has been a proven technique for improving the impact properties of many materials. Other objectives were: 3. To study the effects of introducing the elastomer on the extent of intercalation/exfoliation of the clay. 4. The effect of introducing the elastomer on other properties such as tensile properties and thermal behavior. 5. To determine the effects of method of preparation of the rubber modified polymer clay nanocomposite on the above mentioned aspects. If we succeed in improving the impact properties on these novel class of materials, without sacrificing other assets ot these materials, then polymer clay nanocomposites would be more complete materials with respect to improved properties in a balanced fashion that could be used for a variety of applications. 57

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58 Figure 3.1 [12] shows a typical trend in the Izod impact strength of montmorillonite-modified polymer, which was Nylon-6 in this case. It was observed that the pure polymer was superior in comparison to the nanocomposites. Figure 3.1. Notched Izod impact strength of nylon 6 and 95/05 composites as a function of clay loading. This is because the large surface area of the clay provides greater space for the polymeric matrix to adhere to it, but at the same time, it also increases the possibility of formation of regions where the polymer does not adhere to the surface of the clay. This could result in microvoids. These really impair the impact properties. This is because they act as stress concentrators and initiators for crack formation. Further, it is also believed that addition of clay also alters local chain dynamics [15].

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59 Michler and coworkers [106] suggested that depending on their orientation with respect to the axis of tension, a role could be attributed to the silicate layers with respect to formation of micro voids. They showed that intercalated morphology showed more cavitation than the exfoliated morphology. Thus, morphological considerations are of great importance in addressing the impact properties of polymer clay nanocomposites. In spite of the fact that the inorganic clays are modified with many additives such alkyl ammonium chloride, that also facilitate improved adhesion between the filler and the matrix, the impact properties do not show significant increase. In fact, in many cases, deterioration has been observed [14, 39, 43, 47, 60,107]. As stated earlier, it has been shown that intercalated polymer clay nanocomposites tend to show extensive cavitation. Figure 3.2 [15] shows this. In this work, it was revealed that at room temperature, the polyamide/clay nanocomposite was quite fragile. Further, the volume strain evolution upon drawing revealed that pristine polymer deformed with little volume variation, whereas the nanocomposite showed cavitation. These observations corroborated the above mentioned reason for describing the stagnant or deteriorating nature of the impact properties. The impact modification of polymer/clay nanocomposites calls for a slightly different approach than for traditional fiber reinforced composites. This is because the way in which the nanocomposite is formed is different. The clay has a layered structure, with the distance between the layers being a few nanometers in size. The polymer chains have to penetrate into these galleries and increase the separation. This also disperses and distributes the clay platelets uniformly throughout the matrix.

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60 Figure 3.2. SEM observation: (a) Cavitated nanocomposite; (b) Fibrillated nanocomposite and polymer/clay interaction.

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61 In doing so, they also have to bond to the surface of the clay platelets. On the other hand, there is no such penetration of polymer chains in case of traditional fiber reinforced composites. Cho et al. reported that for a given loading of clay, the Izod impact strength increased with increasing temperature. But still, the pure polymer showed better impact properties at any given temperature than the montmorillonite-modified nanocomposites [12]. Figure 3.3 [12] shows this. Figure 3.3. Notched Izod impact strength of nylon 6 and 95/05 composites as a function of temperature. The rationale of Cho et al. was the following: Upon increasing the temperature, the softness of the material is increased, and so are the motions between the polymer chains. This indicates that the volume occupied by the voids decreases and hence, impact properties improve. However, increased

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62 temperature has adverse effects on other properties such as storage modulus and tensile strength, which are very important engineering properties for material selection. So, it is seen that improving the impact properties of polymer clay nanocomposites is not an easy task. It is however, envisioned that there are certain strategies, which will be discussed in the next section, that could possibly overcome this problem. 3.2 Research Strategies Blending or reactive blending with elastomeric materials seemed to be an interesting possibility. This was because imparting rubbery domains would greatly enhance energy dissipation during fracture. Figure 3.4 illustrates this. Figure 3.4. Effect of addition of elastomer on craze crack structure. (a) Propagating crack along the matrix material, along with craze fibrils. (b) Propagating crack in a material with rubbery domains. Here, the rubbery domains absorb the energy due to their extremely large size of plastic zone so that fracture process is retarded. Also there is little crazing upon introducing elastomers. Elastomers undergo tearing phenomena due to their large plastic zone. This method for improving the impact properties of a wide variety of materials has been employed since 1960s [110-117], and is being used till date [118-124]. However, due to dearth of publications regarding rubber toughening of polymer clay nanocomposites, nothing definite could be stated about the outcomes of this method

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63 prior to performing experiments. But the organically modified clays were not as hydrophilic as glass fibers were. So the issues related to compatibilization of the interface between the matrix polymer, clay and the elastomer were alleviated to a considerable extent. This was corroborated by the fact that elastomers being liquids at room temperature possessed better wetting characteristics. However, it is well known that the elastomers also tend to reduce the tensile modulus because of their liquid like behavior. Figure 3.5 illustrates this. Hence, attempts were made towards improving the impact properties of the nanocomposites, without sacrificing the tensile properties significantly. 3.3 Materials Montell (now Basell) supplied PP used for this study. Table 3.1 enlists its properties. The compatibilizer used was Epolene G-3003, supplied by Eastman Chemical Company. Table 3.2 lists some of its properties. The clay used for this study was Nanomer I.34TCN, supplied by Nanocor Inc. Table 3.3 describes some of its properties. Two different elastomers were used for this research. DuPont Dow Elastomers supplied the first, a polyolefin elastomer, under the trade name Engage (grade 8842). Table 3.4 shows some of its properties. The other elastomer was an oligomeric polybutadiene whose ends are functionalized with epoxy and hydroxyl groups. Aldrich chemicals supplied this. Table 3.5 shows some of its properties. Sigma Aldrich supplied Glycidyl methacrylate used for this research. Table 3.6 enlists some of its properties.

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64 Figure 3.5. Stress strain curves for different types of materials.

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65 Table 3.1. Properties of Basell Profax 6523 Polypropylene used for the research. PROPERTY VALUE TEST METHOD PHYSICAL Specific Gravity 0.9 ASTM D792 Melt Flow Rate (230 C) 4.00 g/10 min ASTM D1238 MECHANICAL Tensile Strength @ Yield 4900 psi ASTM D638 Tensile Elongation @ Yield 12 % ASTM D638 Flexural Modulus (Procedure A) 1% Secant: 200000 psi ASTM D790 Notched Izod Impact (73 F) 0.7 ft-lb/in ASTM D256 Rockwell Hardness (R-Scale) 86 ASTM D785 THERMAL DTUL @66psi Unannealed 199 oF ASTM D648 Table 3.2. Properties of Epolene G-3003. PROPERTY VALUE Ring & Ball Softening Point (C) 158h Penetration Hardness <1 Density @ 25 C 0.912 Acid Number 8 Viscosity, cP (mPas) @ 190 C 60,000 Melt Index @ 190C 12.7 Color (Gardner) 25 Molecular Weight 27,200 Manufacturer Eastman Chemical Company Table 3.3. Physical properties of Nanomer I.34 TCN. PROPERTY VALUE Appearance White Powder Mean Dry Particle Size (Microns) 16-22 + 325 Mesh Residue (%) 0.1 Specific Gravity 2.0 Moisture (%) 3.0 Bulk Density (gms/cc) 0.30-0.36 Purity (% min) 98.5 Manufacturer Nanocor

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66 Table 3.4. Properties of Engage 8842. PROPERTY VALUE Co monomer Content (wt%) by 13C NMR/FTIR 45 Density (g/cm3), ASTM D-792 0.857 Mooney Viscosity ASTM D-1646 ML at 121 C 26 Melt Index (dg/min) ASTM D-1238 190 C, 2.16kg 1.0 Durometer Hardness, Shore A ASTM D-2240 50 DSC Melting Peak (C) Rate 10 C/min 33 Ultimate Tensile Strength, MPa ASTM D-638, 508 mm/min 2.1 Ultimate Elongation (%) ASTM D-638, 508 mm/min 975 Manufacturer DuPont Dow Elastomers. Table 3.5. Properties of oligomeric, epoxy and hydroxyl end functionalized polybutadiene. PROPERTY VALUE Mn 1,300 Mw 2,600 Microstructure 55% 1,4-trans; 15% 1,4-cis; vinyl 30% Viscosity 250 poise Fp >230 F Density 1.01 g/mL Manufacturer Aldrich Chemicals.

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67 Table 3.6. Properties of Glycidyl methacrylate PROPERTY VALUE Molecular Formula C7 H10 O3 Weight % epichlorohydrin 0.2% Weight % R-glycidol ~ 1 Boiling point 189 C/760 mm Hg Freezing point 169 F Density 1.042 g/mL Structural formula Manufacturer Aldrich Chemicals. 3.4 Processing The main equipment used for processing the nanocomposites was a 30mm APV co-rotating reactive twin-screw extruder. This extruder had eight temperature zones from feed zone to die zone. Hence, the processing temperature ranged from 200 C (feed zone) to 234 C (die zone). The screw L/D was 40. PP and Epolene pellets were dried in an air-circulating oven at 80 C for 24 hrs. Different processing protocols were employed. The following protocol was used in preparing the functionalized oligomer impact-modified polymer nanocomposite. This was labeled as protocol A. First, the compatibilizer (Epolene) and end-functionalized oligomeric elastomer were blended together in a batch mixer (150 oC, for 2 hours) in the weight ratio of (4.75: 0.25). The elastomer was dissolved in xylene. Figure 3.6 shows the details of this operation. This product was designated as Comp/F-olig. The resulting product was crushed and dried for 24 hours in an air-circulating oven at 80 C.

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68 Next, PP and Comp/F-olig, mixed in the weight ratio (90:5) were blended in the twin-screw extruder. The resulting strands were pelletized and dried for 30 hours under conditions described above. Subsequently, the PP+Comp/F-olig pellets were melt-compounded with 5-wt % clay. To ensure good mixing, the clay was also dispersed in xylene, before being added to the molten PP/Comp/F-Olig mixture at the feed zone along the screw channel. The resulting strands were pelletized and dried as described above. This product was designated as PP/Comp/F-Olig /Clay. The feed rate of PP, PP/Comp and other blends described earlier was 40 grams/min., whereas the feed rate of clay was 2 grams/min. In order to verify that the characteristics of the compounded materials were not significantly influenced by the sequence of the preparation, two other impact-modified nanocomposites were prepared. The polymeric elastomer was used for this purpose. For the first sample, designated PP/Comp/F-POE/Clay, protocol B was used. Here, the polyolefin elastomer (POE) was first functionalized with Glycidyl methacrylate (GMA) in the reactive twin-screw extruder. Next, PP and Epolene were blended in the extruder in the weight ratio 90:4.75. The functionalized elastomer was then added to the PP/Compatibilizer blend in the weight ratio of 94.75:0.25. Finally, clay (dispersed in xylene) was added to the above blend. Xylene: clay used was 5:1 by weight. The weight ratio of PP, Epolene, polyolefin elastomer and Clay now became 90:4.75:0.25:5. For the second sample, designated PP/Comp/Clay/F-POE, protocol C was employed.

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69 Figure 3.6. Schematic representation showing mixing of Epolene with oligomeric polybutadiene. Here, the sequence from functionalized POE and clay was reversed, that is, the clay was added to PP/Compatibilizer mixture before the functionalized POE. The weight percentage of each component remained the same. The reference material used for comparing the properties of the impact-modified nanocomposites was PP/Comp/Clay (90:5:5). Table 3.7 summarizes the designations of different nanocomposites and their method of preparation. Table 3.8 summarizes the weight percentage of different components in various nanocomposites processed. Figure 3.7 shows the operation in the form of a block diagram.

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70 3.5 Characterization The following characterization are used to obtain an understanding of the structure property relationships in the nanocomposites processed: Tensile testing X-Ray Diffraction Izod impact testing Differential Scanning Calorimetry Transmission electron microscopy Table 3.7. Preparation of Impact modified nanocomposites. MATERIAL METHOD OF PREPARATION PP/EP/F-OLIG /CLAY (PROTOCOL A) Epolene is blended with functionalized oligomeric polybutadiene (95% Epolene and 5% F-olig PB by weight). The matrix is prepared by taking 90 parts of pure PP and 5 parts of (epolene+f-oligomeric PB). 95 parts of this matrix are added to 5 parts of clay (by weight). Hence in 100 parts of the nanocomposite, there is 90 % PP, 4.75%Epolene, 0.25% F-olig PB, 5% clay. PP/EP/F-POE/CLAY (PROTOCOL B) PP is blended with Epolene. F-POE is added to this. Thus the matrix material is prepared, which is PP/Epolene/F-POE. To this, clay is added to make the nanocomposite. PP/EP/CLAY/F-POE (PROTOCOL C) The nanocomposite is prepared first by blending PP, Epolene and clay. F-POE is then added to this nanocomposite. PP/EP/CLAY (90:5:5) (REFERENCE MATERIAL) 90 parts of PP (by weight) are blended with 5 parts of Epolene. 5 parts by wt. of the montmorillonite clay is added to make the nanocomposite.

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71 Table 3.8. Percent composition of different nanocomposites by weight (dry basis). SAMPLE DESIGNATION WT. % PP WT. % EPOLENE WT. % CLAY WT. % POE WT. % F-OLIGOMER PP/COMP/CLAY 90 5 5 0 0 PP/COMP/F/OLIG/CLAY 90 4.75 5 0 0.25 PP/COMP/CLAY/F-POE 90 4.75 5 0.25 0 PP/COMP/F-POE/CLAY 90 4.75 5 0.25 0 Figure 3.7. Synthesis of impact modified nanocomposites using a reactive twin-screw extruder. 3.5.1 Specimen Preparation Specimens for the listed techniques were prepared using compression molding. The temperature used was 205 oC, and the pressure used was 10, 000 psi. Sheets were prepared for pure PP, and the nanocomposites. In order to prepare the specimens, the press was first heated to 420 oF. The mold used was square in shape, with dimensions of 70 mm X 70 mm X 0.8 mm. The mold was placed on a metal plate covered with Teflon coated aluminum foil. The mold was then

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72 filled with dried pellets. This plate with mold and the pellets was placed on the bottom plate of the press. Another Teflon coated aluminum foil covered metal plate was placed on top of the mold bearing plate, to give a sandwiched assembly. The bottom plate of the press was raised until the assembly just touched the top plate of the press. The pellets were then allowed to convert into a liquid state by heat transfer from the press. This took about 5-6 minutes. After that the pressure of the system was raised to 10, 000 psi. Initially, due to resistance offered by the liquid polymer as well relatively incomplete conversion to liquid, the pressure dropped below 10,000 psi. Under these circumstances, it was necessary again to raise the pressure to 10,000 psi. This was repeated until the pressure attained a steady value of 10,000 psi. The pressure could be measured using a gauge attached to the press. A pressure of 10, 000 psi. on the gauge corresponded to 9302 psi. on the sample. This was calculated using the formula: AgPgAsPs (Equation 3.1) Where, Ps = Pressure on the sample As = Cross sectional area of the sample Pg = Gauge pressure Ag = Cross sectional area of the piston of the press. As = 70 X 70 mm2 Ag = 3.14 X (32)/4 Pg = 10, 000 psi. After the gauge pressure became steady at 10, 000 psi., the mold was allowed to rest at the abovementioned temperature and pressure for 10 minutes. After that, the heat supply to the press was turned off. Immediately after this, the pressure-release screw was

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73 turned. The hot plate assembly containing the mold between the two metal plates was removed and was immersed in a cold-water reservoir and kept for 3 minutes. Then, the entire assembly was flipped over and was replaced in the reservoir for 3 more minutes. After the mold cooled down, the solidified sheet was then taken out of the mold. Sheets were prepared in this way for pure PP, and the various nanocomposites. These sheets served as specimens for all the characterization techniques. 3.5.2 Tensile Testing The aim of performing tensile testing was to evaluate the mechanical response of the materials to a known strain or deformation rate. This gives us a plot of stress versus strain from which we can obtain a wealth of information such as the brittle or ductile behavior, tensile modulus or an indication of stiffness of the material, tensile strength etc. Tensile testing was carried out using an EnduraTEC ELF 3200 series machine. It consisted of the following components: The linear motor assembly: Had a patented high-bandwidth, low-distortion actuator from Bose Corporation. Testing Chamber: Had facilities for introducing hot air, for increasing temperature as well as introducing liquid nitrogen. A bulb for viewing the test in case liquid nitrogen made the chamber cloudy was also provided. The door had a transparent section for enabling to view testing while in progress. There were two sets of grips. The bottom grip was stationary and was connected to the load cell. The upper grip was mobile and its motion was regulated by the Wintest software, and ultimately, the linear motor. Temperature Control: With the help of the software, temperature could be varied between oC to 150 oC. Controller box, that acts as an interface between the computer and the machine itself. Strain rate used was 0.01 mm/sec and temperature of testing was 28 oC. Figure 3.8 presents the results obtained from tensile testing.

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74 051015202500.050.10.150.20.250.3Strain (absolute)Stress (N/mm2) PP PP/COMP/F-OLIG/CLAY(90:4.75:0.25:5) PP/COMP/CLAY/F-POE(85.72:4.76:4.76:4.76) PP/COMP/CLAY (90:5:5) PP/COMP/F-POE/CLAY(85.72:4.76:4.76:4.76) Figure 3.8. Tensile behavior of PP and impact modified PP/Clay nanocomposites at 0.01 mm/sec., 28 oC.

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75 Table 3.9. Tensile properties of PP and impact modified PPCNs. MATERIAL MODULUS (N/mm2) TENSILE STRSNGTH N/mm2 PP 949.25 22.3 PP/COMP/CLAY (90:5:5) 1892.1 21.68 PP/COMP/CLAY/F-POE 1023.1 19.89 PP/COMP/F-POE/CLAY 1185.3 21.7 PP/COMP/CLAY/F-OLIG 1307.6 22.67 3.5.3 X-Ray Diffraction The objective of performing XRD was to explore the possibility of any intercalation or exfoliation in the layered silicates due to possible penetration by the polymer into the clay layers. This is usually determined by the shifts in low angle peaks for the clay. This is because according to Braggs law: )sin2/( dnd (Equation 3.2) d = interplanar spacing, n = order of diffraction = wavelength of X-Ray source, and = semi-angle of diffraction So, as the semi angle varies, the d spacing between the clay layers varies. If the polymer is successful in penetrating the clay layers, then the d spacing of the clay layers increases, thereby reducing the angle corresponding to the peak observed. XRD was performed using a Philips APD 3720 instrument using a Cu-K X-Ray source (Wavelength = 1.54 ). The range of angles swept was 0-75 degrees. Reflective

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76 mode was used and temperature was 15 oC. Figure 3.9 and Figure 3.10 present the results obtained from XRD. Figure 3.9. XRD patterns for PP and impact modified PP clay nanocomposites in reflective mode, at 15 oC.

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77 Figure 3.10. Low angle region of XRD plot shown in figure 3.9 in reflective mode, at 15 oC. 3.5.4 Izod Impact Testing In this method to determine impact strength, a metallic pendulum swings on its track and strikes a notched, cantilevered plastic sample. The energy lost (required to break the sample) as the pendulum continues on its path is measured from the distance of its follow through. Figure 3.11 shows the instrument. Impact testing was carried using a TMI #41869 model machine.

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78 Figure 3.11. Izod impact testing apparatus. In this research while making impact testing bars as per as ASTM D-256, formation of air bubbles could not be avoided, even after repeated trials. Hence, impact testing was carried out with a specimen that had lesser thickness and width than the prescribed standard. For the same reason, it could not be notched as well. Hence, the impact testing was performed in the un-notched mode. Table 3.10 summarizes the results obtained. Table 3.10. Impact strengths of impact modified PP/clay nanocomposites at 25 oC. MATERIAL IMPACT STRENGTH IN ft. lb / sq. in PP 15.91 PP/COMP/CLAY 14.85 PP/COMP/CLAY/F-POE 16.98 PP/COMP/CLAY/F-OLIG 26.52

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79 3.5.5 Differential Scanning Calorimetry DSC describes the behavior of a material when subjected to heat at a controlled rate. This enables us to determine different transitions associated with the polymer such as glass transition, melting transition, besides crystallization behavior etc. DSC on the samples was performed using a ThermoHaake DSC 220 C model instrument. Heating rate used was 10 oC/minute, while cooling rate was 50 oC/min. Two sweeps of this thermal treatment were performed. The output of the instrument is a plot between heat supplied in microwatts versus temperature. The heat supplied is directly proportional to the specific heat of the material being tested. Figure 3.12 shows the heating thermogram. Figures 3.13 and 3.14 show the Tg and Tm transitions separately for the purpose of clarity. Figure 3.15 shows the cooling thermogram. 3.5.6 Transmission Electron Microscopy TEM images usually complement XRD data and also enable us to see details at a nanometer scale. However, it should be noted that this technique gives image of a very small section of the material. Transmission electron microscopy was performed on PP/COMP/F-POE/CLAY using a JEOL 2010 Field emission TEM instrument. For PP/COMP/F-OLIG/CLAY, a JEOL 200 CX instrument was used. It has a tungsten based thermionic gun. Figure 3.16 shows the TEM image for the oligomer-modified nanocomposite. Figures 3.17 and Figure 3.18 present the TEM images for polyolefin-modified elastomer. Use of two different instruments for the samples may result in difficulty in comparing the details with respect to intercalation of clay platelets.

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80 Figure 3.12. DSC heating thermogram for PP and impact modified PP/clay nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min.

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81 Figure 3.13.Tg region of DSC heating thermograms presented in Figure 3.12. Heating rate = 10 oC/min., cooling rate = 50 oC/min.

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82 Figure 3.14. Tm region of DSC heating thermograms presented in Figure 3.12. Heating rate = 10 oC/min., cooling rate = 50 oC/min.

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83 Figure 3.15. DSC cooling thermogram for PP and impact modified PP/clay nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min.

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84 Figure 3.16. TEM micrograph of PP/COMP/F-OLIG/CLAY. Figure 3.17. TEM micrographs of PP/COMP/F-POE/CLAY

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85 Figure 3.18. TEM micrographs of PP/COMP/F-POE/CLAY at a higher magnification.. 3.6 Discussion of Results Having employed different characterization techniques for analyzing the mechanical behavior and microstructure of the impact modified nanocomposites, it is essential that the results obtained from these be analyzed and interpreted appropriately in order to explain different phenomena occurring in these materials. This section deals with the same. 3.6.1 Tensile Testing From Figure 3.8 it is evident that the nanocomposite labeled PP/Comp/Clay/F-olig shows the highest tensile strength. Its modulus is higher than PP as well as any other nanocomposite prepared by any other impact modification route employed during processing. It is also clear that the sequence of addition of elastomers, i.e., prior and after the addition of clay also has a significant influence on the tensile behavior. It can be

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86 concluded from Table 3.9 that between PP/Comp/Clay/F-POE and PP/Comp/F-POE/Clay, the nanocomposite in which the elastomer has been added prior to addition of clay shows better tensile modulus, tensile strength as well as impact strength. It is also noteworthy that for the oligomeric impact modification route, the elastomer was added prior to the addition of clay. So, the tensile testing results indicate that the addition of elastomr prior to the addition of clay gives better mechanical properties. The tensile modulus of all the impact-modified nanocomposites is however, lower than PP/Comp/Clay (90:5:5). The modulus of PP/Comp/Clay/F-Olig is about 31% lower than PP/Comp/Clay (90:5:5), but is still about 37% higher than pure PP. This can be explained on the basis of fundamental tensile behavior of elastomers. Elastomers have very low glass transitions (usually much below 0 oC), so at room temperature, they are liquids, so they exhibit liquid like flow upon subject to tensile stress. This means that for a small deforming force, they exhibit much larger extensions, than regular solids. As a result, the overall tensile modulus (an indication of solid like behavior) is reduced. 3.6.2 X-Ray Diffraction It can be inferred from figure 3.9 and figure 3.10 that the use of oligomeric elastomer in much more effective than using a polymeric elastomer, with respect to intercalation. It is seen that the clay spacing for this case has increased significantly, as the Sid=001 peak at ca 2.4 o has shifted to ca 1.2 o. The interlayer spacing corresponding to these angles, can be calculated by using Braggs law: sin2dN (Equation 3.3) where N = order of diffraction = wavelength of X-Ray d = interplanar spacing, and

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87 = semi-angle of diffraction. Here, wavelength used = 1.4 N = 1. So, for = 1.2 o, d = 33.4 For = 0.6 o, d = 66.8 Hence, it can be concluded that the interlayer spacing has increased by 100%. So, a lot of surface area of clay is now available to the polymer for bonding. This also serves as an explanation for the high tensile strength of oligomer-modified nanocomposite. This is not observed for the polymeric elastomer modification of PP/clay nanocomposite. This could be because of the smaller size of the oligomeric chains and hence greater mobility. So, these chains are likely to penetrate the galleries of the clay better than the polyolefin elastomer and therefore, aid chain intercalation better. Figure 3.19 illustrates this concept. 3.6.3 Differential Scanning Calorimetry The DSC heating thermograms (Figures 3.12 through 3.15) do not show significant changes in Tg for any of the impact-modified nanocomposites. A possible explanation for this behavior is that the elastomer chains might have preferentially penetrated into the clay galleries, and spread them apart. Added to this is the low molecular weight of the polyolefin elastomer compared to PP and also the oligomeric nature of the end functionalized elastomer. The heat requirement for Tg transition is greatest for PP. This is expected because the clay has a lower specific heat than PP and so does Epolene, due to its low molecular weight.

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88 Figure 3.19. Schematic showing that oligomeric elastomers may be more effective in aiding chain intercalation than polymeric elastomers. The cooling thermogram (Figure 3.15) shows some interesting details. The most striking feature of the plot is the significant shift in the Tc (crystallization temperature) for the nanocomposites, ranging from about 4-12 degrees. This means that crystallization phenomenon begins much earlier for the nanocomposites. This indicates that the clay might be acting as a nucleating agent. It is also seen that the oligomer-modified nanocomposite shows highest % crystallinity on a relative scale. This may be explained by the fact that these were able to penetrate the clay galleries more effectively, so that now, there are more nucleation sites per unit volume of the material. This is corroborated by the enhanced tensile strength of the oligomer-modified nanocomposite.

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89 The fact that the polymeric elastomer modified nanocomposite also shows enhanced crystallinity indicates that there is some penetration of these molecules inside the clay galleries. But this is certainly less than its oligomer-modified counterpart, as indicated by XRD data. 3.6.4 Izod Impact Testing From Table 3.10, it is seen that the oligomeric route for impact modification works the best. Even though the tests were not conducted in accordance with ASTM standards, it was ensured that each material was tested in the same way. Specimen preparation, placement of specimen on the test apparatus, etc. were kept the same. The impact strength of the oligomer-modified nanocomposite is about 78% greater than the unmodified nanocomposite and 67% greater than pure polypropylene. This is a significant improvement in the impact strength of PP, which is otherwise known for its poor impact properties. This behavior may be once again explained by the smaller molecular size of the oligomeric impact modifier, which can penetrate into the clay intergalleries more easily than the polymeric impact modifier, due to increased mobility. The smaller size of molecules account for enhanced mobility and hence, aids better in chain intercalation. Another possibility is bonding between Epolene and oligomeric elastomer. It is possible that the oligomeric elastomer chains are grafted onto Epolene chains by reaction with the maleic groups. It is also possible that the other free end of the graft could bond with the clay. This is because the oligomer has greater mobility. This could mean enhanced adhesion, and consequently higher impact strength.

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90 Tensile testing results (Figure 3.8) indicated that the oligomer-modified nanocomposite occupied the highest area under the stress-strain curve. This could also mean highest fracture toughness. 3.6.5 TEM TEM images for both routes of impact modification show significant amount of intercalation. However, a good comparison cannot be drawn due to difference in the instruments used for taking the images. However, as seen from the results of other characterization techniques, the oligomeric, end functionalized elastomer is able to penetrate into the galleries more effectively. 3.7 Conclusions From this research, we can draw the following conclusions: Impact modification of polypropylene clay nanocomposites could be done by the addition of functionalized elastomeric species. The sequence of addition of addition of elastomer had a significant effect on the mechanical behavior of the resulting nanocomposites. It was observed that if the elastomer was added prior to addition of clay, the mechanical properties of the resulting nanocomposites were better than if the elastomer was added after the addition of clay. Impact modification of the nanocomposite involved some sacrifice of tensile properties. However, this was seen to be the least in case of oligomer-modified nanocomposite The addition of elastomer also altered the crystallization behavior of the nanocomposites. The impact-modified nanocomposites showed enhanced crystallinity.

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CHAPTER 4 PMMA / LAPONITE NANOCOMPOSITES 4.1 Introduction Poly (methyl methacrylate) or PMMA is a transparent polymer. It is used in several applications such as windows, paints, intra-ocular lenses, bone cement, lubricating oils and hydraulic fluids. The polymer is transparent due to its amorphous character (atactic PMMA). PMMA is used in windows, because its optical clarity is not adversely affected by increasing thickness, as the case is with silica based inorganic glasses. Figure 4.1 shows the structural formula of atactic PMMA. Figure 4.1. Structural formula of atactic PMMA. 4.2 Research Objectives and Strategy The aim of the research was to enhance the hardness, and abrasion resistance of PMMA, for window based applications. However, in doing so, the optical clarity of PMMA had to be preserved. This is because it is this key emotive property that makes PMMA based products a valuable commodity. The method chosen for the improvement of hardness and abrasion resistance was the formation of a nanocomposite with clay. Montmorillonite, the clay used for earlier 91

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92 research is not a good choice for this research. This is because the mean particle size of montmorillonite is of the order of several microns. Further, the light absorbing chromophores due to the presence of iron oxide in montmorillonite pose additional difficulties in preparing optically clear nanocomposites. Hence, it was proposed that synthetic clay be used. Several authors have reported the preparation and characterization of PMMA/Montmorillonite Clay nanocomposites [125-127]. Hwu et al. have reported a method in which both polymer and clay were dissolved separately and then mixed together [128]. Lee et al. reported a method based on emulsion polymerization with clay [129]. These papers discussed different approaches for synthesizing PMMA/montmorillonite clay nanocomposites such as solution dispersion of clay in MMA followed by polymerization, melt blending etc. However, most of them did not address a key issue associated with PMMA/montmorillonite Clay nanocomposites, which was the transparency or the optical clarity of the nanocomposites. Publications regarding PMMA/montmorillonite Clay nanocomposites did not address the use of synthetic clays as an alternative. So an attempt was made here to enhance the wear/abrasion properties of PMMA and yet keeping it transparent, by forming a nanocomposite with synthetic clay. 4.3 Materials The clay used for the research was Laponite. Laponite is an entirely synthetic product. It is synthesized by treating salts of sodium, lithium and magnesium with sodium silicate under controlled conditions. Milling is done to carry out size reduction of the resulting product. Figure 4.2 shows the layered structure of clay. In the layered structure, there are six magnesium ions sandwiched between two rows of four silicon atoms.

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93 trioctahedral smectite Figure 4.2. Layered structure of Laponite. The magnesium ions are octahedral in shape and the silicon atoms are tetrahedral in shape. This gives a positive forty-four units of charge. Twenty oxygen atoms and four hydroxyl groups balance this. When dispersed in water, the particles exhibit a disc like shape, with a diameter or 25 nm and a thickness of 0.92 nm. Figure 4.3 shows this. Southern Clay Company supplies Laponite clays under different trade names. Figure 4.3. Idealized, average shape of laponite particles when dispersed in water. Laponite has been used for a wide variety of applications such as catalyst components [130-131], biological applications [132-133], electrodes [134], as well as with polymers [135-139]. Three different clays, supplied by Southern Clay Company were examined, namely Laponite RD, Laponite JS and Laponite RDS. The clay used for this research was

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94 Laponite JS. This was a fluorosilicate-modified laponite. Table 4.1 lists its chemical composition. Table 4.2 shows some of its properties. Table 4.1. Chemical composition of Laponites. COMPOSITION (DRY BASIS), WT % MATERIAL JS RD RDS SiO2 50.2% 59.5% 54.5% MgO 22.2% 27.5% 26.0% Li2O 1.2% 0.8% 0.8% Na2 O 7.5% 2.8% 5.6% P2O5 5.4% 4.4% F 4.8% The reason for using JS was that it was the only variety that did not form a thick gel when dispersed in water. Other varieties of Laponite did so, thereby posing processing problems, as far as melt processing was concerned. It is worth mentioning that even though other varieties formed thick gels, they could still be used for modifying PMMA, but with processing difficulties [140]. A significant advantage of using Laponite is that it does not have any chromophores. This is because the synthetic clay is thoroughly purified. Atoglas, under the trade name Plexiglass, supplied the PMMA for this research. The product name was V-825. Table 4.3 lists some of its properties. A compatibilizer material such as Epolene for PP clay nanocomposites because PMMA being a polar polymer was expected to show interactions with clay.

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95 Table 4.2. Physical properties of Laponites. PROPERTY JS RD RDS Appearance Free flowing white powder Free flowing white powder Free flowing white powder Bulk Density 950 kg/m3 1000 kg/m3 1000 kg/m3 Surface Area 300 m2/g 370 m2/g 330 m2/g Loss on ignition 8.7% 8.2% 8.0% PH (2% suspension) 10 9.8 9.7 Storage Hygroscopic, should be stored under dry conditions. Hygroscopic and should be stored under dry conditions. Hygroscopic and should be stored under dry conditions. 4.4 Processing In order to obtain a good dispersion of Laponite JS in water, it is important to adjust the pH of the dispersion. This is because the clay has a net negative charge associated with it. So, by maintaining a pH of about 10 using 1 M NaOH solution, the sodium ions are drawn towards the crystal surface of the clay due to electrostatic attraction. But the osmotic pressure from the water present in bulk pulls them away. So, equilibrium is established in which an electrical double layer is formed. So, when two particles approach each other, they are repelled due to similar charge. Hence, the particles remain dispersed. PMMA pellets were dried for about 30 hours in an air-circulating oven at about 80 oC prior to melt blending. The clay was dispersed in water, to which 2 drops of 1 M NaOH solution were added.

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96 Table 4.3. Properties of PMMA. PROPERTY VALUE TEST METHOD PHYSICAL Melt flow rate (230 oC / 3.8 kg) 3.7 g/10 min. ASTM D1238 Specific Gravity 1.19 ASTM D792 Water Absorption (24 hr. immersion) 0.3% weight gain ASTM D570 MECHANICAL Tensile Strength @ Maximum 10200 psi ASTM D638 Tensile Elongation @ Break 6 % ASTM D638 Tensile Modulus 450000 psi ASTM D638 Flexural Modulus 450000 psi ASTM D790 Notched Izod (73 F/23 C) 0.3 ft-lb/in notch ASTM D256 Rockwell Hardness 93 M ASTM D785 THERMAL HDT (455 kPa; annealed) 221 oF ASTM D648 Thermal Conductivity 1.3 BTU/hr*ft2 *F/in ASTM C177 OPTICAL Refractive Index (ND @ 73 F) 1.49 ASTM D542 However, all mass balance was carried out on a dry basis. Melt processing of the nanocomposites was carried out in a 30mm APV co-rotating reactive twin-screw extruder. This extruder had eight temperature zones from feed to die (including the die zone). The screw L/D was 40. The temperature range used for processing the nanocomposites was 190 oC to 225 oC. Figure 4.4 shows the operation in greater detail.

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97 Figure 4.4. Synthesis of PMMA/Laponite JS nanocomposites using a reactive twin-screw extruder. The clay, dispersed in water/NaOH was placed in an ultrasonicator (Mettler Electronics, 105-120 V, 2 Amperes, 50-60 Hz ultrasonicator) for about 20 minutes, prior to adding it to the polymer. This dispersion was fed to the molten polymer at the feed zone of the extruder. The resulting strands that came out of the die zone were collected in a flowing water bath. Then they were pelletized, and the pellets were dried in an air-circulating oven at about 80 oC. Nanocomposites containing 2 wt% and 5 wt% of the clay were prepared in the way described above. Pure PMMA was also ran through the extruder under identical conditions of processing in order to keep the thermal history of each material same. 4.5 Characterization The following analytical tools were employed in order to measure various properties as well as for obtaining an insight into the microstructure of the processed nanocomposites:

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98 Tensile Testing X-Ray Diffraction Differential Scanning Calorimetry Transmission Electron Microscopy Nano-indentation 4.5.1 Sample preparation Samples for the listed techniques were prepared using compression molding. Compression molding is a process in which a polymer is made to take the shape of a mold by pressing it between two heated plates. The heat melts the polymer (if semi-crystalline) or takes the polymer chains well above the glass transition temperature (if amorphous). The press used for compression molding was a Carver, model C-81000-141 press. In order to prepare the samples, the press was first heated to 450 oF. The mold used was square in shape, with dimensions of 70 mm X 70 mm X 0.8 mm. The mold was placed on a metal plate covered with Teflon coated aluminum foil. The mold was then filled with dried pellets. This plate with mold and the pellets was placed on the bottom plate of the press. Another Teflon coated aluminum foil covered metal plate was placed on top of the mold bearing plate, to give a sandwiched assembly. The bottom plate of the press was raised until the assembly just touched the top plate of the press. The pellets were then allowed to convert into a liquid state by heat transfer from the press. This took about 5-6 minutes. After that the pressure of the system was raised to 10, 000 psi. Initially, due to resistance offered by the liquid polymer as well relatively incomplete conversion to liquid, the pressure dropped below 10,000 psi. Under these circumstances, it was necessary again to raise the pressure to 10,000 psi. This was repeated until the pressure attained a steady value of 10,000 psi. The

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99 pressure could be measured using a gauge attached to the press. A pressure of 10, 000 psi. on the gauge corresponded to 9302 psi. on the sample. This was calculated using the formula: AgPgAsPs (Equation 4.1) Where, Ps = Pressure on the sample As = Cross sectional area of the sample Pg = Gauge pressure Ag = Cross sectional area of the piston of the press. As = 4900 mm2 Ag = 3.14. (32)/4 Pg = 10, 000 psi. After the gauge pressure became steady at 10, 000 psi., the mold was allowed to rest at the abovementioned temperature and pressure for 10 minutes. After that, the heat supply to the press was turned off. The mold was allowed to cool to ambient temperature. The mold containing the solidified sheet was taken out. These sheets served as specimens for all the characterization techniques. 4.5.2 Tensile Testing The aim of performing tensile testing was to evaluate the mechanical response of the materials to a known strain or deformation rate. This gives us a plot of stress versus strain from which we can obtain a wealth of information such as the brittle or ductile behavior, tensile modulus or an indication of stiffness of the material, tensile strength etc. Tensile testing was carried out using an EnduraTEC ELF 3200 series machine. It consisted of the following components:

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100 The linear motor assembly: Had a patented high-bandwidth, low-distortion actuator from Bose Corporation. Testing Chamber: Had facilities for introducing hot air, for increasing temperature as well as introducing liquid nitrogen. A bulb for viewing the test in case liquid nitrogen makes the chamber cloudy was also provided. The door had a transparent section for enabling to view testing while in progress. There were two sets of grips. The bottom grip was stationary and was connected to the load cell. The upper grip was mobile and its motion was regulated by the Wintest software, and ultimately, the linear motor. Temperature Control: With the help of the software, temperature could be varied between oC to 150 oC. Controller box that acted as an interface between the computer and the machine itself. The strain rate used was 0.05 mm/sec. and the testing temperature was 28 oC. Tensile testing data could be obtained for PMMA and PMMA/2 wt% Laponite nanocomposite only. The nanocomposite containing 5-wt % clay was too brittle. Consequently, strips could not be cut, without introducing cracks or notches. Thus, the material was rendered unfit for testing. Figures 4.5 and 4.6 show the results obtained from tensile testing. 4.5.3 X-Ray Diffraction The objective of performing XRD was to explore the possibility of any intercalation or exfoliation in the layered silicates due to possible penetration by the polymer into the clay layers. This is usually determined by the shifts in low angle peaks for the clay. This is because according to Braggs law: sin2dn (Equation 4.2) d = interplanar spacing, n = order of diffraction = wavelength of X-Ray source, and

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101 = semi-angle of diffraction 05101520253000.0050.010.0150.020.0250.03Strain (absolute)Stress (N/mm2) PMMA PMMA+Laponite JS (2% by weight) Figure 4.5. Tensile testing results for PMMA and PMMA + 2 wt % Laponite JS at 0.05 mm/sec, 28 oC. All samples tested showed failure.

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102 12401260128013001320134013601380140014201440146000.511.522.5Clay Loading (wt. %)Tenslie Modulus (N/mm^2) Modulus (N/mm2) Figure 4.6. Dependence of tensile modulus on clay loading. Modulus values were obtained from linear region of the curves in Figure 4.5. Strain rate = 0.05 mm/sec, temperature = 28 oC.

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103 So, as the semi angle varies, the d spacing between the clay layers varies. If the polymer is successful in penetrating the clay layers, then the d spacing of the clay layers increases, thereby reducing the angle corresponding to the peak observed. XRD was performed using a Philips APD 3720 instrument. This uses a Cu-K X-ray source (Wavelength = 1.54 ). The range of angles swept was 0-75 degrees. Reflective mode was used and temperature was 15 oC. Figure 4.7 presents the results obtained from XRD. 4.5.4 Differential Scanning Calorimetry (DSC) DSC describes the behavior of a material when subjected to heat at a controlled rate. This enables us to determine different transitions associated with the polymer such as glass transition, melting transition, besides crystallization behavior etc. DSC on the samples was performed using a ThermoHaake DSC 220 C model instrument. Heating rate used was 10 oC/minute, while cooling rate was 50 oC/min. Two sweeps of this thermal treatment were performed. Figure 4.8 shows the DSC thermograms. Note that in this case, procurement of cooling thermograms is not necessary, because atactic PMMA being an amorphous polymer does not crystallize. The output from the instrument is the heat supplied in microwatts versus temperature. The heat supplied by the instrument is directly proportional to the specific heat of the material. TEM complements XRD by observing a very small section of the material for the possibility of intercalation or exfoliation. It can also provide information on dispersion of particles. It however, supplies information on a very local scale. However, it is a valuable tool because it enables us to see the polymer and the clay on a nanometer scale. 4.5.5 Transmission Electron Microscopy (TEM)

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104 Transmission electron microscopy was performed on the nanocomposites using a JEOL 2010 field emission TEM instrument. Figures 4.9 through 4.14 show the TEM images. Figure 4.7. XRD patterns (reflective mode) for PMMA and PMMA/Laponite nanocomposites. Reflective mode, temperature = 15 oC.

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105 Figure 4.8. DSC thermograms for PMMA and PMMA/Laponite JS nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min.

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106 Figure 4.10. TEM micrograph of PMMA/2 wt % Laponite JS at 100 kX. Figure 4.9. TEM micrograph of PMMA/2 wt % Laponite JS at 60 kX.

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107 Figure 4.11. TEM micrograph of PMMA/2 wt % Laponite JS at 200 kX. Figure 4.12. TEM micrograph of PMMA/5 wt % Laponite JS at 50 kX.

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108 Figure 4.13. TEM micrograph of PMMA/5 wt % Laponite JS at 100 kX. Figure 4.14. TEM micrograph of PMMA/5 wt % Laponite JS at 150 kX.

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109 4.5.6 Nanoindentation Nanoindenting is a relatively new method for characterization of materials mechanical properties on a very small scale. Features less than 100 nm across and thin films less than 5 nm thickness can be evaluated [141-152]. Test methods include indentation for comparative and qualitative hardness measurements. The instrument used for performing nanoindentation characterization was a Hysitron Inc. Micro Nanoindentor. The maximum and minimum load force that could be applied were approximately 5 mN and 5 N, respectively, with a force resolution of 100 nN. A three-sided, pyramid-shaped diamond probe tip was used for indenting the sample. For indenting, the probe was forced into the surface at 100 nN/sec. and to a selected maximum force. The test consisted of a loading and a de-loading cycle, yielding a force-displacement curve for each cycle. The instrument was first calibrated with a standard quartz sample prior to testing the specimens. Four different loads, namely 250, 500, 1000 and 5000 micronewtons were employed. Nanoindentation was done at six different points per sample to ensure consistency in results. Figures 4.15 through 4.18 show representative results. Table 4.4 summarizes the results for every specimen, and includes maximum displacement, force applied and rate of application of force. For preparing specimens, a triangular section of the material from the compression-molded sheet was cut using a penknife. This was mounted on a circular specimen mount, made out of glass using a two-part epoxy mixture. The specimen adhered firmly to the mount upon setting of epoxy.

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110 Figure 4.15. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 250 N. Force was applied at 100 nN/sec.

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111 Figure 4.16. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 500 N. Force was applied at 100 nN/sec.

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112 Figure 4.17. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 1000 N. Force was applied at 100 nN/sec.

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113 Figure 4.18. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites at 5000 N. Force was applied at 100 nN/sec.

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Table 4.4. Nanoindentation results showing force and peak displacements for each specimen tested. Force was applied at 100nN/sec. FORCE (N) DISPLACEMENT (nm) PMMA PMMA + 2 WT % LAPONITE JS PMMA + 5 WT % LAPONITE JS 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 250 175 205 187 196 189 182 154 160 145 161 142 163 132 126 139 141 144 118 500 240 237 239 249 251 255 210 220 218 221 207 219 184 192 200 181 188 190 1000 356 380 375 366 358 371 324 336 318 323 311 339 288 279 274 293 280 276 5000 998 967 972 991 983 973 720 754 731 742 716 725 567 589 580 577 560 581 114

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115 4.6 Discussion of Results Having characterized the materials for different properties and microstructure, it is now important to interpret the results in order to obtain an understanding of different phenomena taking place. From figure 4.5, it is evident that the nanocomposite containing 2 wt% clay has a greater tensile strength. In fact, its tensile strength is 47.3% greater than pure PMMA. The variation of modulus is amplified in Figure 4.6. We see that the modulus of the 2 wt% Laponite JS nanocomposite has increased from 1265 N/mm2 to 1440 N/mm2, an increase of 13.83%. This could be attributed to the addition of clay. Also, PMMA being a polar polymer tends to exhibit stronger interactions (e.g. polar interactions) with clays than non-polar polymers such as PP. The increase in modulus and tensile strength indicated a greater area under the stress-strain curve, which means greater energy to failure, which could possibly convert to higher fracture toughness also. This was indeed one of the goals of the research. Figure 4.7 shows the entire XRD pattern for each material, including pure clay. Being a silicate based material; this also exhibits a low angle peak like montmorillonite. We can also see that there are two high angle peaks for Laponite JS; at ca 56 degrees and ca 68 degrees. From Braggs law, We have d = n / (2 sin ). d = / (2 sin ). Here, = 1.54 4.6.1 Tensile Testing 4.6.2 X-Ray Diffraction Assuming n=1, i.e., first order diffraction,

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116 2 = 56 degrees. So, d = 1.64 Similarly, d-spacing corresponding to the peak at 68 degrees is 1.37 These high angle peaks disappear in the nanocomposites. This could be possibly because of interactions between clay and the polymer. There is not much evidence indicating intercalation or exfoliation. So a concrete explanation could not be provided with the data available. Evidence for interactions between clay and polymer are also furnished by TEM images, besides tensile testing, which are discussed in a later section. However, it should be noted here that in this case, our main aim is to disperse and distribute the nano-size discs uniformly into PMMA. Intercalation or exfoliation due to penetration by polymer chains into clay layers would be an added advantage. 4.6.3 DSC The heat requirements for transition increase as we add clay to the polymer. However, the increase is only 15%. Many reasons are possible. Firstly, clay particles tend It is possible that these d-spacings correspond to the lattice spacings of the crystalline unit cells. DSC thermograms presented in Figure 4.8 do not show a significant shift in Tg. The Tg of the 2 wt% nanocomposite is 1 oC greater than PMMA, while that of 5 wt % nanocomposite is about 2 oC greater than PMMA. This is again because in this case, unlike montmorillonite, our primary objective is not to exfoliate or intercalate the clay with the polymer, but to uniformly disperse the clay nanoparticles. So there is not much chain confinement effect, which would result form the penetration of polymer chains into clay layers, due to addition of clay. The slight in Tg is possibly due to bonding between PMMA and laponite.

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117 to retain moisture. The specific heat of water is 1 cal/goC, whereas Cp values for PMMA and clay are 0.32 cal/goC and 0.27 cal/goC respectively. So, the Cp of water is more than 3 times that of PMMA. So even low moisture content increases the heat requirement for the transition significantly. Further, as stated earlier, the heat supplied by the instrument is directly proportional to the Cp of the material being tested. Secondly, the polymer could be interacting with the clay, through polar interactions. This is supported by the slightly higher Tg values of the nanocomposites. 4.6.4 TEM TEM micrographs are shown in figures 4.9 through 4.14. For the nanocomposite containing 2-wt% clay, we see that even at low magnifications (50 kX), there are domains formed by the aggregation of clay particles. But the particles appear to be separate and not in the form of stacks. This indicates significant dispersion of particles in PMMA matrix. This is of course, facilitated by shearing inside the extruder. At higher magnifications, namely 100 kX and 200 kX, we can observe many gray regions. The regions that appear dark (or black on a relative scale) represent clay, which are composed of higher atomic weight elements. On the other hand, the light background represents primarily the polymer. The marker for 100-kX image indicates that the domain size is approximately 80 nm, which corresponds to three laponite particles juxtaposed. The surrounding region entirely consists of polymer. This is good dispersion, considering the fact that we have used melt compounding. The image obtained at 200 kX shows that just one clay particle is being viewed. As evident from the figure, there is a gray region that separates the two dark regions. This could possibly be due to interactions between polymer and the clay, thereby breaking the 25 nm disks into smaller units. This could

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118 however, be a localized case since XRD does not show any evidence of intercalation or exfoliation. TEM images for the 5 wt % clay nanocomposite show that the domains or agglomerates are much bigger than those found in 2 wt % clay nanocomposite. There is also some stacking of the particles over one other, which was not observed for its lower wt% counterpart. This accounts for the fact that upon visual examination, the 2 wt % clay nanocomposite was almost as clear as PMMA, whereas the 5 wt % clay nanocomposite was translucent. The domain size of 2 wt % PMMA/Laponite JS nanohybrid was around 75 nm, still less than the smallest size discernible to unaided human eyes, which is about 200 nm. An interesting feature of Figure 4.14 is the presence of ridge-like lines. The spacing between these lines is approximately 2-3 nm, while their lateral dimensions are of the order of 25-30 nm. These are possibly due to a stack of clay particles being viewed sideways from the TEM. Using a slightly higher boiling dispersing agent than water could do an improvement in dispersion. Water boils at 100 oC, whereas the processing temperatures exceed 150 oC easily. So, when the clay-dispersion is introduced at the feed zone, the water boils off quickly, leading to agglomeration of particles. Using a higher boiling solvent might ensure that the dispersion stays as a fluid for a longer time inside the extruder. Nanoindentation results shown in Figures 4.15 through 4.18 are in the form of force versus displacement curves. It is necessary to understand what these plots indicate. Firstly, there are two parts for each curve: the ascending part, or the loading region, and then the descending or the de-loading region. 4.6.5 Nanoindentation

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119 Consider the force versus displacement plot for 250 N (Figure 4.15). Upon drawing a horizontal line from 150 micronewtons, marking the points where this line intersected the loading region for each material, and dropping perpendiculars from each of these points, displacement for each material could be obtained. This is nothing but the depth of penetration caused by the tip. Figure 4.19 demonstrates the same. Now, lesser the depth of penetration for a given force, greater is the resistance offered by the material to the penetration of the tip, and consequently, harder that material is. From Figure 4.19 we see that for 150 N, the displacement for PMMA is about 170 nm, whereas it is 160 nm for PMMA + 2 wt % clay and 140 nm for PMMA + 5 wt% clay. Figure 4.19. Interpretation of nanoindentation data.

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120 Thus, it can be said that the 5 wt% clay nanocomposite is the hardest material out of the three. This is quite expected, since it has maximum amount of clay. Figure 4.20 shows a plot of load versus peak displacement in order to make the interpretation easier. 010002000300040005000600010020030040050060070080090010001100Maximum displacement (nm)Load (microNewtons) PMMA PMMA + 2 WT % LAPONITE JS PMMA + 5 WT % LAPONITE JS Figure 4.20. Load versus maximum distance penetrated by the tip. The curves show that the nanocomposite containing 5-wt % clay is the hardest material. Force was applied at 100 nN/sec.

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121 From Figure 4.20 it can be seen that the curve for the 5 wt % clay nanocomposite shows least displacement for a given indenting force, suggesting that it is the hardest material. This is, however, a qualitative measure. Table 4.4 shows the peak displacement and force values for different materials at six different indents for each material tested. The following can be concluded about the research: 4.7 Conclusions Nanocomposites of PMMA and synthetic Laponite JS were prepared with 2 and 5 wt% loadings of clay, and were characterized for different properties. The 2 wt% nanocomposite looked almost as transparent as PMMA, where as its 5 wt% counterpart appeared translucent. This was explained on the basis of domain sizes of clay particles that aggregated. TEM images help elucidating the same. The nanocomposite showed superior mechanical properties, both in terms of modulus and tensile strength. It also showed increased hardness. This was explained on the basis of addition of clay. The primary goal of the research, i.e., obtaining optically clear PMMA with enhanced hardness and abrasion resistance was met with some success. These properties were evaluated using nanoindentation technique, which showed significant increase in hardness upon the addition of clay. It is suggested that the dispersion of the clay could be improved by the use of a higher boiling dispersing agent.

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CHAPTER 5 POLYCARBONATE-FERITE MAGNETIC NANOCOMPOSITES 5.1 Introduction Polycarbonate (PC) is an engineering plastic. It is a transparent polymer, known for its toughness and excellent optical properties. PC gets its name from the carbonate group that is present in its backbone. Bisphenol A and phosgene chemistry is used for producing high molecular weight PC. Figure 5.1 shows the structure of PC. Figure 5.1. Structure of Polycarbonate. PC is used for making shatterproof windows, lightweight eyeglass and lenses. Besides, blends of PC with ABS (Acrylonitrile Butadiene Styrene terpolymer) find extensive use in a variety of appliances. PC can be made as a thermoplastic or as a thermoset, depending on the chemistry used. 5.2 Research Objectives and Strategy Cellular phones have become an integral part of our day-to-day lives. They have made communication very easy and have become quite affordable. The use and production of cellular phones have skyrocketed within the last decade, with many technologies focusing on making these cellular phones lighter in weight and smaller in 122

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123 size. However, the fact remains that the component that accounts for most of their mass is the antenna. This is because it is metallic in nature. Metals have a higher density than polymers. The function of the antenna is to pick up different electromagnetic signals that enable communication. Therefore, it is an indispensable component of a cell phone. However, most of the other components are made out of plastics. For example, the housing is quite often made out of PC/ABS blend. The circuit board is made of epoxy resin. Hence, if we could make the plastic housing magnetic enough to pick up the signals that are normally received by the antenna, tremendous savings in weight of these cell phones could be made. The objective of this research was therefore, to disperse nano-size, magnetic ferrite particles into a polymeric matrix. The matrix material chosen for this research was PC. This is because it is a transparent polymer, and is also a key plastic used in making the housings. Further, the optical clarity of the resulting nanocomposite serves as a guide for determining the extent of dispersion of these nanoparticles. Poly (Vinyl Alcohol) (PVA) used for this research was supplied by Aldrich Chemicals and had a molecular weight of about 13,000 23,000and it was 87-89% hydrolyzed. The role of PVA is expected to be similar to that of a compatibilizer. It can interact with both ferrites and PC, due to its polar character. Figure. 5.5 shows the interactions envisioned between PC, PVA and ferrites 5.3 Materials GE Plastics supplied the PC required for the research, under the trade name Lexan. The name of the product was 123R. Table 5.1 lists some of its properties.

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124 Table 5.1. Properties of Lexan. PROPERTY VALUE UNIT METHOD MECHANICAL Tensile Stress, yield 9000 psi ASTM D 638 Tensile Stress, break 9500 psi ASTM D 638 Flex Stress, yield 13500 psi ASTM D 790 Hardness, Rockwell M 70 ASTM D 785 Taber Abrasion, CS-17, 1 kg 10 MG/1000cy ASTM D 1044 Izod Impact, notched, 73 oF 13.0 ft-lb/in ASTM D 256 THERMAL Vicat Softening Temp, Rate B 310 oF ASTM D 1525 HDT 280 oF ASTM D 648 Thermal Conductivity 0.19 W/moC ASTM C 177 PHYSICAL Specific Gravity, solid 1.20 ASTM D 792 Water Absorption, 24 hours @ 73 oF 0.150 % ASTM D 570 Melt Flow Rate, 300C/1.2 kgf 17.5 g/10 min ASTM D 1238 OPTICAL AND ELECTRICAL Light Transmission, 0.100" 88.0 % ASTM D 1003 Haze, 0.100" 1.0 % ASTM D 1003 Refractive Index 1.586 ASTM D 542 Dielectric Strength, in air, 125 mils 380 V/MIL ASTM D 149 Dielectric Constant, 1 MHz 2.96 ASTM D 150

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125 The nano size ferrite particles for this research were synthesized at the Department of Materials Science and Engineering, University of Florida. Several methods have been reported for synthesis of nanoparticles, such as sol-gel processing [153-154], irradiation [155-156], hydrothermal synthesis [157-158], co precipitation [159-161], aerogel techniques [162-163], mechanical methods [164-165], as well as other techniques [166-172]. The ferrite nano particles for this research were prepared by using a co-precipitation method. The starting materials were: Fe (NO3)3.9H2O = 12.12 g Ni (NO3)3.6H2O = 2.18 g Zn(NO3) 2.6H2O = 2.23 g 50% NaOH & Deionized (DI) water (150 ml). The salts were taken in a small round-bottomed flask with three openings, one for adding DI water and NaOH solution, second for inserting the thermometer and the other for inserting the pH meter. After adding the salts into the flask, 150 mL of DI water was poured into the same. This flask was now placed in a water bath. From then onwards, the flask was stirred magnetically at all times. The water bath was maintained at 70 oC. After ensuring that the temperature was constant at 70 oC, the pH meters probe was inserted into the round-bottomed flask. Next, NaOH solution was added drop wise till the pH reached a value of 11. Now, the mixture was allowed to stir magnetically for 1 hour. After an hour, the flask was taken out of the water bath. The ferrite nanoparticles were separated from the NaOH solution using centrifugation The centrifuge used was an Eppendorf Centrifuge 5810 machine with interchangeable swing-bucket and high-speed

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126 fixed-angle rotors for spinning micro centrifuge tubes. The speed used was 6000 rpm and the time for centrifugation was 5 minutes. The separated ferrite nanoparticles were re-dispersed in DI water. Junyeon Hwang, who performs research for Professor Darryl P Butt at the department of Materials Science and Engineering, University of Florida, characterized these nanoparticles. The primary purpose of characterization was to obtain the particle size distribution of the nanoparticles. However, the microstructure of these nanoparticles was also examined using Scanning Electron Microscopy and X-Ray Diffraction. Figures 5.2 through 5.4 show the results obtained. It seen from these figures that the particles have a size distribution ranging from 0.05 to 1. The mean particle size was found to be 200 nm. XRD showed that the nanoparticles had a crystal lattice parameter of 8.3688 The SEM image also shows that the particles are small in size and have a particle size distribution. Visual inspection revealed that these nanoparticles were brown in color. So, it was expected that the nanocomposites to have a brown tinge associated with them. 5.4 Processing of nanocomposites Several papers on composites of ferrites with polymers have been published. Most of them report solution based processing techniques [173-175]. Mohammed et al. reported a melt processing technique for preparing natural rubber-ferrite composites using a brabender [176]. The nanocomposites for this research were prepared by melt compounding using a 30 mm APV co-rotating twin crew extruder, with 8-zone temperature settings. The temperature range used was 230 C (feed zone) to 255 C (die zone).

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127 0.010.1101234567891011 Particle Size (um )Vol (%) NiZnFerrite Figure 5.2. Results of particle size distribution of as-synthesized by particle size analyzer (UPA). It is measured after high power (650 W) ultrasonication for 10 min. 2030405060708050100150200250300350400450 (440)(311)(533)(511)(422)(400)(222)(220) NiZnFe2O4 Figure 5.3. XRD patterns of NiZnFe2O4 after drying at 60 oC for 3 hours in oven. Lattice parameter, a = 8.368

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128 Figure 5.4. SEM image of Ni-Zn Ferrite after3 drying at 60 for 3 hours in oven. Figure 5.5. Proposed role of PVA in the formation of PC/ferrite nanocomposites.

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129 The screw L/D was 40.The PC pellets were dried in an air-circulating oven for 24 hrs. at 85 oC prior to melt compounding. Table 5.2 shows the temperature settings in each zone. Figure 5.6 shows the operation in the form of a block diagram. Table 5.2. Temperature settings in temperature zones of the twin-screw extruder. Zone Temperature ( oC) Zone 1 (Feed Zone) 230 Zone 2 235 Zone 3 237 Zone 4 240 Zone 5 245 Zone 6 247 Zone 7 250 Zone 8 (Die Zone) 255 5 c.c (equivalent to 5 grams of the nanoparticles) of the ferrite nanoparticles dispersion was taken in a measuring cylinder. This was added to an aqueous solution containing 15 g of PVA (Poly Vinyl Alcohol). The dispersion was magnetically stirred for 1 hour. For melt compounding of PC with the PVA coated ferrite nanoparticles, the mass feed rate of PC used was 42 grams/min. About 500 grams of PC was used. The ferrite/PVA dispersion was introduced at the feed zone of the extruder. The screw rpm was 125. The extruded strands were pelletized and dried in an air-circulating oven for 24 hours at 75 oC. Pure PC was also run through the extruder under the same processing conditions to ensure uniform thermal history for all materials. 5.5 Characterization In this section, the examination of mechanical behavior, thermal behavior, microstructure and extent of dispersion of ferrite nanoparticles is discussed. The following techniques were employed to investigate the same:

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130 Figure 5.6. Block diagram for the processing of PC/Ferrite nanocomposites. Tensile testing X-Ray Diffraction Differential Scanning Calorimetry Transmission electron microscopy SQUID magnetometer 5.5.1 Specimen preparation Specimens were prepared using compression molding. Compression molding is a process in which a polymer is made to take the shape of a mold by pressing it between two heated plates. The heat melts the polymer (if semi-crystalline) or takes the polymer chains well above the glass transition temperature (if amorphous). The press used for compression molding was a Carver, model C-81000-141 press. In order to prepare the specimens, the press was first heated to 450 oF. The mold used was square in shape, with dimensions of 70 mm X 70 mm X 0.8 mm. The mold was placed on a metal plate covered with Teflon coated aluminum foil. The mold was then filled with dried pellets. This plate with mold and the pellets was placed on the bottom plate of the press. Another Teflon coated aluminum foil covered metal plate was placed on top of the mold bearing plate, to give a sandwiched assembly. The bottom plate of the

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131 press was raised until the assembly just touched the top plate of the press. The pellets were then allowed to convert into a liquid state by heat transfer from the press. This took about 5-6 minutes. After that the pressure of the system was raised to 10, 000 psi. Initially, due to resistance offered by the liquid polymer as well relatively incomplete conversion to liquid, the pressure dropped below 10,000 psi. Under these circumstances, it was necessary again to raise the pressure to 10,000 psi. This was repeated until the pressure attained a steady value of 10,000 psi. The pressure could be measured using a gauge attached to the press. A pressure of 10, 000 psi. on the gauge corresponded to 9302 psi. on the sample. This was calculated using the formula: AgPgAsPs (Equation 5.1) Where, Ps = Pressure on the sample As = Cross sectional area of the sample Pg = Gauge pressure Ag = Cross sectional area of the piston of the press. As = 4900 mm2 Ag = 3.14. (32)/4 Pg = 10, 000 psi. After the gauge pressure became steady at 10, 000 psi., the mold was allowed to rest at the abovementioned temperature and pressure for 10 minutes. After that, the heat supply to the press was turned off. The mold was allowed to cool to ambient temperature. The mold containing the solidified sheet was taken out. These sheets served as specimens for all the characterization techniques.

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132 5.5.2 Tensile Testing Tensile testing enables us to evaluate the mechanical response of the materials to a known strain or deformation rate. This gives us a plot of stress versus strain from which we can obtain a wealth of information such as the brittle or ductile behavior, tensile modulus or an indication of stiffness of the material, tensile strength etc. Tensile testing was carried out using an EnduraTEC ELF 3200 series machine. It consisted of the following components: 6. The linear motor assembly: Had a patented high-bandwidth, low-distortion actuator from Bose Corporation. 7. Testing Chamber: Had facilities for introducing hot air, for increasing temperature as well as introducing liquid nitrogen. A bulb for viewing the test in case liquid nitrogen made the chamber cloudy was also provided. The door had a transparent section for viewing testing while under progress. There were two sets of grips. The bottom grip was stationary and was connected to the load cell. The upper grip was mobile and its motion was regulated by the Wintest software, and ultimately, the linear motor. 8. Temperature Controller: With the help of the software, temperature could be varied between oC to 150 oC. 9. Controller box, which acted as an interface between the computer and the machine itself. The deformation rate used was 0.05 mm/sec., and the testing temperature was 30 oC. Figure. 5.7 and Table 5.3 show the results obtained from tensile testing. Table 5.3. Tensile modulus of PC and PC/Ferrite nanocomposite. MATERIAL MODULUS (N/mm2) PURE PC 1604.4 PC/FERRITES/PVA 1742.8 PC/FERRITES 2100

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133 0510152025303540455000.010.020.030.040.050.06Strain (absolute)Stress (N/mm2) PC PC/FERRITES/PVA Figure 5.7. Tensile test comparisons at 0.05 mm/sec., 30 oC. All samples tested showed failure. 5.5.3 X-Ray Diffraction XRD was performed using a Philips APD 3720 instrument. The objective was to investigate shifts in peaks associated with ferrite nanoparticles, giving an indication of interactions between PVA, ferrites and PC. The range of angles swept was 0-75 degrees. Reflective mode was used and the temperature was 15 oC. Figure 5.7 shows the results obtained.

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134 Figure 5.8. XRD patterns for PC and PC/Ferrite nanocomposite using reflective mode at 15 oC. 5.5.4 Differential Scanning Calorimetry (DSC) DSC describes the behavior of a material when subjected to heat at a controlled rate. This enables us to determine different transitions associated with the polymer such as glass transition, melting transition, besides crystallization behavior etc. DSC on the samples was performed using a ThermoHaake DSC 220 C model instrument. Heating rate used was 10 oC/minute, while cooling rate was 50 oC/min. Two sweeps of this thermal treatment were performed. The output of the instrument is a plot between heat supplied in microwatts versus temperature. The heat supplied is directly proportional to

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135 the specific heat of the material being tested. Figure 5.9 shows the results obtained from DSC. It is noteworthy that in this case, obtaining cooling thermograms was not necessary, because PC is an amorphous polymer, and therefore, does not crystallize. Figure 5.9. DSC thermograms for PC and PC/PVA/ferrite nanocomposite. Heating rate =10 oC/min., cooling rate = 50 oC/min.

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136 5.5.5 Transmission Electron Microscopy (TEM) Transmission electron microscopy was performed on the nanocomposites using a JEOL 200 CX TEM instrument. It had a tungsten based thermionic gun. TEM images usually complement XRD data and also enable us to view details on a nanometer scale. Figure 5.10. TEM images of PC/PVA/Ferrite nanocomposite. Figure 5.10 shows the TEM images for PC/PVA/ferrites nanocomposite. We can actually see the polymer and the ferrite nanoparticles and therefore, obtain an idea of

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137 dispersion and distribution of the nanoparticles. However, it should be noted that this technique gives image of a very small section of the material. 5.6 Discussion of Results Having characterized the materials, it was attempted to interpret the results and study the phenomena that possibly occurred in these materials, on a macroscopic as well as microscopic level. A few points were worth noting. The melt viscosity of PC/PVA/Ferrite nanocomposite was unusually low in comparison to pure PC. This was suspected to be due to degradation of PVA. So, it was thought that if this were the case, then the composite without any PVA would exhibit a melt viscosity similar to that of pure PC. Hence, another sample containing PC and ferrite nanoparticles, without PVA was prepared under identical conditions of processing, described earlier, and was designated as PC/ferrites. This product had a slightly lower viscosity than pure PC. This was speculated to be due to alignment of particles in the shear field. Such observations have been reported for polymer silicate nanocomposites [177]. Another sample with PC/PVA without any ferrites was also processed under identical conditions. It was found to be brown in color. Thus, our hypothesis was confirmed. 5.6.1 Tensile Testing Figure 5.7 shows the tensile behavior of both materials, namely PC and PC/PVA/ferrite nanocomposite. From Table 5.3, we can infer that the nanocomposite has a slightly higher modulus and exhibits much brittle behavior in comparison to the pristine polymer, i.e. polycarbonate. This can be explained by the addition of two new phases, namely low molecular weight PVA and ferrites, both contributing to brittle behavior.

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138 This would explain the increased modulus. However, PVA is expected to have poor mechanical properties in comparison to ferrites and PC. So, it can be inferred that if there were no PVA, then the composite should exhibit a higher modulus value and more brittle behavior than if PVA were present. Figure 5.11 shows the results of tensile tests, performed on PC/ferrites under identical conditions and is compared with other materials. 0510152025303540455000.010.020.030.040.050.06Strain (absolute)Stress (N/mm2) PC PC/FERRITES/PVA PC/FERRITES Figure 5.11. Stress strain comparisons for PC/Ferrites with and without PVA, at 0.05 mm/sec., 30 oC. All samples tested showed failure. It shows that PC/ferrites had the greatest modulus and was most brittle. This again, confirmed our hypothesis. Table 5.3 also shows the modulus value for PC/ferrites, which is 30.8% greater than pure PC and 20.5% greater than PC/PVA/ferrites. This shows that

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139 the addition of PVA serves to reduce the tensile modulus, or in other words it tends to make the tensile behavior more ductile. This is also indicated by the lower strain to failure for PC/ferrites in comparison to PC/PVA/ferrites. 5.6.2 XRD XRD patterns (Figure 5.8) showed that the high angle peaks for pure ferrites, at ca 52 degrees and ca 58 degrees disappear in the nanocomposite. This indicates some interaction between the polymers and the nanoparticles, and possibly that significant dispersion of the nanoparticles has been achieved. TEM images support this observation, and these are discussed in a later section. XRD analysis was also done for PC/Ferrites. Figures 5.12 and 5.13 present the results obtained. It was observed from Figure 5.12 that the higher angle peaks disappear. But Figure 5.13 showed that the peak at ca 25 degrees has not disappeared completely in PC/Ferrites. On the other hand, in the nanocomposite containing PVA, this peak disappeared completely. This indicated that the extent of interaction between the components is better in case of PC/PVA/ferrites. This could also possibly mean that the dispersion of ferrite nanoparticles is also better for PC/PVA/ferrites. This could also explain the fact that the physical appearance of PC/Ferrites was much darker than the nanocomposite containing PVA. TEM analysis was performed in order to confirm these findings further and the results are discussed in a later section. 5.6.3 DSC From Figure 5.9, it was seen that Tg of the nanocomposite PC/PVA/ferrite was slightly lower than pure PC. One possibility is that two new phases have been added to

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140 PC. First being the ferrite nanoparticles, which do not show any transitions within the given temperature range, and the second being the low molecular weight PVA. 010020030040050060070045474951535557592 theta (degrees)Intensity (counts) PC/PVA/Ferrites PC/FERRITES (NO PVA) Pure ferrites Figure 5.12 High angle XRD region for various nanocomposites using reflective mode at 15 oC.

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141 1001502002503003504002022242628303234362 theta (degrees)Intensit y ( counts ) PC/PVA/Ferrites PC/FERRITES (NO PV A ) Pure ferrites Figure 5.13. Lower angle region for various nanocomposites using reflective mode at 15 oC. These chains are much easier to move than the bulky and stiff backbone chains of PC, and also have much higher free volume associated with them than PC, due to lower

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142 molecular weight. This is because lower molecular weight translates into greater number of chain ends per unit volume. Also, degradation of PVA was suspected, leading to higher free volume due to creation of low molecular weight species. Thus, the Tg of the composite decreased. However, the Tg of PC/ferrites was found to be almost same in comparison to PC/PVA/ferrites. It is seen that this decrease is approximately 5 degrees, as seen from the DSC thermograms (Figure 5.9). No concrete explanation could be provided but Jiang et al. reported such a lowering in Tg for PC/potassium titanate whisker composites using different coupling agents by [178]. They suggested that such a lowering could occur due to lowering in the overall number average molecular weight. They also proposed that the whiskers and the coupling agent synergistically acted to degrade PC. But in their research, the filler content was much higher (about 10-15% by weight). In this case the amount of filler is quite low (1 % by weight). Another observation was made regarding the heat required for transition (which is an indication of specific heat). The heat required for PC was highest among all the materials. This is expected because PC also has the highest specific heat. However, the low molecular weight PVA and ferrites have a much lower value of specific heat. So it is possible that upon adding them, the heat required for transition for nanocomposites decreased. The observation that the heat requirement for PC/PVA/ferrites was higher than PC/ferrites could be possibly due to the presence of PVA, which could tie the ferrites and PC together.

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143 -8000-7000-6000-5000-4000-3000-2000120125130135140145150155160165Temperature ( OC)DSC (Microwatts) PC PC/PVA/FERRITES PC/FERRITES Figure 5.14. DSC Thermograms for PC and various nanocomposites. Heating rate = 10 oC/min., cooling rate = 50 oC/min.

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144 5.6.4 TEM TEM images shown in Figure 5.10 indicate that the particles are well dispersed and the domains are quite small in size. At many places they are certainly smaller than 100 nm (Figure 5.10 (b)), whereas at some other regions, they can get as big as 200 nm (Figure 5.10 (a)). After the interesting observation was made regarding the melt viscosity of PC/PVA/Ferrites, the material labeled PC/Ferrites was prepared and characterized for different properties. TEM analysis was also performed on the same. Figures 5.15 and 5.16 show the images. Figure 5.15. Dark Field TEM micrographs of PC/Ferrites, without PVA

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145 Figure 5.16. Dark Field TEM micrographs of PC/Ferrites, without PVA at a lower magnification. It should be noted that these images are dark field TEM images. This means that here, instead of direct beam, the diffracted beam is imaged. Thus, the nanoparticles, due to crystalline morphology, appear bright whereas PC being amorphous appears dark. From Figures 5.15 and 5.16, it can be said that the domain sizes are bigger in case of PC/Ferrites than in PC/PVA/Ferrites. Hence, even though addition of PVA has a deleterious effect on the mechanical properties of the nanocomposite, it is still necessary to obtain good dispersion and distribution. 5.6.5 SQUID Magnetometer The materials, namely PC, PC/PVA/Ferrites, and PC/Ferrites were characterized with a SQUID magnetometer at Physics Department, University of Florida. Professor Mark Meisel and J. H Park performed the characterization. The results showed that both

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146 PC/PVA/Ferrites and PC/Ferrites were magnetic in nature [Park, J.H., Meisel, M., 2003. Private unpublished communication]. 5.7 Conclusions From the research performed on PC/ferrite nanocomposites, the following can be concluded. Magnetic nanocomposites with optical clarity comparable to that of pure PC were prepared. A species that interacts with both ferrites and PC is necessary in order to prevent agglomeration of ferrite nanoparticles that leads to the formation of large domains. Such a molecule used for this research was PVA. Such a molecule may tie the filler and the matrix together. A similar theory has been proposed for the role of PVA, but it hasnt been confirmed. Different characterization techniques were performed on the nanocomposites and an insight into their microstructure was obtained. It was found that the nanocomposites exhibited more brittle behavior than pure PC. SQUID magnetometer studies showed that the resulting nanocomposites were magnetic in nature.

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CHAPTER 6 FUTURE RESEARCH 6.1 Introduction This chapter outlines the plans for various experiments and strategies for acquiring a better insight into existing studies as well as exploring novel avenues for the application of polymer nanocomposites. Also included are short notes on recycling ground fiberglass and impact modified fibers. These ideas were inspired from some of the strategies employed in previous research. As far as clay nanocomposites are concerned, prime focus would be on PP/clay nanocomposites. This is because PP is a commercial plastic used over a wide range of applications. It is quite inexpensive as well. 6.2 Polypropylene/Clay Nanocomposites The following studies would help elucidating the structure-property relationships in PP/clay nanocomposites: 1. To study the effect of processing parameters such as temperature, screw speed etc. 2. To study the effect of molecular weight of compatibilizer. 3. To study the effect of extent of maleic anhydride grafting on the morphology and properties of nanocomposites. 4. To compare PP backbone chains modified with functional groups through reactive extrusion with blends of PP and maleic anhydride modified PP as matrix materials for PP/clay nanocomposites. 5. To study the effect of different surface modifications on clay surface on the properties and structure of nanocomposites. 147

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148 6.3 Impact Modification of Nanocomposites Prime focus would be on designing novel processing protocols for improving the impact properties of polymer/clay nanocomposites. For example, in the previous research (Chapter 3), the low molecular weight, end functionalized elastomer was added to Epolene. A modification would be to dissolve it in xylene and add it to the clay. This may result in intercalation of the oligomeric chains inside the clay galleries. This might eventually result in exfoliation of the clay platelets upon adding polymer and compatibilizer. 6.4 Polymer/Nanoclay Modified Cement Cement is a fundamental construction material used for a variety of structural applications. It is known that cements have excellent compression strength. However, they do not have an excellent tensile strength. They exhibit a brittle behavior. It is proposed that by exfoliating montmorillonite clay with the help of a polymer, ductile cements may be prepared that may be possibly used for construction applications where resistance to high velocity projectiles or high seismic shocks is required. However, cement is completely inorganic. Introducing organically modified clay might hinder the solubility of the components as well as alter hydration mechanisms. Hence, it is suggested that montmorillonite in its unmodified form should be used. As a result, the polymer selected for separating the clay platelets should also be polar in nature. PVA might be a good choice. This is suggested on the basis of earlier research performed with ferrite nanoparticles, where the nanoparticles were coated with PVA. Both were easily handled in water. PVA is easily soluble in water. Also, an organic ammonium salt (also soluble in water) could be used to enhance compatibility between the clay and polymer.

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149 6.5 Impact Modified Glass Fibers Some of the fundamental problems associated with glass fiber reinforced polymer composites are interfacial adhesion and formation of voids. Both lead to reduced impact properties. It is suggested on the basis of research on impact modification of PP/clay nanocomposites that an end functionalized oligomeric elastomer may be used with glass fibers for achieving enhanced impact properties. It is possible that one end of the elastomer would bond to the surface of the glass fiber and the other to the matrix resin. In order to enhance adhesion, a possibility that could be explored is the addition of a reactive monomer that would polymerize and bond to the elastomer and the matrix resin. Different parameters such as concentrations of different species, curing temperature etc. could be studied. 6.6 Recycling of Ground Fiberglass Recycling is a subject that has always attracted considerable attention. Recycling of wastes is very important in order to maintain equilibrium in environment. Further, most of the industrial wastes are not biodegradable and therefore create imbalance in ecosystems. One such material is fiberglass. A strategy is proposed here to recycle used fiberglass. The fiberglass could be ground and soaked in a reactive monomer and initiator. The resulting polymerization reaction could help bonding between the new polymer formed and the existing thermoset polymer on the fiberglass. These modified fibers could then be re-used with traditional thermosetting materials such as unsaturated polyester etc. The choice of the monomer should be such that the resulting composite should exhibit good mechanical properties. Different concentrations of the monomer and

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150 initiator could be studied. This idea is proposed on the basis of earlier suggestion for obtaining high-impact glass fibers. 6.7 Characterization of Nanocomposites Several characterization techniques need to be employed for understanding the microstructure of the polymer/clay nanocomposites better. Techniques such as FTIR would elucidate as to which species are bonded to which. SEM with EDS capability would help investigating the dispersion and distribution of clay platelets within the polymer matrix. Permeability measurements may explain the decreased permeation of gases and moisture through nanocomposite films due to a hindered and tortuous pathway offered by the clay platelets. Dynamical mechanical thermal analysis (DMTA) could be an effective tool in obtaining the response of the material to dynamic loading, as well as different transitions associated with the material. Dielectric relaxation techniques could complement DMTA results. Positron annihilation measurements could be performed for obtaining a free volume analysis on the nanocomposites. Further insight into the microstructure of PMMA/Laponite nanocomposites could be obtained through DMTA. Permeability measurements could help in deciding the suitability of their application as coatings. Regarding PC/ferrite nanocomposites, the possibility of PVA acting as a tethering agent between the ferrites and PC needs to be investigated. FTIR, NMR, SEM, DMTA could be used to investigate this. Also, detailed measurements on magnetometers for both A.C and D.C characteristics would elucidate the magnetic behavior of the nanocomposites.

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151 6.8 Conclusions It is seen that the concepts applicable to nanocomposites could possibly extend to other avenues as well, such as recycling of fiberglass and modification of glass fibers. Also, besides using nanocomposites for automotive applications, they may be also used for resistant coating as well as cellular phone housings. Nanocomposite cement seems to be an exciting possibility. The research possibilities seem to be endless. However, one of the aims of this thesis is to outline certain ideas that could possibly develop into potential applications in a systematic way.

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APPENDIX A REPRESENTATIVE DATA FROM WINTEST SOFTWARE Displacement (mm) Load (N) Axial Command (mm) Stress* (N/ mm2) Strain* (Absolute) 0 2.417 0 0 0 0.047 5.603 0.049 1.740603 0.001741 0.096 8.597 0.098 3.376311 0.003556 0.145 11.357 0.146 4.884178 0.00537 0.193 13.953 0.195 6.302448 0.007148 0.243 16.109 0.244 7.480332 0.009 0.292 18.265 0.293 8.658217 0.010815 0.34 19.989 0.342 9.600087 0.012593 0.389 21.664 0.391 10.51519 0.014407 0.438 23.251 0.439 11.38221 0.016222 0.487 24.541 0.488 12.08698 0.018037 0.536 25.688 0.537 12.71361 0.019852 0.585 0.586 13.26541 0.633 0.635 13.8467 0.682 0.684 14.30452 0.731 0.732 14.82572 0.78 0.781 15.2311 0.829 0.83 15.61353 0.877 0.879 16.079 0.927 0.928 16.33031 0.976 0.977 16.73896 1.024 Table A.1 : Tensile testing data for pure polypropylene. 26.698 0.021667 27.762 0.023444 28.6 0.025259 29.554 0.027074 30.296 0.028889 30.996 0.030704 31.848 0.032481 32.308 0.034333 33.056 0.036148 33.654 1.025 17.06567 0.037926 1.073 34.292 1.074 17.41423 0.039741 1.122 34.711 1.123 17.64314 0.041556 1.171 35.315 1.172 17.97312 0.04337 1.219 35.72 1.221 18.19438 0.045148 1.268 1.27 18.43477 0.046963 1.317 36.668 1.318 18.7123 0.048778 1.366 36.97 1.367 18.87729 0.050593 1.415 37.465 1.416 19.14773 0.052407 1.464 37.822 1.465 19.34277 0.054222 1.513 38.158 1.514 19.52633 0.056037 1.561 38.474 1.562 19.69897 0.057815 1.61 38.79 1.611 19.87161 0.05963 1.659 39.058 1.66 20.01803 0.061444 1.708 39.312 1.709 20.1568 0.063259 1.757 39.648 1.758 20.34036 0.065074 1.805 39.806 1.807 20.42668 0.066852 1.854 40.129 1.855 20.60315 0.068667 1.903 40.252 1.904 20.67035 0.070481 1.952 40.493 1.953 20.80201 0.072296 2.001 40.74 2.002 20.93695 0.074111 2.049 40.884 2.051 21.01563 0.075889 36.16 152

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153 2.098 41.111 2.1 21.13964 0.077704 2.147 41.269 2.148 21.22596 0.079519 2.196 41.42 2.197 21.30846 0.081333 2.245 41.488 2.246 21.34561 0.083148 2.294 41.784 2.295 21.50732 0.084963 2.343 41.804 2.344 21.51825 0.086778 2.391 41.887 2.393 21.56359 0.088556 2.44 42.134 2.441 21.69854 0.09037 2.489 42.196 2.49 21.73241 0.092185 2.538 42.34 2.539 21.81108 0.094 2.587 42.415 2.588 21.85205 0.095815 2.636 42.546 2.637 21.92362 0.09763 2.684 42.546 2.686 21.92362 0.099407 2.733 42.649 2.734 21.9799 0.101222 2.782 42.8 2.783 22.06239 0.103037 2.831 42.793 2.832 22.05857 0.104852 2.88 42.917 2.881 22.12631 0.106667 2.929 42.965 2.93 22.15253 0.108481 2.977 43.075 2.979 22.21263 0.110259 3.026 43.102 3.027 22.22738 0.112074 3.075 43.123 3.076 22.23885 0.113889 3.124 43.233 3.125 22.29895 0.115704 3.173 43.191 3.174 22.27601 0.117519 3.222 43.349 3.223 22.36233 0.119333 3.27 43.342 3.272 22.3585 0.121111 3.319 43.432 3.32 22.40767 0.122926 3.368 43.363 3.369 22.36997 0.124741 3.417 43.459 3.418 22.42242 0.126556 3.466 43.459 3.467 22.42242 0.12837 3.514 43.432 3.516 22.40767 0.130148 3.563 43.5 3.565 22.44482 0.131963 3.612 43.487 3.613 22.43772 0.133778 3.661 43.576 3.662 22.48634 0.135593 3.71 43.507 3.711 22.44865 0.137407 3.759 43.466 3.76 22.42625 0.139222 3.807 43.596 3.809 22.49727 0.141 3.856 43.466 3.858 22.42625 0.142815 3.905 43.645 3.906 22.52404 0.14463 3.954 43.542 3.955 22.46777 0.146444 4.003 43.61 4.004 22.50492 0.148259 4.052 43.507 4.053 22.44865 0.150074 4.1 43.583 4.102 22.49017 0.151852 4.149 43.521 4.151 22.45629 0.153667 4.198 43.466 4.199 22.42625 0.155481 4.246 43.576 4.248 22.48634 0.157259 4.295 43.452 4.297 22.4186 0.159074 4.345 43.493 4.346 22.441 0.160926 4.394 43.425 4.394 22.40385 0.162741 4.442 43.418 4.443 22.40002 0.164519 4.491 43.439 4.492 22.41149 0.166333 4.54 43.322 4.541 22.34757 0.168148 4.589 43.308 4.59 22.33993 0.169963 4.637 43.26 4.639 22.3137 0.171741 4.686 43.315 4.687 22.34375 0.173556 4.735 43.349 4.736 22.36233 0.17537 4.784 43.315 4.785 22.34375 0.177185

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154 4.833 43.315 4.834 22.34375 0.179 4.881 43.068 4.883 22.20881 0.180778 4.93 43.171 4.932 22.26508 0.182593 4.978 43.033 4.98 22.18969 0.18437 5.028 43.006 5.029 22.17493 0.186222 5.077 42.999 5.078 22.17111 0.188037 5.125 42.862 5.127 22.09626 0.189815 5.174 42.862 5.176 22.09626 0.19163 5.224 42.759 5.225 22.03999 0.193481 5.272 42.807 5.273 22.06622 0.195259 5.321 42.759 5.322 22.03999 0.197074 5.37 42.553 5.371 21.92745 0.198889 5.418 42.443 5.42 21.86735 0.200667 5.467 42.608 5.469 21.9575 0.202481 5.516 42.649 5.518 21.9799 0.204296 5.565 42.388 5.566 21.8373 0.206111 5.614 42.23 5.615 21.75098 0.207926 5.662 42.168 5.664 21.71711 0.209704 5.711 42.168 5.713 21.71711 0.211519 5.76 42.175 5.762 21.72094 0.213333 5.809 41.9 5.811 21.57069 0.215148 5.858 41.88 5.859 21.55977 0.216963 5.906 41.77 5.908 21.49967 0.218741 5.955 41.591 5.957 21.40188 0.220556 6.004 41.742 6.006 21.48438 0.22237 6.053 41.475 6.055 21.33851 0.224185 6.102 41.468 6.104 21.33468 0.226 6.151 41.303 6.152 21.24454 0.227815 6.199 41.227 6.201 21.20302 0.229593 6.249 40.953 6.25 21.05332 0.231444 6.297 40.884 6.299 21.01563 0.233222 6.345 40.685 6.348 20.90691 0.235 6.395 40.575 6.397 20.84681 0.236852 6.443 40.397 6.445 20.74956 0.23863 6.492 40.149 6.494 20.61407 0.240444 -0.752 -0.137 4.633 -1.39532 -0.02785 -0.319 -0.295 0.373 -1.48164 -0.01181

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APPENDIX B REPRESENTATIVE DATA FROM DSC SOFTWARE Table B.1 : DSC data for pure polypropylene. Time (X 0.1 sec.) Temperature (oC) DSC (W) DDSC (W/min.) 36590 -9.93558 -3002.01 113.566 36595 -9.85018 -3004.29 136.74 36600 -9.76277 -3004.34 140.007 36605 -9.67569 -3006.38 168.615 36610 -9.59319 -3007.81 178.21 36615 -9.50938 -3008.92 173.35 36620 -9.42523 -3010.51 168.337 36625 -9.33843 -3011.93 193.74 36630 -9.25329 -3013.32 193.465 36635 -9.16815 -3015.94 200.268 36640 -9.08334 -3016.45 231.861 36645 -8.99919 -3018.32 245.941 36650 -8.91504 -3020.48 268.799 36655 -8.83023 -3022.5 304.676 36660 -8.74509 -3024.5 320.739 36665 -8.66094 -3028.24 369.108 36670 -8.57514 -3031.01 405.636 36675 -8.49066 -3034.33 446.256 36680 -8.40518 -3038.71 489.252 36685 -8.32037 -3042.67 536.892 36690 -8.23523 -3047.21 572.271 36695 -8.1491 -3052.13 625.128 36700 -8.06395 -3057.67 680.496 36705 -7.97914 -3063.27 712.131 36710 -7.89433 -3069.24 766.318 36715 -7.80853 -3075.93 844.608 36720 -7.72405 -3083.1 893.64 36725 -7.63891 -3091.04 925.585 36730 -7.5541 -3098.06 1010.28 36735 -7.46929 -3106.53 1036.68 36740 -7.38348 -3117.59 1083.74 36745 -7.29768 -3126.6 1153.88 36750 -7.21254 -3134.8 1174.96 36755 -7.12839 -3147.46 1223.95 36760 -7.04258 -3155.63 1300.49 36765 -6.95711 -3166.24 1298.95 36770 -6.87197 -3179.26 1361.23 36775 -6.78848 -3188.95 1381.28 36780 -6.70434 -3200.05 1369.97 36785 -6.60329 -3214.91 1406.05 36790 -6.51881 -3225.84 1451.18 36795 -6.43467 -3240.03 1406.9 36800 -6.34986 -3249.91 1452.02 155

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156 36805 -6.26438 -3261.63 1450.91 36810 -6.18123 -3272.8 1431.74 36815 -6.09741 -3287.17 1450.67 36820 -6.01393 -3296.5 1451.48 36825 -5.93077 -3309.95 1515.17 36830 -5.84795 -3320.96 1610.64 36835 -5.7638 -3334.22 1658.34 36840 -5.68032 -3346.73 1708.18 36845 -5.59716 -3360.99 1893.76 36850 -5.51533 -3376.17 2021.28 36855 -5.43252 -3395.85 2134.43 36860 -5.3479 -3410.99 2389.12 36865 -5.26361 -3429.52 2614.44 36870 -5.17932 -3454.31 2822.53 36875 -5.09503 -3478.39 3056.73 36880 -5.00975 -3498.83 3327.62 36885 -4.9248 -3533.31 3603.43 36890 -4.84117 -3564.6 3762.24 36895 -4.75688 -3596.2 4039.54 36900 -4.67127 -3630.9 4147.27 36905 -4.58665 -3673.15 4406.98 36910 -4.50203 -3711.28 4487.52 36915 -4.41807 -3743.04 4627.68 36920 -4.33444 -3790.94 4765.68 36925 -4.24982 -3824 4974.48 36930 -4.16421 -3866.08 4999.32 36935 -4.08025 -3907.27 4976.16 36940 -3.99563 -3950.24 5245.32 36945 -3.91134 -3993.34 5227.92 36950 -3.82705 -4045.44 5259.96 36955 -3.7421 -4089.76 5301.36 36960 -3.65814 -4125.96 5460.96 36965 -3.57319 -4180.15 5393.4 36970 -3.4889 -4226.6 5527.92 36975 -3.40428 -4262.33 5318.04 36980 -3.31999 -4307.86 5430.36 36985 -3.23603 -4362.35 5501.76 36990 -3.15241 -4399.69 5267.53 36995 -3.06812 -4454 5220.12 37000 -2.98184 -4488.61 5365.32 37005 -2.89656 -4542.29 5196.01 37010 -2.81095 -4584.44 5096.4 37015 -2.72666 -4619.11 4985.04 37020 -2.64171 -4661.61 4758.48 37025 -2.55577 -4709.44 4762.32 37030 -2.47115 -4740.86 4523.16 37035 -2.38653 -4787.05 4410.72 37040 -2.30092 -4815.11 4364.75 37045 -2.21498 -4850.54 4169.04 37050 -2.13102 -4885.47 3938.16 37055 -2.04739 -4919.22 3960.23 37060 -1.96376 -4952 3631.92 37065 -1.8798 -4982.84 3651.96 37070 -1.79254 -5009.03 3476.4 37075 -1.70726 -5037.62 3315.84 37080 -1.62231 -5070.88 3097.21

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157 37085 -1.53669 -5089.71 2939.04 37090 -1.45042 -5119.44 2719.21 37095 -1.36481 -5140.24 2622.12 37100 -1.27986 -5161.79 2452.8 37105 -1.19458 -5177.32 2163.6 37110 -1.10996 -5196.92 2091.96 37115 -1.02369 -5209.44 1812.6 37120 -0.9394 -5227.54 1636.56 37125 -0.85478 -5242.02 1439.64 37130 -0.77016 -5251.18 1307.4 37135 -0.68521 -5264.04 1112.64 37140 -0.60059 -5270.49 980.039 37145 -0.51597 -5276.62 767.883 37150 -0.43036 -5281.76 561.604 37155 -0.34474 -5286.27 389.285 37160 -0.25814 -5289.64 193.441 37165 -0.17154 -5291.11 66 37170 -0.08659 -5291.53 -126 37175 -0.00197 -5288.82 -262.676 37180 0.083314 -5283.62 -453.357 37185 0.169587 -5280.16 -638.754 37190 0.254207 -5275.99 -783.246 37195 0.338827 -5266.12 -961.922 37200 0.423116 -5259.87 -1164.36 37205 0.507736 -5248.49 -1274.4 37210 0.592025 -5236.41 -1449.6 37215 0.675654 -5225.84 -1567.8 37220 0.759943 -5211.37 -1737.84 37225 0.844563 -5191.79 -1896 37230 0.930175 -5177.42 -2078.77 37235 1.01513 -5159.36 -2283.84 37240 1.09908 -5145.34 -2424.12 37245 1.20188 -5121.3 -2493.12 37250 1.28584 -5101.87 -2616.96 37255 1.37212 -5075.26 -2755.68 37260 1.45806 -5046.09 -2846.04 37265 1.54268 -5023.83 -3006.84 37270 1.6273 -5003.61 -2954.28 37275 1.71126 -4973.71 -3060.6 37280 1.79488 -4947.78 -3069.84 37285 1.87818 -4922.19 -3056.88 37290 1.9628 -4894.77 -3216.24 37295 2.0461 -4875.11 -3327.24 37300 2.13105 -4846.82 -3250.44 37305 2.21501 -4819.44 -3291.72 37310 2.29864 -4791.35 -3463.2 37315 2.38326 -4755.81 -3437.04 37320 2.46887 -4726.34 -3674.99 37325 2.55679 -4702.84 -3705.73 37330 2.64241 -4673.47 -3699.36 37335 2.72934 -4633.59 -3756.6 37340 2.81495 -4608.35 -3816.72 37345 2.90089 -4568.86 -3757.2 37350 2.9875 -4538.01 -3875.16 37355 3.07288 -4511.16 -3936 37360 3.15745 -4478.3 -3962.4

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158 37365 3.24203 -4437.75 -3967.2 37370 3.32725 -4413.24 -3906.25 37375 3.41019 -4379.91 -4062.47 37380 3.49477 -4345.47 -4073.28 37385 3.57934 -4303.39 -4177.56 37390 3.66424 -4277.75 -4009.08 37395 3.74816 -4243.34 -4136.16 37400 3.83306 -4199.47 -4239.84 37405 3.91731 -4171.72 -4162.92 37410 4.00188 -4130.17 -4064.64 37415 4.08743 -4103.66 -4253.88 37420 4.17233 -4068.56 -4263.48 37425 4.25756 -4026.59 -4031.04 37430 4.34246 -3998.56 -4092.36 37435 4.42638 -3964.67 -4083.36 37440 4.51194 -3923.26 -4187.28 37445 4.59814 -3888.05 -4093.56 37450 4.68174 -3863.55 -4066.02 37455 4.765 -3830.69 -4133.29 37460 4.8499 -3789.89 -4042.22 37465 4.93317 -3754.72 -4007.65 37470 5.01644 -3727.43 -3971.26 37475 5.10003 -3687.75 -4038.2 37480 5.1833 -3654.12 -4040.16 37485 5.26787 -3627.82 -3940.34 37490 5.35179 -3589.29 -3981.7 37495 5.43539 -3557.11 -3924.84 37500 5.51931 -3527.03 -3846.72 37505 5.60486 -3494.01 -3888.37 37510 5.68944 -3461.53 -3862.34 37515 5.77434 -3422.91 -3870.85 37520 5.85858 -3400.36 -3770.99 37525 5.94348 -3367.19 -3840 37530 6.02838 -3330.09 -3727.85 37535 6.11296 -3305.96 -3757.42 37540 6.1972 -3266.72 -3570.79 37545 6.2821 -3242.86 -3753.29 37550 6.36635 -3207.03 -3692.53 37555 6.45092 -3183.36 -3589.42 37560 6.53517 -3148.41 -3555.88 37565 6.61909 -3125.35 -3418.29 37570 6.70367 -3087.59 -3518.38 37575 6.78693 -3059.48 -3357.02 37580 6.87183 -3030.97 -3367.86 37585 6.95641 -3009.63 -3341.99 37590 7.04 -2981.86 -3361.1 37595 7.12359 -2949.66 -3143.2 37600 7.20947 -2927.28 -3101.07 37605 7.29437 -2902.7 -3110.77 37610 7.37927 -2869.91 -3095.29 37615 7.46352 -2845.25 -3040.18 37620 7.54712 -2825.65 -2936.35 37625 7.633 -2801.06 -2950.92 37630 7.7179 -2771.74 -2921.89 37635 7.82043 -2751.69 -2853.72 37640 7.90631 -2728.51 -2780.63

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159 37645 7.99251 -2704.97 -2857.25 37650 8.07774 -2681.37 -2824.21 37655 8.16362 -2659.21 -2679.14 37660 8.24819 -2632.1 -2714.53 37665 8.33244 -2613.5437670 -2583.768.50028-2548.4837685 -2356.138.84837-2489.668.93131-2197.989.014269.098189.1834-2182.8837725 9.35157-2043.329.68595-2248.3 -2633.52 8.41702 -2587.55 37675 -2565.71 -2584.02 37680 8.58322 -2537.24 8.66551 -2525.48 37690 8.74845 -2509.05 -2352.47 37695 -2305.34 37700 -2466.04 37705 -2447.77 -2198.65 37710 -2435.76 -2146.14 37715 -2417.5 37720 9.26863 -2395.44 -2094.33 -2382.54 37730 9.43549 -2365.26 -1962.86 37735 9.51811 -2346.64 -2086.31 37740 9.60268 -2327.15 -2030.41 37745 -2315.13 -1904.75 37750 9.76889 -2295.76 -1932.83 37755 9.85183 -2284.2 -1889.88 37760 9.93412 -2261.9 -1828.37 37765 10.0158 -1791.01

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APPENDIX CREPRESENTATIVE DATA FROM XRD SOFTWARE Table C.1 : XRD data for PP/COMP/F-OLIG/CLAY (90:4.75:0.25:5) 2* Counts 400 0.02 372 0.04 365 0.06 0.08 0.2 0.3 0.34 357 0.36 0.56 0.62 396 0.64 396 0.66 369 0.68 392 0.7 369 0.72 376 0.74 396 0.76 392 0.78 400 0.8 416 0.82 380 0.84 380 0.86 384 0.88 365 324 0.1 384 0.12 365 0.14 400 0.16 350 0.18 384 384 0.22 376 0.24 376 0.26 384 0.28 342 357 0.32 342 350 0.38 365 0.4 350 0.42 331 0.44 369 0.46 372 0.48 346 0.5 369 0.52 346 0.54 365 353 0.58 353 0.6 342 160

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161 396 0.9 404 0.92 404 0.94 404 0.96 412 0.98 276 1.98 279 2 412 1 396 1.02 396 1.04 420 1.06 441 1.08 437 1.1 384 1.12 424 1.14 428 1.16 408 1.18 392 1.2 437 1.22 404 1.24 437 1.26 388 1.28 396 1.3 441 1.32 433 1.34 384 1.36 420 1.38 445 1.4 380 1.42 353 1.44 396 1.46 380 1.48 404 1.5 392 1.52 350 1.54 353 1.56 365 1.58 306 1.6 376 1.62 331 1.64 328 1.66 346 1.68 365 1.7 335 1.72 313 1.74 303 1.76 324 1.78 296 1.8 313 1.82 282 1.84 276 1.86 317 1.88 286 1.9 331 1.92 276 1.94 253 1.96

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162 253 2.02 296 2.04 292 2.06 276 2.08 279 2.1 320 2.12 282 2.14 246 2.16 292 2.18 266 2.2 296 2.22 296 2.24 256 2.26 266 2.28 292 2.3 282 2.32 296 2.34 296 2.36 269 2.38 313 2.4 279 2.42 317 2.44 296 2.46 269 2.48 259 2.5 299 2.52 310 2.54 272 2.56 296 2.58 289 2.6 276 2.62 296 2.64 299 2.66 266 2.68 272 2.7 259 2.72 269 2.74 228 2.76 259 2.78 240 2.8 246 2.82 250 2.84 228 2.86 219 2.88 243 2.9 246 2.92 213 2.94 225 2.96 202 2.98 219 3 231 3.02 180 3.04 196 3.06 210 3.08 180 3.1 185 3.12

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163 182 3.14 169 3.16 169 3.18 139 3.22 174 3.26 142 3.3 137 3.34 156 3.38 144 3.42 121 3.46 139 3.5 117 3.54 119 3.58 112 3.62 112 3.66 110 3.7 108 3.74 92 3.78 94 3.82 102 3.86 94 3.9 85 3.94 88 3.98 88 4.02 90 4.06 85 4.1 98 4.14 90 4.18 106 4.22 149 3.2 154 3.24 161 3.28 154 3.32 172 3.36 125 3.4 144 3.44 154 3.48 119 3.52 128 3.56 98 3.6 119 3.64 94 3.68 110 3.72 96 3.76 98 3.8 100 3.84 110 3.88 121 3.92 98 3.96 98 4 94 4.04 92 4.08 108 4.12 106 4.16 96 4.2 90 4.24

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164 67 4.26 104 4.28 110 4.3 98 4.34 102 4.38 108 4.42 108 4.46 112 4.5 106 4.54 112 4.58 86 4.62 96 4.66 85 4.7 98 4.74 112 4.78 100 4.82 110 4.86 114 4.9 96 4.94 104 4.98 108 5.02 123 5.06 104 5.1 94 5.14 98 5.18 117 5.22 104 5.26 94 5.3 112 5.34 94 4.32 102 4.36 94 4.4 112 4.44 86 4.48 96 4.52 121 4.56 90 4.6 100 4.64 106 4.68 94 4.72 94 4.76 92 4.8 88 4.84 90 4.88 104 4.92 98 4.96 100 5 98 5.04 90 5.08 102 5.12 108 5.16 98 5.2 114 5.24 102 5.28 106 5.32 114 5.36

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165 112 5.38 94 5.4 106 5.42 130 5.46 104 5.5 90 5.54 112 5.58 108 5.62 112 5.66 96 5.7 83 5.74 119 5.78 106 5.82 117 5.86 96 5.9 114 5.94 108 5.98 123 6.02 121 6.06 132 6.1 96 6.14 123 6.18 139 6.22 110 6.26 130 6.3 112 6.34 112 6.38 130 6.42 114 6.46 102 5.44 94 5.48 114 5.52 119 5.56 98 5.6 117 5.64 117 5.68 92 5.72 119 5.76 100 5.8 102 5.84 117 5.88 110 5.92 102 5.96 112 6 117 6.04 112 6.08 108 6.12 130 6.16 121 6.2 130 6.24 112 6.28 132 6.32 128 6.36 117 6.4 121 6.44 135 6.48

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166 123 6.5 114 6.52 146 6.54 125 6.58 125 6.62 123 6.66 130 6.7 139 6.74 137 6.78 137 6.82 128 6.86 144 6.9 132 6.94 128 6.98 137 7.02 139 7.06 142 7.1 139 7.14 137 7.18 159 7.22 174 7.26 154 7.3 177 7.34 164 7.38 130 7.42 166 7.46 156 7.5 154 7.54 169 7.58 123 6.56 117 6.6 110 6.64 130 6.68 132 6.72 123 6.76 137 6.8 137 6.84 151 6.88 149 6.92 114 6.96 154 7 132 7.04 137 7.08 154 7.12 154 7.16 161 7.2 177 7.24 159 7.28 164 7.32 130 7.36 174 7.4 169 7.44 169 7.48 154 7.52 190 7.56 185 7.6

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167 156 7.62 196 7.64 177 7.66 144 7.7 182 7.74 190 7.78 188 7.82 188 7.86 204 7.9 188 7.94 177 7.98 219 8.02 216 8.06 225 8.1 228 8.14 193 8.18 207 8.22 246 8.26 222 8.3 262 8.34 299 8.38 292 8.42 292 8.46 292 8.5 346 8.54 342 8.58 380 8.62 408 8.64 445 8.66 182 7.68 199 7.72 177 7.76 202 7.8 193 7.84 182 7.88 188 7.92 182 7.96 213 8 216 8.04 188 8.08 243 8.12 210 8.16 237 8.2 231 8.24 256 8.28 250 8.32 250 8.36 262 8.4 276 8.44 320 8.48 342 8.52 365 8.56 376 8.6 408 8.68 458 8.7 524 8.72

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168 534 8.74 538 8.76 562 8.78 595 8.8 660 8.84 8.9 795 8.94 9 924 9.04 9.1 1197 9.14 9.2 1282 9.24 9.3 1225 9.34 9.4 930 9.44 9.5 713 9.54 9.6 497 9.64 9.7 396 9.74 9.8 372 9.84 615 8.82 660 8.86 655 8.88 740 778 8.92 894 8.96 900 8.98 936 924 9.02 1024 9.06 1056 9.08 1096 1116 9.12 1183 9.16 1183 9.18 1303 1303 9.22 1274 9.26 1332 9.28 1246 1218 9.32 1183 9.36 1129 9.38 961 1050 9.42 829 9.46 773 9.48 784 692 9.52 625 9.56 566 9.58 538 497 9.62 467 9.66 408 9.68 433 380 9.72 412 9.76 353 9.78 372 384 9.82

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169 306 9.86 328 9.88 384 9.9 303 9.94 10 339 10.04 10.1 324 10.14 10.2 289 10.24 10.3 303 10.34 10.4 282 10.44 10.5 296 10.54 10.6 279 10.64 10.7 296 10.74 10.8 299 10.84 10.9 320 10.94 328 9.92 350 9.96 331 9.98 357 353 10.02 320 10.06 320 10.08 328 317 10.12 320 10.16 342 10.18 335 339 10.22 289 10.26 303 10.28 303 328 10.32 292 10.36 335 10.38 303 313 10.42 331 10.46 310 10.48 342 286 10.52 320 10.56 292 10.58 269 310 10.62 286 10.66 313 10.68 289 320 10.72 299 10.76 296 10.78 303 317 10.82 320 10.86 331 10.88 335 342 10.92 324 10.96

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170 342 10.98 328 11 346 11.04 11.1 369 11.14 11.2 392 11.24 11.3 384 11.34 11.4 428 11.44 11.5 475 11.54 11.6 576 11.64 11.7 708 11.74 11.8 942 11.84 11.9 1082 11.94 12 1218 12.04 376 11.02 372 11.06 357 11.08 372 353 11.12 380 11.16 369 11.18 384 392 11.22 357 11.26 380 11.28 369 400 11.32 384 11.36 392 11.38 400 400 11.42 396 11.46 412 11.48 441 428 11.52 493 11.56 484 11.58 566 520 11.62 566 11.66 610 11.68 645 702 11.72 713 11.76 812 11.78 807 847 11.82 961 11.86 949 11.88 1018 1076 11.92 1129 11.96 1218 11.98 1218 1282 12.02 1260 12.06 1267 12.08

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171 1183 12.1 1089 12.12 1163 12.14 12.2 961 12.24 12.3 600 12.34 12.4 497 12.44 12.5 424 12.54 12.6 380 12.64 12.7 346 12.74 12.8 361 12.84 12.9 396 12.94 13 437 13.04 13.1 449 13.14 13.2 1109 12.16 1024 12.18 1011 930 12.22 870 12.26 784 12.28 724 681 12.32 600 12.36 562 12.38 538 520 12.42 493 12.46 416 12.48 416 392 12.52 396 12.56 396 12.58 369 372 12.62 388 12.66 376 12.68 396 372 12.72 380 12.76 400 12.78 404 388 12.82 404 12.86 420 12.88 380 404 12.92 441 12.96 412 12.98 412 412 13.02 412 13.06 449 13.08 467 445 13.12 449 13.16 471 13.18 506

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172 529 13.22 543 13.26 566 13.28 562 586 13.32 660 13.36 692 13.38 650 676 13.42 718 13.46 718 13.48 756 790 13.52 858 13.56 841 13.58 829 906 13.62 912 13.66 841 13.68 888 870 13.72 888 13.76 888 13.78 790 801 13.82 807 13.86 778 13.88 729 708 13.92 666 13.96 650 13.98 640 615 14.02 600 14.04 571 14.06 595 14.08 538 14.1 524 14.12 506 14.16 543 14.18 502 14.2 502 14.22 488 14.26 454 14.28 471 441 14.32 529 13.24 13.3 586 13.34 13.4 697 13.44 13.5 824 13.54 13.6 918 13.64 13.7 930 13.74 13.8 807 13.84 13.9 671 13.94 14 529 14.14 488 14.24 14.3

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173 428 14.34 424 14.36 458 14.38 462 14.4 449 14.44 14.5 14.7 445 14.74 14.8 15 424 14.42 404 14.46 445 14.48 475 408 14.52 384 14.54 449 14.56 433 14.58 408 14.6 428 14.62 384 14.64 380 14.66 428 14.68 396 369 14.72 416 14.76 369 14.78 428 392 14.82 400 14.84 404 14.86 437 14.88 408 14.9 412 14.92 400 14.94 404 14.96 376 14.98 372 388 15.02 412 15.04 416 15.06 392 15.08 384 15.1 376 15.12 400 15.14 353 15.16 376 15.18 400 15.2 396 15.22 396 15.24 404 15.26 376 15.28 357 15.3 396 15.32 396 15.34 376 15.36 384 15.38 353 15.4 400 15.42 380 15.44

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174 384 15.46 361 15.48 412 15.5 437 15.52 404 15.54 15.6 15.92 15.94 15.96 15.98 16 16.02 16.04 16.06 762 16.12 773 16.14 16.16 16.18 16.2 858 16.22 16.26 876 16.32 404 15.56 424 15.58 428 445 15.62 400 15.64 437 15.66 384 15.68 488 15.7 437 15.72 471 15.74 458 15.76 484 15.78 520 15.8 524 15.82 571 15.84 557 15.86 557 15.88 576 15.9 566 692 666 610 650 686 692 767 762 16.08 745 16.1 790 829 853 853 16.24 858 888 16.28 858 16.3 853 16.34 882 16.36 818 16.38 912 16.4 858 16.42 847 16.44 824 16.46 835 16.48 853 16.5 824 16.52 900 16.54 853 16.56

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175 858 16.58 870 16.6 894 16.62 853 16.64 841 16.66 876 16.68 870 16.7 918 16.72 912 16.74 942 16.76 967 16.78 942 16.8 1005 16.82 980 16.84 1037 16.86 1063 16.88 1024 16.9 1005 16.92 1030 16.94 1063 16.96 1037 16.98 986 17 1050 17.02 1056 17.04 767 17.26 740 17.3 635 17.32 645 17.34 625 17.36 586 17.38 534 17.4 548 17.42 529 17.44 480 17.46 449 17.48 437 17.5 449 17.52 424 17.54 380 17.56 433 17.58 365 17.6 357 17.62 357 17.64 310 17.66 369 17.68 1024 17.06 1030 17.08 973 17.1 980 17.12 912 17.14 961 17.16 888 17.18 894 17.2 829 17.22 790 17.24 740 17.28

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176 342 17.7 320 17.72 292 17.74 299 17.76 320 17.78 219 18.78 219 18.8 313 17.8 279 17.82 289 17.84 250 17.86 289 17.88 266 17.9 292 17.92 266 17.94 282 17.96 269 17.98 253 18 266 18.02 262 18.04 266 18.06 282 18.08 272 18.1 234 18.12 266 18.14 234 18.16 262 18.18 272 18.2 240 18.22 250 18.24 266 18.26 276 18.28 256 18.3 246 18.32 246 18.34 243 18.36 256 18.38 237 18.4 250 18.42 279 18.44 234 18.46 243 18.48 269 18.5 222 18.52 262 18.54 243 18.56 243 18.58 231 18.6 225 18.62 269 18.64 266 18.66 219 18.68 282 18.7 237 18.72 237 18.74 240 18.76

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177 228 18.82 216 18.84 250 18.86 210 18.88 259 18.9 231 18.92 240 18.94 237 18.96 240 18.98 228 19 240 19.02 237 19.04 286 19.06 246 19.08 269 19.1 237 19.12 266 19.14 228 19.16 250 19.18 282 19.2 262 19.22 240 19.24 276 19.26 269 19.28 272 19.3 240 19.32 272 19.34 256 19.36 262 19.38 262 19.4 289 19.42 269 19.44 250 19.46 256 19.48 266 19.5 276 19.52 276 19.54 286 19.56 243 19.58 286 19.6 262 19.62 276 19.64 269 19.66 279 19.68 276 19.7 282 19.72 276 19.74 272 19.76 19.84 19.88 19.92 276 19.78 259 19.8 259 19.82 286 256 19.86 269 262 19.9 286

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178 289 19.94 266 19.96 20 20.04 20.08 20.12 20.16 20.2 20.24 20.28 20.32 262 19.98 269 262 20.02 269 289 20.06 317 269 20.1 282 317 20.14 313 310 20.18 324 313 20.22 331 320 20.26 335 331 20.3 353

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BIOGRAPHICAL SKETCH The author was born in Tiruvallur, a small district near Chennai in Tamil Nadu, India. He obtained his high school diploma from Kendriya Vidyalaya, IFFCO, Gandhidham, Gujrat, India. He then pursued a Bachelor of Engineering degree in chemical engineering at Sardar Vallabhbhai Regional College of Engineering and Technology, Surat, Gujrat, India. He then attended University of Florida for pursuing a Master of Science degree in materials science and engineering. He worked with Professor Charles Beatty as a research assistant and performed research on polymeric nanocomposites. 193


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Permanent Link: http://ufdc.ufl.edu/UFE0001201/00001

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Title: Polymer silicate and magnetic polymer nanocomposites: processing and characterization
Physical Description: Mixed Material
Creator: Bhaskar, Ajit ( Author, Primary )
Publication Date: 2003
Copyright Date: 2003

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Material Information

Title: Polymer silicate and magnetic polymer nanocomposites: processing and characterization
Physical Description: Mixed Material
Creator: Bhaskar, Ajit ( Author, Primary )
Publication Date: 2003
Copyright Date: 2003

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Source Institution: University of Florida
Holding Location: University of Florida
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POLYMER SILICATE AND MAGNETIC POLYMER NANOCOMPOSITES:
PROCESSING AND CHARACTERIZATION















By

AJIT BHASKAR


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

UNIVERSITY OF FLORIDA


2003
































Copyright 2003

by

Ajit Bhaskar

































This document is dedicated to Professor Beatty, my parents and my sister.















ACKNOWLEDGMENTS

First of all, I would like to express my heartfelt gratitude to Professor Beatty, my

committee chair and mentor. He not only taught me the fundamentals of polymers, but

also provided me financial support, and showed me the meaning of the word "research."

I would like to thank my committee members Professor Abbas A Zaman and

Professor Hassan El-Shall for their invaluable guidance and support.

I would also like to thank Professor Beatty's graduate students Nathan Tortorella,

Woo-Hyuk Jung and Xiaosang Huang, not only for helping me with my research but also

for making research a pleasant and memorable experience.

I am also very thankful to my parents and younger sister who have encouraged me

for all these years.

Finally I would like to thank all the funding agencies.
















TABLE OF CONTENTS

page

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

LIST OF TABLES ........ ........... ....... .................... ............. viii

LIST OF FIGURES ............................... ... ...... ... ................. .x

A B S T R A C T .........v.................................... ....................... ................. xv

CHAPTER

1 IN TR OD U CTION ............................................... .. ......................... ..

1.1 P olym er N anocom posites ................................................................ ............... ....2
1.1.1 Effect of Compatibilizer Concentration on the Mechanical Properties
of Polypropylene-Montmorillonite Nanocomposites .............. .................2
1.1.2 Improving Impact Properties of Polypropylene/Clay Nanocomposites.......4
1.1.3 PMMA/Laponite Nanocomposites .....................................................5
1.1.4 Polycarbonate-Ferrite Nanocomposites.........................................5
1.1.5 F uture R research ..... ............ .. ..... ..... .................... .......... ......... .... .....6
1.2 A Word on Processing and Characterization of Nanocomposites..........................6

2 EFFECT OF COMPATIBILIZER CONCENTRATION ON MECHANICAL
PROPERTIES OF POLYPROPYLENE/MONTMORILLONITE
N A N O C O M P O SIT E S ......... .. ............. ..............................................................8

2.1 Introduction ......... ....................................................... .... ............... ... 8
2.2 Polypropylene Clay N anocom posites................................................................ 11
2.3 Research Objectives and Strategy ............................................. ............... 13
2 .4 M a te ria ls ............................................................................................................... 1 3
2.5 Processing ..................................................................... ......... 15
2.6 C characterization ..... ............................ ........................... .. ......18
2.6.1 Specim en Preparation.......................................................... ............... 19
2 .6.2 T ensile T testing ..................... .. .... ................... .... .. ........... 23
2.6.3 X-Ray Diffraction...................................................... 29
2.6.4 Differential Scanning Calorimetry (DSC)............................................35
2.6.5 Transmission Electron Microscopy (TEM)..............................................45
2.7 D discussion of R esults......... ................. ....................................... ............... 50
2 .7.1 T ensile T testing ..................... .. .... ................... .... .. ........... 50









2 .7 .2 X -R ay D iffraction ............................................................ .....................52
2 .7 .3 D S C ................................................................5 3
2 .7.4 T E M ............................................................ 55
2 .8 C o n c lu sio n s ..................................................................................................... 5 6

3 IMPACT MODIFICATION OF POLYPROPYLENE/MONTMORILONITE
CLAY NANOCOMPOSITES ................................................. ...............57

3.1 Introduction .............................................................................. ...... ................. 57
3.2 Research Strategies .................. ....... ............. 62
3 .3 M a te ria ls ............................................................................................................... 6 3
3.4 Processing ............ ................ ..................................................................67
3.5 Characterization ...... ............... ...... .............70
3.5.1 Specim en Preparation............................................ 71
3 .5 .2 T en sile T e stin g ..................................................................................... 7 3
3 .5 .3 X -R ay D iffraction ................................................................................. 7 5
3.5.4 Izod Impact Testing ......... .... ......... ...............77
3.5.5 Differential Scanning Calorimetry ........................................ ....79
3.5.6 Transmission Electron Microscopy ............................... ............79
3.6 Discussion of Results ............. .... ......... ..... ........85
3 .6 .1 T en sile T e stin g ..................................................................................... 8 5
3 .6 .2 X -R ay D iffraction ................................................................................. 86
3.6.3 D ifferential Scanning Calorim etry ........................................ ............ 87
3 .6 .4 Izod Im pact T testing .............................................................................. 89
3.6.5 TEM ................. ....... ..... .......... 90
3 .7 C o n c lu sio n s ..................................................................................................... 9 0

4 PMMA / LAPONITE NANOCOMPOSITES ................................................... 91

4 .1 In tro d u ctio n ................. .................................................................................... 9 1
4.2 Research Objectives and Strategy ............................. ............... 91
4 .3 M a te ria ls ............................................................................................................... 9 2
4 .4 P ro c e ssin g ...............................................................................................9 5
4.5 Characterization ............. ..... ............. ............... 97
4.5.1 Sample preparation ............... ..... ........ ........... 98
4 .5 .2 T en sile T estin g ..................................................................................... 9 9
4.5.3 X -R ay D iffraction ............................ .................................. 100
4.5.4 Differential Scanning Calorimetry (DSC)................................ 103
4.5.5 Transmission Electron M icroscopy (TEM ) ..............................................103
4.5.6 N anoindentation ............................................. ............... 109
4.6 D discussion of R results ................................... ........ ................................115
4.6.1 Tensile Testing ................................ ............ ............ 115
4.6.2 X-Ray Diffraction ............................ .......... ............ 115
4.6.3 D SC ........................................................................... ..............................116
4 .6 .4 T E M .................................................................................................... 1 1 7
4 .6.5 N anoindentation ................................18.............................
4 .7 C o n c lu sio n s ................................................................................................... 12 1









5 POLYCARBONATE-FERITE MAGNETIC NANOCOMPOSITES................ 122

5 .1 In tro d u ctio n ........................ .... ................ ............. ................ 12 2
5.2 Research Objectives and Strategy ........................................... ............... 122
5.3 M materials ...................................................... ................. 123
5.4 Processing of nanocomposites................................ ......................... ........ 126
5.5 Characterization .................................................... ........................ 129
5.5.1 Specim en preparation ...................................................... ................. 130
5.5.2 Tensile Testing ................... ................ .................. ..... .... 132
5.5.3 X -R ay D iffraction ................... ....... ..................................................... 133
5.5.4 Differential Scanning Calorimetry (DSC)........................................134
5.5.5 Transmission Electron M icroscopy (TEM ).............................................136
5.6 D discussion of R esults...................... .. .. .................... ................. ............... 137
5.6.1 Tensile Testing ................................ .. ... .... .... ...............137
5 .6 .2 X R D .................................................................................................... 1 3 9
5 .6 .3 D S C .................................................................................................... 1 3 9
5.6 .4 T E M ........................................................... 144
5.6.5 SQUID Magnetometer ............. .. ............ .............. ........... 145
5 .7 C on clu sion s............................................................................................. 14 6

6 FUTURE RESEARCH ............... ....................................... 147

6.1 Introduction ......... ......... ..... ..........................147
6.2 Polypropylene/Clay Nanocomposites ............. ........................... .................147
6.3 Impact M odification of Nanocomposites ...................................... ............... 148
6.4 Polymer/Nanoclay M odified Cement ......... ................ ..............................148
6.5 Im pact M odified G lass Fibers ........................................ ........................ 149
6.6 Recycling of Ground Fiberglass .... ................... ...............149
6.7 Characterization of N anocom posites............................................................... 150
6 .8 C o n clu sio n s................................................. ................ 15 1

APPENDIX

A REPRESENTATIVE DATA FROM WINTEST SOFTWARE ...........................152

B REPRESENTATIVE DATA FROM DSC SOFTWARE ........................................155

C REPRESENTATIVE DATA FROM XRD SOFTWARE ......................................160

L IST O F R E F E R E N C E S ...................................................................... ..................... 179

BIOGRAPHICAL SKETCH ............................................................. ............... 193
















LIST OF TABLES


Table page

2.1. Properties of Polypropylene used for the research. ............................... ..................14

2.2. Physical properties ofNanomer 1.34 TCN. ................................... ............... 14

2.3. Properties of Epolene G -3003......... ............. ............................... ............... 15

2.4. Different temperature Zones of the twin screw extruder................ ..................17

2.5. D resignation of different PPCN s....................................................... ............... 18

2.6. Tensile moduli and tensile strengths of PP and PPCNs. Strain rate = 0.01
mm/sec., temperature of testing = 29C. ................. ........ ....................30

3.1. Properties of Basell Polypropylene used for the research. ...................................65

3.2. Properties of Epolene G -3003......... ............................................ ............... 65

3.3. Physical properties ofNanomer 1.34 TCN. ................................... ............... 65

3.4. Properties of Engage 8842. ............................................... ............................. 66

3.5. Properties of oligomeric, epoxy and hydroxyl end functionalized polybutadiene. ....66

3.6. Properties of Glycidyl m ethacrylate ........................................ ....................... 67

3.7. Preparation of Impact modified nanocomposites. .....................................................70

3.8. Percent compositions of different nanocomposites by weight (dry basis). ...............71

3.9. Tensile properties of impact modified PPCNs........................................................75

3.10. Impact strengths of impact modified PP/clay nanocomposites. ............................78

4.1. Chem ical composition of Laponites. ........................................ ....... ............... 94

4.2. Physical properties of L aponites .................................................................... .. .... 95

4 .3 P properties of P M M A ................................................................................. ......... 96









4.4. Nanoindentation results showing force and peak displacements for each
specimen tested. Force was applied at 100nN/sec. ................................................114

5.1. Properties of Lexan. .................. .............................. ......... .. ........ .... 124

5.2. Temperature settings in temperature zones of the twin-screw extruder .................129

5.3. Tensile modulus of PC and PC/Ferrite nanocomposite ..................................132
















LIST OF FIGURES


Figure p

1.1. Classification of research areas on the basis of filler employed..............................1

1.2. Structure of m ontm orillonite clay ..............................................................................3

1.3. Different types of clay platelet dispersion by diffusion of polymer chains ..............3

2.1. Schem atic illustrations. ............................................... ........ .. ............ 10

2.2. A model for the torturous zigzag diffusion path in an exfoliated polymer clay
nanocomposite when used as a gas barrier.............. .............................................. 11

2.3. Orientations of alkyl ammonium ions in the galleries of layered silicates with
different layer charge densities. ........................................ ......................... 12

2.4. A M aleic anhydride group. ............................................... .............................. 15

2.5. Schematic of reactive twin-screw extruder .... ........... .................................... 16

2.6. Block diagram of the extruder showing different zones.....................................17

2.7. Schematic diagram of Carver compression molding press.................. ...............20

2.8. Placement of mold between two metal plates covered with Teflon coated
alum inum foil. ........................................................................2 1

2.9. The EnduraTEC ELF 3200 series machine. .................................... .................25

2.10. Specim en testing cham ber. .............................................. ............................. 26

2.11. Temperature control box and emergency stop buttons...................... ..............27

2.12. Control unit. This acts as an interface between the computer and software............27

2.13. Stress versus strain plots for different PPCNs. Strain rate = 0.01 mm/sec.,
tem perature of testing = 29 C ......................................................................... ..3 1

2.14. Dependence of tensile modulus on compatibilizer concentration.
Strain rate = 0.01 mm/sec., temperature of testing = 29 C. ..................................32









2.15. Dependence of tensile strength on compatibilizer concentration.
Strain rate = 0.01 mm/sec., temperature of testing = 29 C. ..................................33

2.16. Fundamentals of X-ray Diffraction. Here, 1= path difference, d= interplanar
spacing and 0 = semi-angle of diffraction. ........................................ ............... 34

2.17. Complete XRD patterns for PP and PPCNs in reflective mode, at 15 oC. ..............36

2.18. Lower angle region of XRD patterns for PP and PPCNs in reflective mode, at
1 5 oC ................................................................................ 3 7

2.19. Glass transition on a DSC thermogram ........................................ ...............39

2.20. Crystallization transition on a DSC thermogram...................................................39

2.21. Melting transition on a DSC thermogram.................................................40

2.22. DSC heating thermograms for PP and PPCNs. Heating rate = 10 oC/minute. .........41

2.23. Tg region of DSC heating thermograms for PP and PPCNs. Heating rate = 10
oC /m inute............................................................... ..... .... ......... 42

2.24. Tm transition for PP and PPCNs obtained from DSC heating thermogram.
H eating rate = 10 0 C /m inute ......................................................................... ..... 43

2.25. DSC cooling thermograms for PP and PPCNs. Cooling rate = 50 oC/minute..........44

2.26. Void formation between the folded silicate layers during the microtoming of the
bulk nanocomposite................... ..... ........... .... ..... .........46

2.27. TEM micrographs of PP/CLAY (95:5).................................. ....................... 47

2.28. TEM micrographs of PP/EP/CLAY (85.5:9.5:5).............. ................ 48

2.29. TEM micrographs of PP/EP/CLAY (85.5:9.5:5).............. ................ 49

3.1. Notched Izod impact strength of nylon 6 and 95/05 composites as a function of
clay lo adin g ....................................................... ................ 5 8

3.2. SEM observation: (a) Cavitated nanocomposite; (b) Fibrillated nanocomposite
and polym er/clay interaction ....................................................... ............... 60

3.3. Notched Izod impact strength of nylon 6 and 95/05 composites as a function of
tem perature............................................................................................... 6 1

3.4. Effect of addition of elastomer on craze crack structure ........................................62

3.5. Stress strain curves for different types of materials.................................................64









3.6. Schematic representation showing mixing of Epolene with oligomeric
polybutadiene. ........................................................................69

3.7. Synthesis of impact modified nanocomposites using a reactive twin-screw
extruder ........................................................................... .. ........ ...... 7 1

3.8. Tensile behavior of PP and impact modified PP/Clay nanocomposites at 0.01
m m /sec., 28 C ....................................................................... 74

3.9. XRD patterns for PP and impact modified PP clay nanocomposites in reflective
m o d e, at 15 .........................................................................................................7 6

3.10. Low angle region of XRD plot. ............. ....................................... ..................... 77

3.11. Izod im pact testing apparatus........................................................ ............... 78

3.12. DSC heating thermogram for PP and impact modified PP/clay nanocomposites.
Heating rate = 10 C/min., cooling rate = 50 C/min. ............................................80

3.13.Tg region of DSC heating thermograms ......... ................. ..... ..................81

3.14. Tm region of DSC heating thermograms....................................... ............... 82

3.15. DSC cooling thermogram for PP and impact modified PP/clay nanocomposites.
Heating rate = 10 C/min., cooling rate = 50 C/min. ............................................83

3.16. TEM micrograph of PP/COMP/F-OLIG/CLAY. ...........................84

3.17. TEM micrographs of PP/COMP/F-POE/CLAY..............................84

3.18. TEM micrographs of PP/COMP/F-POE/CLAY at a higher magnification .............85

3.19. Schematic showing that oligomeric elastomers may be more effective in aiding
chain intercalation than polymeric elastomers. .................. ........................ 88

4.1. Structural formula of atactic PM M A. ......................... ....................................... 91

4.2. L ayered structure of L aponite ........................................................................ .. ..... 93

4.3. Idealized, average shape of laponite particles when dispersed in water...................93

4.4. Synthesis of PMMA/Laponite JS nanocomposites using a reactive twin-screw
extruder ........................................................................... .. ........ ...... 97

4.5. Tensile testing results for PMMA and PMMA + 2 wt % Laponite JS at 0.05
mm/sec, 28 C. All samples tested showed failure. ............................................. 101









4.6. Dependence of tensile modulus on clay loading. Modulus values were obtained
from linear region of the curves in 4.5. Strain rate = 0.05 mm/sec,
tem perature = 28 C ....................... .... .............. .......................... 102

4.7. XRD patterns (reflective mode) for PMMA and PMMA/Laponite
nanocomposites. Reflective mode, temperature = 15 C. ......................................104

4.8. DSC thermograms for PMMA and PMMA/Laponite JS nanocomposites.
Heating rate = 10 C/min., cooling rate = 50 C/min. .........................................105

4.9. TEM micrograph of PMMA/2 wt % Laponite JS at 60 kX................................ 106

4.10. TEM micrograph of PMMA/2 wt % Laponite JS at 100 kX............................. 106

4.11. TEM micrograph of PMMA/2 wt % Laponite JS at 200 kX..............................107

4.12. TEM micrograph of PMMA/5 wt % Laponite JS at 50 kX............................... 107

4.13. TEM micrograph of PMMA/5 wt % Laponite JS at 100 kX............................. 108

4.14. TEM micrograph of PMMA/5 wt % Laponite JS at 150 kX............................. 108

4.15. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites
at 250 aN Force w as applied at 100 nN /sec...................................... .................. 110

4.16. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites
at 500 aN. Force was applied at 100 nN/sec .............. .................. .................. 11

4.17. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites
at 1000 aN Force was applied at 100 nN/sec .................................. ................. 112

4.18. Nanoindentation results for PMMA and PMMA/Laponite JS nanocomposites
at 5000 aN Force was applied at 100 nN/sec .................................. .................113

4.19. Interpretation of nanoindentation data. .............. ........ .................... 119

4.20. Load versus maximum distance penetrated by the tip. The curves show that the
nanocomposite containing 5-wt % clay is the hardest material. Force was
applied at 100 nN /sec. ...................... .. .................... ............................ 120

5.1. Structure of Polycarbonate ...................................................................... 122

5.2. Results of particle size distribution of as-synthesized by particle size analyzer
(UPA). It is measured after high power (650 W) ultrasonication for 10 min........127

5.3. XRD patterns of NiZnFe204 after drying at 60 C for 3 hours in oven. Lattice
param eter, a = 8.368 A .......................... .. ............ .......................... ..... 127

5.4. SEM image of Ni-Zn Ferrite after3 drying at 60 C for 3 hours in oven. .................128









5.5. Proposed role of PVA in the formation of PC/ferrite nanocomposites. .................128

5.6. Block diagram for the processing of PC/Ferrite nanocomposites. ...........................130

5.7. Tensile test comparisons at 0.05 mm/sec., 30 C................... ............................... 133

5.8. XRD patterns for PC and PC/Ferrite nanocomposite using reflective
m ode at 15 C ..................................................................... 134

5.9. DSC thermograms for PC and PC/PVA/ferrite nanocomposite. Heating rate =10
C/m in., cooling rate = 50 C/m in. ........................................ ....... ............... 135

5.10. TEM images of PC/PVA/Ferrite nanocomposite. ................. .............. 136

5.11. Stress strain comparisons for PC/Ferrites with and without PVA, at 0.05
mm/sec., 30 C. All samples tested showed failure. ............................................138

5.12 High angle XRD region for various nanocomposites using reflective mode at
1 5 oC .......................................................................... 1 4 0

5.13. Lower angle region for various nanocomposites using reflective mode at
1 5 oC .......................................................................... 1 4 1

5.14. DSC Thermograms for PC and various nanocomposites. Heating rate =
10 oC/min., cooling rate = 50 oC/min. ........................................ ............... 143

5.15. Dark Field TEM micrographs of PC/Ferrites, without PVA..............................144

5.16. Dark Field TEM micrographs of PC/Ferrites, without PVA at a lower
m agnification............................................................................................145















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

POLYMER-SILICATE AND MAGNETIC POLYMER NANOCOMPOSITES:
PROCESSING AND CHARACTERIZATION

By

Ajit Bhaskar

August 2003

Chair: Charles L Beatty
Major Department: Materials Science and Engineering

The research can be categorized with respect to the fillers used, namely clay and

ferrite magnetic nanoparticles. Polymer layered silicate nanocomposites (PLSNs) are

nanocomposites of polymers and clays.

One of the investigations carried out was regarding the amount of compatibilizer

necessary to get the optimum adhesion between the hydrophobic polymer and the

hydrophilic clay. The matrix used was polypropylene (PP) and the clay used was an

organically modified montmorillonite. It was found that beyond a certain concentration of

the compatibilizer, the mechanical properties deteriorated. This was explained on the

basis of the ways in which the compatibilizer, a maleic anhydride grafted polypropylene,

influenced the nanocomposites.

In another work, the impact properties of the nanocomposites processed above were

attempted to be improved using different elastomeric species and using different

processing protocols. It was observed that a low molecular weight oligomeric elastomer









produced the best results. It was also found that the sequence of addition of elastomer

affected the mechanical and impact properties.

Nanocomposites of PMMA and Laponite were prepared for enhanced abrasion and

wear resistance, for window-based applications. However, the major challenge was to

preserve the optical clarity of PMMA, a key emotive property that makes it a commodity

plastic. A recent technique called nano-indentation was employed for assessing the

hardness of these materials.

Nanocomposites of polymers using magnetic nanoparticles offer an interesting

research avenue. Nanocomposites using Polycarbonate (PC) and Ni-Zn based ferrite

nanoparticles were prepared. They were found to be clear with a brown tinge, and were

characterized for different properties. It was found that the melt viscosities of these

nanocomposites were significantly lower than the pure polymer. This was explained on

the basis of the different phases added to PC.

Most of the processing for the research was carried out using a reactive twin-screw

extruder, which simulates continuous, mass-production operations to a considerable

extent. An insight into the microstructure was obtained using various techniques such as

differential scanning calorimetry, X-Ray diffraction, transmission electron microscopy,

and nanoindentation. Mechanical properties were evaluated using tensile tests and Izod

impact testing. The results obtained from these analytical tools were interpreted and a

coherent explanation of different phenomena occurring on a macroscopic as well as

microscopic level was attempted.














CHAPTER 1
INTRODUCTION

My research focuses on polymer nanocomposites. Nanocomposites of polymers

with different fillers were processed and characterized. The entire research can be

classified based on the nature of filler employed, namely clay and ferrite nanoparticles.

Figure 1.1 shows a schematic describing the same.


Figure 1.1. Classification of research areas on the basis of filler employed.









Two different clays were used, montmorillonite and laponite. Chapters 2 and 3

describe research on polypropylene/montmorillonite nanocomposites. Chapter 4 deals

with Poly (methyl methacrylate)/laponite nanocomposites. Finally, Chapter 5 describes

Polycarbonate/ferrite nanocomposites. Chapter 6 discusses suggestions for future

research. Here, many ideas and concepts from earlier research have been attempted to be

applied to different avenues having different applications. The following section gives a

summary of each of these chapters.

1.1 Polymer Nanocomposites

1.1.1 Effect of Compatibilizer Concentration on the Mechanical Properties of
Polypropylene-Montmorillonite Nanocomposites

One of the objectives of this research was to demonstrate that addition of clay to a

polymeric matrix not only enhanced the properties of the pristine polymer, but it could

also achieve the same with small loadings. This could be attributed to the large surface to

mass ratio when compared to traditional fillers used for polymeric composites. However,

the major difficulty in preparing these nanocomposites was exfoliation of clay.

Exfoliation is one of the terms used to determine the extent of dispersion of clay in the

polymer matrix. The clay used for this work was montmorillonite, a smectite clay. The

clay structure comprised of tetrahedral layers of silica sandwiching octahedral layers of

alumina. On a whole, the structure looked like nearly parallel layers of silica held by

alumina pillars. Figure 1.2 shows the structure of montmorillonite clay.

When these galleries (i.e, the clay interlayers) are split far apart by the application

of high temperature and shear force generated due to the molten polymer and the extruder

in which it is processed, this type of dispersion is called exfoliation.









-O A, To, IeLi M













Figure 1.2. Structure of montmorillonite clay.


Other type of clay platelet separation possible is intercalation. Figure 1.3 shows the

different types of clay platelet separations. Several publications involving polymer clay

nanocomposites have been published with polar polymers (such as Nylon 6, Nylon 6,6,

Polyurethane) as the matrix material. In this work, a non-polar polymer, namely

polypropylene was chosen.















Intercalation Exfoliation
"--




































Figure 1.3. Different types of clay platelet dispersion by diffusion of polymer chains.


This is because PP is an inexpensive commercial plastic used for a variety of

applications. Besides, it is difficult for the clay to bond to a non-polar polymer, which can

be attributed to the hydrophilic nature of the clay and organophilic nature of the matrix.









So, the clay used in this study was organically modified. However, it was found that the

use of a compatibilizer between the polymer and the clay yielded better mechanical

properties. The compatibilizer used in this work was a maleic anhydride modified

polypropylene. It was also found out that when no compatibilizer was added, the

mechanical properties were inferior in comparison to the pure polymer. Thus it could be

deduced that in spite of the clay being modified to behave in an organophilic manner, the

use of a compatibilizer was necessary. To acquire an in depth insight into the effect of the

compatibilizer, its concentration in the nanocomposite was varied. It was observed that

after a certain percentage of the compatibilizer, the mechanical properties started to

degrade. It was concluded that compatibilizers were necessary components for good

dispersion of clay, but beyond a certain concentration, they had deleterious effects on the

mechanical properties of the nanocomposite.

1.1.2 Improving Impact Properties of Polypropylene/Clay Nanocomposites

Several publications show property enhancement in polymers upon the addition of

clay, but most of the publications do not address impact properties in detail. Hence, a

study was done in order to investigate the impact behavior of polymer clay

nanocomposites and schemes for improving their impact properties were proposed.

In one scheme, a functionalized elastomer was added before and after processing

the polymer clay nanocomposite in two different processing protocols.

In another scheme, an oligomeric, end functionalized elastomer was melt blended

with the compatibilizer, and the resulting modified compatibilizer was then used for

processing the nanocomposite.

It was found that the second scheme produced better mechanical properties. Thus, it

was speculated that oligomeric elastomer was able to penetrate into the clay galleries









more easily and because of functional groups present; it could also bond well to create a

more stable composite with respect to interfacial behavior. In addition, other mechanical

properties of the nanocomposite were not sacrificed significantly.

The functionalization of the polymeric elastomer used was carried out in a reactive

twin-screw extruder, so this work was a combination of nanotechnology and reactive

extrusion. The functionalizing agent used was glycidyl methacrylate.

1.1.3 PMMA/Laponite Nanocomposites

This research was focused on making wear/abrasion resistant PMMA for superior

windows based applications. The clay used here was Laponite JS, a synthetic clay, which

already existed as nanoparticles when dispersed in water. These particles were disc-

shaped. Two different loadings of clay were chosen, namely 2-wt % and 5-wt %. The

surface hardness was characterized using nanoindentation technique. It was found that the

addition of clay significantly reduced the penetration of the probe and hence, these

nanocomposites exhibited increased hardness. However, it was also observed that only

the 2-wt % nanocomposite exhibited optical clarity close to pure PMMA. The

nanocomposite containing 5-wt % clay was translucent.

1.1.4 Polycarbonate-Ferrite Nanocomposites

The aim of this research was to obtain magnetic nanocomposite materials. Nano-

sized ferrite particles prepared at the Department of Materials Science and Engineering,

University of Florida with help from Junyeon Hwang (working for Professor Darryl P.

Butt). These particles were prepared using a co-precipitation method, with carefully

controlled parameters such as temperature and pH.

The synthesized particles were dispersed in a polymer matrix. The matrix material

chosen was polycarbonate (PC). This is a transparent polymer, and is completely









amorphous. The ferrites were first coated with a low molecular weight PVA (Poly Vinyl

Alcohol). The ferrites are known to bond with alcoholic groups by means of silanol

reaction. After coating the ferrites with PVA, these were dispersed in molten

polycarbonate. The resulting material was still optically clear, with a brown tinge to it.

With respect to mechanical behavior, the nanocomposite was more brittle than the virgin

polymer, and exhibited a higher tensile modulus than pure PC. Characterization using a

SQUID magnetometer showed that the nanocomposite was magnetic in nature.

1.1.5 Future Research

Several concepts applied in the above research may be extended to other avenues as

well. Few of these include polymer/clay modified cement. It is suggested that this

approach may produce cement with good tensile properties. Another area is that of glass

fibers. Recycling of glass fibers is one of the interests. It is possible that by imparting

appropriate chemical treatment to the waste, ground fiberglass, they could be used again

with resins such as unsaturated polyesters, epoxy, etc. Impact modified glass fibers is

another area of interest. It is again possible that by giving the appropriate chemical

treatment, glass fibers when introduced into resins yield composites with better impact

properties without significant loss in tensile properties.

1.2 A Word on Processing and Characterization of Nanocomposites

The equipment used for processing the nanocomposites by melt blending was a

30mm APV reactive twin-screw extruder, with a co-rotating intermeshing configuration

of the screws. The length to diameter ratio (also addressed as l/d) was 40. The extruder

had eight temperature zones, including feed and die zones.

Characterization of nanocomposites prepared was performed using the following

techniques:









1. Tensile testing: Helps in comparing the tensile behavior of different materials and
their tensile moduli. This test also tells us about the relative stiffness of different
materials.

2. X-Ray Diffraction: The shift in diffraction peaks shows the extent of exfoliation or
intercalation that has taken place. This also helps in getting an overall picture of
intercalation/exfoliation in bulk.

3. Transmission Electron Microscopy (TEM): Is very effective in studying a local
region of the nanocomposite for exfoliation. The greater the number of individual
platelets that could be counted in a TEM micrograph, greater the extent of
intercalation/exfoliation.

4. Nanoindentation: A very novel and useful tool for probing hardness of
nanocomposite materials, especially at the surface. Its details are described later in
appropriate sections.

5. Izod Impact Testing: It gives the impact strength of a material. Here, a swinging
hammer is made to impact a specimen and the energy lost by the hammer upon
impact is a measure of the impact strength of the material.

6. Differential Scanning Calorimetry: This technique is used to evaluate the behavior
of a material upon heating. Different transitions such as melting, glass transition
and crystallization behavior can be studied with this technique.














CHAPTER 2
EFFECT OF COMPATIBILIZER CONCENTRATION ON MECHANICAL
PROPERTIES OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES

2.1 Introduction

A nanocomposite is defined as a material in which the dispersing phase has at least

one of its dimensions in the order of nano (10-9) meters.

Polymer clay nanocomposites are a class of hybrid materials in which clays having

a layered silicate structure are dispersed into a polymeric matrix. The spacing between

these layers is of the order of few (2-3) nanometers prior to dispersion of polymer. Hence

the hybrid is called a polymer clay nanocomposite [1-6].

The use of clays instead of traditional fillers is being encouraged for numerous

reasons. First and foremost, due to high surface to mass ratio of clays, the same amount

of property enhancement may be achieved with lesser quantity of clay than traditional

fillers such as glass fibers. This is because increased surface/mass ratio means greater

area available for adhesion. Thus, tremendous savings may be made with respect to

weight of the end product. This may also make processing easier. Further, research at

Toyota motor company has shown that for nylon-6/montmorillonite clay nanocomposites,

at a loading of only 4.2 wt% clay, the modulus doubled, the tensile strength increased by

more than 50%, and the heat distortion temperature increased by 80 C compared to the

pure polymer [7-8]. Researchers also demonstrated that organoclays exfoliated in nylon 6

matrix and greatly improved the dimensional stability, the barrier properties and even

flame retardance [9-11].









However, the clay nanolayers are not easily dispersed in polymers due to their

preferred face-to-face stacking tactoids. Dispersion of tactoids is further hindered by the

fact that clays are hydrophilic in nature, and are therefore, incompatible with majority of

polymers that are primarily hydrophobic. Hence, these clays are surface-modified

(usually with an organic ammonium salt) in order to enhance compatibility between the

matrix polymer and the clay. Such clays are termed as organoclays. This concept has

been extended into various polymer systems including polyamides [12-17], epoxies [18-

29], polyurethanes [30-38], polypropylene [39-62], polyesters [63-66], polystyrene [67-

81], polyethylene [82], elastomers [83-87] and polysiloxanes [88] among others. Many

liquid crystalline polymers have also been explored [89-92].

For true nanocomposites, the clay nanolayers must be uniformly dispersed

exfoliatedd) in the polymer matrix, as opposed to being aggregated intercalatedd) into

clusters of layers [1]. Figure 2.1 shows this. Dispersion and distribution of the filler is

achieved when the hydrodynamic separation forces of the polymer melt overcome the

agglomerating forces between the clay interlayers [12]. The exfoliation of clay in a

polymer optimizes the number of reinforcing elements for carrying the applied load and

deflecting cracks. The coupling between tremendous surface area of the clay (-760 m2/g)

and the polymer matrix facilitates stress transfer to the reinforcement phase, allowing for

such tensile improvements. High aspect ratio nanolayers also provide properties that are

not possible for larger-scaled composites.

The impermeable clay layers pose a tortuous pathway for a permeant to traverse the

nanocomposite. Figure 2.2 demonstrates the same.
















o re iated- oliat



IM. LiI)IAN("



:Ly
.














nanocomposite. On the other hand, in an exfoliated nanocomposite, the
average gallery height is determined by clay silicate loading. The difference







can be detected by X-ray diffraction and the latter is X-ray amorphous.

The enhanced barrier characteristics, chemical resistance, reduced solvent uptake

and flame retardance of polymer clay nanocomposites all benefit from the hindered

diffusion pathways through the nanocomposite. The replacement of inorganic nations by

organic onium ions on the gallery surfaces of smectite clays not only serves to match the

clay surface polarmposite. Onh the polarity of the polymer, but it also expands the clay

galleries. Depending on the charge density of clay and the onium ion surfactant, different

arrangements of the onium ions are possible. In general, longer the surfactant chain

length, and the higher the charge density of the clay, further apart the clay layers will be

forced.






11









: I" ,'-i ".l ......






Figure 2.2. A model for the torturous zigzag diffusion path in an exfoliated polymer clay
nanocomposite when used as a gas barrier.

This is expected since both of these parameters contribute to increasing the volume

occupied by the intragallery surfactant [1, 93]. Depending on the charge density of the

clay, the onium ions may lie parallel to the clay surface as a monolayer, a lateral bilayer,

a pseudo-trimolecular layer, or an inclined paraffin structure. At very high charge

densities, large surfactant ions can adopt lipid bilayer orientations in the clay galleries.

Figure 2.3 shows this. Polymer clay nanocomposites are being used in under the hood

applications in automotive industry [1, 94].

2.2 Polypropylene Clay Nanocomposites

Polypropylene is a thermoplastic polymer, and is one of the most widely used

polymers in the industry. It is inexpensive and is relatively easier to recycle and offers

versatility in terms is properties and applications. The introduction of traditional fillers

into PP requires special processing technologies involving prepreg preparation and fiber

impregnation [39, 95-96].

This is the reason special emphasis is being laid on PP/clay nano-hybrids. These

can be synthesized using a relatively easier approach of melt blending.
















Monolayer


Bilayer


--- -^c ~ ----~- ^ \

Pseudo-trirayer Paraffin structure


Figure 2.3. Orientations of alkyl ammonium ions in the galleries of layered silicates with
different layer charge densities.

Researchers at Toyota and other laboratories [1, 46, 61, 97, 98, 99] have reported

that it is possible to prepare PP-clay hybrids by simple melt mixing of three components,

i.e., PP, maleic anhydride-modified polypropylene oligomers (PP-MA), and clay

intercalated with alkyl ammonium ions [51, 61, 97, 100-101]. Some of the common

approaches adopted for preparing PP/Clay nanocomposites (PPCNs) are:

1. The clay is first blended with polar oligomeric species. Strong interactions result
between the polar groups on the oligomeric species and the oxygen based groups
on the clay. Examples of polar oligomers are maleic anhydride grafted PP and
certain alcohol based oligomers. This system is then blended with PP for increasing
the gallery spacing in the clay.

2. The clay is dispersed in a solvent, followed by the addition of a monomer. Then the
monomer is polymerized to prepare a system compatible with PP. This clay-
polymer hybrid is then blended with PP.

From a processing perspective of nanocomposites, many methods have been

reported. These include melt intercalation [12-14, 39-49, 51-58, 70, 80], solution

blending [69, 74, 78] and in-situ polymerization [67, 71-73, 75, 77,79, 81].









2.3 Research Objectives and Strategy

In this research, the nanocomposites were prepared by combining the two above

mentioned approaches. The clay was dispersed in a solvent. The low molecular weight

compatibilizer was blended with PP instead of clay. The dispersed clay was then blended

with the modified PP blend to give a nanocomposite.

An attempt was made for studying the effects of the compatibilizer concentration

on mechanical properties of PPCNs. Primary emphasis was laid on tensile properties.

This is because the tensile properties are a very important criterion for materials selection

for most of the applications. It has been reported in literature that using method #1 listed

in the previous section for preparing PPCNs, a compatibilizer to clay ratio of 3:1 worked

best.

Kato et al. have observed that the density of the compatibilizer, a maleic anhydride

modified PP, had a remarkable effect on the final morphology of the nanocomposite [61].

However, in their work, the authors did not make comments about the mechanical and

thermal properties of the nanocomposites. Thus, it was shown that the ratio of 3:1 was

best from an exfoliation/intercalation point of view.

D. Garcia Lopez et al. [59] have also observed a similar ratio. However, it was seen

from their work that the increase in tensile strength was not very significant.

Hence, an attempt was made to study in depth, the role of the compatibilizer and

the effect of its concentration on various mechanical properties of the nanocomposite.

2.4 Materials

Montell (now Basell) supplied PP used for this research. The grade was Profax

6523. This was an extrusion grade plastic. Table 2.1 shows some of its properties.









Table2.1. Properties of Polypropylene (Basell Profax 6523) used for the research.
PROPERTY VALUE TEST METHOD

PHYSICAL

Specific Gravity 0.9 ASTM D792
Melt Flow Rate (230 C) 4.00 g/10 min ASTM D1238

MECHANICAL

Tensile Strength @ Yield 4900 psi ASTM D638
Tensile Elongation @ Yield 12% ASTM D638
Flexural Modulus (Procedure A) 1% Secant: 200000 psi ASTM D790
Notched Izod Impact (73 F) 0.7 ft-lb/in ASTM D256
Rockwell Hardness (R-Scale) 86 ASTM D785
THERMAL

DTUL @66psi Unannealed 199 OF ASTM D648

Nanocor supplied the clay used for this study. The name of the product was

Nanomer" I.34TCN. It was specifically designed for extrusion compounding. Table 2.2

enlists some of its properties. However, it is worth mentioning that this clay was not

designed for moisture barrier applications [102].

Table 2.2. Physical properties of Nanomer 1.34 TCN.
PROPERTY VALUE

Appearance White Powder
Mean Dry Particle Size 16-22
(Microns)
+ 325 Mesh Residue (%) 0.1
Specific Gravity 2.0
Moisture (%) 3.0
Bulk Density (gms/cc) 0.30-0.36

Purity (%) 98.5

The agent used for dispersing the clay was Xylene, supplied by Fisher Scientific.

Eastman Chemical Company supplied the compatibilizer used for the research under the

trade name Epolene G-3003. Table 2.3 describes some of its properties.









Table 2.3. Properties of Epolene G-3003.
PROPERTY VALUE

Ring & Ball Softening Point, C 158
Penetration Hardness <1
Density @ 25 C 0.912
Acid Number 8
Viscosity, cP (mPa*s) @ 190 C 60,000
Melt Index @ 190 C 12.7
Color (Gardner) 25
Molecular Weight 27,200


Epolene is a maleic anhydride grafted PP. It has a much lower molecular weight

and consequently a lower softening point than PP. Thus, its chains exhibit greater

mobility. Figure 2.4 shows the structure of a maleic anhydride group.






Figure 2.4. A Maleic anhydride group.

2.5 Processing

The nanocomposites were processed by melt compounding using a 30 mm APV

co-rotating twin crew extruder, with 8-zone temperature settings ranging from 200 C

(feed zone) to 234 C (die zone). The screw length to diameter ratio (L/D) was 40.

Figures 2.5 shows a schematic representation of the extruder.

Figure 2.6 shows the processing in the form of a block diagram. The Zenith pump

is generally used for introducing the reactive species. However, upon preparing the clay

dispersion, it was feared that the same might plug the pump. Hence, it was not used. The

clay dispersion was introduced at the feed zone.









Zenith Pjump
Power






















Figure 2.5. Schematic of reactive twin-screw extruder.
IF II 1 ol



Wa[ III t



Coolant out





Figure 2.5. Schematic of reactive twin-screw extruder.

Table 2.4 shows the temperature profile along the different zones of the extruder.

PP and Epolene were dried in an air-circulating oven prior to any melt compounding

operation. The temperature was 80 TC. Drying was done to ensure removal of moisture.

This was particularly important for Epolene, which had polar groups associated with it.






















V


Deone ZoZne2 Zone I
U~e Z~e Zoe 7 Z~e v ane 5Z cae ne a


Figure 2.6. Block diagram of the extruder showing different zones.
The preparation of the sample containing 90-wt % PP, 5-wt % Epolene and 5-wt %

clay is described. Nanocomposites with other compatibilizer concentrations were

prepared in a similar fashion.

Table 2.4. Different temperature Zones of the twin screw extruder.
Zone Temperature ( C)

Zone 1 (Feed Zone) 200
Zone 2 204
Zone 3 208
Zone 4 214
Zone 5 218
Zone 6 223
Zone 7 227
Zone 8 (Die Zone) 234

PP was blended with Epolene in the weight ratio 90:5 in the extruder. The extruded

strands were received in a flowing water bath, which formed a part of the extruder. These









strands were pelletized and dried for 24 hrs. in a vacuum oven at 95 C. These pellets

were melt-compounded with the clay.

The clay was dispersed in xylene (clay: xylene used was approximately 1:5 by

weight). The dispersion was magnetically stirred for 10 minutes prior to addition to

pellets at the feed zone of the extruder. The resulting strands were received in a flowing

water bath, pelletized and vacuum dried for 24 hours under conditions described above.

Table 2.5 summarizes the compositions (by weight, dry basis) of different

nanocomposites thus prepared.

A sample without any compatibilizer was also prepared in order to demonstrate the

effect and necessity of Epolene. Pure PP was also run through the extruder under

identical conditions in order to ensure uniform thermal history for all the materials

compared for different properties.

Table 2.5. Designation of different PPCNs. All compositions are in weight%.
SAMPLE DESIGNATION % POLYPROPYLENE % EPOLENE % CLAY
PP/Clay (95:5) 95 0 5
PP/EP/Clay (90:5:5) 90 5 5
PP/EP/Clay (85.5:9.5: 5) 85.5 9.5 5
PP/EP/Clay (76:19:5) 76 19 5
PP/EP/Clay (47.5:47.5:5) 47.5 47.5 5

2.6 Characterization

Polymer characterization is considered to be a separate discipline of study in the

field of polymers. It involves the investigation of the microstructure-property

relationships of a polymeric material. Examination of microscopic details of the structure

in order to understand the morphology, measurement of mechanical and thermal

properties are all part of the characterization process. The following analytical tools were

employed for characterizing the PPCNs:









* Tensile Testing
* X-Ray Diffraction
* Differential Scanning Calorimetry
* Transmission Electron Microscopy

2.6.1 Specimen Preparation

Specimens for all the above mentioned techniques were prepared by compression

molding. Compression molding is a process in which a polymer is made to take the shape

of a mold by pressing it between two heated plates. The heat melts the polymer (if semi-

crystalline) or takes the polymer chains well above the glass transition temperature (if

amorphous). The machine used for compression molding was a Carver, model C-81000-

141 press. Figure 2.7 shows the details of the press. Figure 2.8 shows the details of the

compression molding process, and the placement of the mold containing polymer pellets

between two metal plates.

In order to prepare the specimens, the press was first heated to 420 F. The mold

used was square in shape, with dimensions of 70 mm X 70 mm X 0.8 mm. The mold was

placed on a metal plate covered with Teflon coated aluminum foil. The mold was then

filled with dried pellets. This plate with mold and the pellets was placed on the bottom

plate of the press. Another Teflon coated aluminum foil covered metal plate was placed

on top of the mold bearing plate, to give a sandwiched assembly.

The bottom plate of the press was raised until the assembly just touched the top

plate of the press. The pellets were then allowed to convert into a liquid state by heat

transfer from the press. This took about 5-6 minutes. After that the pressure of the system

was raised to 10, 000 psi. Initially, due to resistance offered by the liquid polymer as well

relatively incomplete conversion to liquid, the pressure dropped below 10,000 psi. Under

these circumstances, it was necessary again to raise the pressure to 10,000 psi.
















































Figure 2.7. Schematic diagram of Carver compression molding press.


IN77
























































Figure 2.8. Placement of mold between two metal plates covered with Teflon coated
aluminum foil.









INDEX:

1. Lever for raising bottom plate
2. Pressure gauge
3. Bottom plate
4. Top plate
5. Temperature dial
6. Temperature controller
7. Pressure release screw
8. Metal plate "a" covered with Teflon coated aluminum foil
9. Mold
10. Pellets
11. Metal plate "b" covered with Teflon coated aluminum foil.

This was repeated until the pressure attained a steady value of 10,000 psi. The pressure

could be measured using a gauge attached to the press.

A pressure of 10, 000 psi. on the gauge corresponded to 9302 psi. on the sample.

This was calculated using the formula:

Ps x As = Pg x Ag (Equation 2.1)

Where, Ps = Pressure on the sample

As = Cross sectional area of the sample

Pg = Gauge pressure

Ag = Cross sectional area of the piston of the press.

As =4900 mm2

Ag =3.14. (32)/4

Pg = 10, 000 psi.

After the gauge pressure became steady at 10, 000 psi., the mold was allowed to

rest at the above mentioned temperature and pressure for 10 minutes. After that, the heat

supply to the press was turned off. Immediately after this, the pressure-release screw was

turned. The hot plate assembly containing the mold between the two metal plates was









removed and was immersed in a cold-water reservoir and kept for 3 minutes. Then, the

entire assembly was flipped over and was immersed in the reservoir for 3 more minutes.

After the mold cooled down to ambient temperature, the solidified sheet was then taken

out of the mold. Sheets were prepared in this way for pure PP, and the various

nanocomposites.

These sheets served as specimens for all the characterization techniques.

2.6.2 Tensile Testing

The aim of tensile testing was to evaluate the mechanical response of the materials

to a known strain or deformation rate. This gives a plot of stress versus strain from which

a wealth of information may be obtained such as the brittle or ductile behavior, tensile

modulus or an indication of stiffness of the material, tensile strength etc.

The instrument used for performing tensile testing was an EnduraTEC ELF 3200

Series machine. The main parts of the system were:

* The linear motor assembly: Had a patented high-bandwidth, low-distortion actuator
from Bose Corporation.

* Testing Chamber: Had facilities for introducing hot air, for increasing temperature
as well as introducing liquid nitrogen. A bulb for viewing the test in case liquid
nitrogen made the chamber cloudy was also provided. The door had a transparent
section for viewing testing while in progress. There were two sets of grips. The
bottom grip was stationary and was connected to the load cell. The upper grip was
mobile and its motion was regulated by the W\i nest' software, and ultimately, the
linear motor.

* Temperature Control: With the help of the software, temperature could be varied
between -50 C to 150 oC.

* Controller box, which acted as an interface between the computer and the machine
itself.

Figure 2.9 shows the front view of the machine. Figure 2.10 describes the testing

chamber. Figure 2.11 provides a rough description of the temperature controlling unit and









the emergency stop button. Figure 2.12 shows the control unit. None of the parts were

hydraulic, so maintenance was quite easy. It should be noted that the test was

displacement controlled, i.e., the specimen was pulled by a pre-determined amount with

each step of testing. The corresponding load exerted on the sample for pulling was

recorded.

The testing procedure can be described in steps as follows:

* The machine and the software were turned on.

* The specimen for tensile testing was a rectangular strip, which was cut from the
compression-molded sheet using a penknife. Its width and thickness were measured
using a micrometer.

* The specimen was placed between the grips and the grips were tightened. Over-
tightening of the grips was avoided, especially for brittle materials, in order to
avoid failure at grips.

* The linear motor was turned on using the "locals" button in the software.

* Load and displacement associated with the grips were tared. After that, the distance
between the ends of the grips was measured. This was the gauge length. This value
was usually 27 mm.

* The system was first tuned for a square wave of certain amplitude. The purpose of
tuning was to make the command given to the machine by the software and the
output generated by the machine match as closely as possible. Adjusting the PID
control parameters during the time when the square wave was acting on the system
did the required tuning.

* The tuning was double checked by re-tuning the system with a sinusoidal
waveform.

* The waveform was set to "ramp". This was the waveform used for tensile testing.
Strain rate could be set according to requirements, by typing the value in the
appropriate box.

* File names for saving the test data were specified using the data acquisition menu.
This menu also allowed deciding the rate of scanning, number of scans and time
between the scans for acquiring data.







* The machine stopped automatically after the specimen failed. In case the specimen
did not fail, the machine stopped acquiring data beyond a critical extension of the
specimen. This value was 7.082 mm.



|


F.ndura I I.1
F I [ 321'i % 11 S


BOSE


I


pI- "


1 II


Figure 2.9. The EnduraTEC ELF 3200 series machine.


I I


r












S ---
-'H

-4'


---- ~ ~~ ~ ---------^ I


Figure 2.10. Specimen testing chamber.









(' LII LMIt '


D (fJL


-LI4


Figure 2.11. Temperature control box and emergency stop buttons.


CONDITIONED )SIGC \LS


0000
wEwE]


COM1\I ND
SIGNALS
00
ELIE


Figure 2.12. Control unit. This acts as an interface between the computer and software.


4- 1


r A









INDEX:
1) Linear motor assembly
2) Connection between linear motor assembly and grips
3) Testing chamber
4) Load cell
5) Door
6) Bulb
7) Liquid nitrogen inlet
8) Hot air blowing unit
9) Grip
10) Transparent portion of door for viewing testing
11) To load cell
12) Air flow warning button
13) Temperature control box
14) Emergency stop button
15) Heat enable button
16) Control unit (acts as an interface between the computer and the machine).

The tensile testing data was obtained as a text file inforce versus displacement

form. Knowing the width and thickness of the specimen, cross-sectional area of the

specimen could be calculated using the formula:

Area = Width x Thickness (Equation 2.2)

The stress on the sample could be calculated by using the formula:

Stress = Force + Area (Equation 2.3)

Now, engineering strain is given by the formula:

S= Al lo (Equation 2.4)

The displacement obtained from the testing data was Al. lo, the initial separation

between the grips (usually 27 mm) was already known. So strain could be calculated.

Knowing stress and strain, stress versus strain curves could be plotted.

temperature of testing was For the purpose of tensile testing, typical specimen

width was between 4-5 mm and the thickness was between 0.6 to 0.9 mm. The strain rate

used was 0.1 mm/sec. The 29 C. 2-3 specimens were tested for each material.









The scatter for modulus and tensile strength values were found to lie between 4-10

%. Figure 2.13 shows the stress strain plots for various materials. Figure 2.14 shows the

variation of tensile modulus with compatibilizer concentration.

The modulus values were obtained by calculating the slopes of the linear regions of

the stress strain curves. Figure 2.15 shows the variation of tensile strength with

compatibilizer concentration. Table 2.6 lists the tensile moduli and tensile strengths of PP

and PPCNs. Representative data points generated by the W\i ntest' software are provided

in Appendix A.

2.6.3 X-Ray Diffraction

When a beam of electron interacts with an atom, some of the incident electrons

have sufficient energy to knock out an inner shell electron of that atom. As a result, an

electron from one of the outer shells jumps in.

In doing so, energy has to be emitted. Emitting X-rays can do this. These X-rays

are characteristic of every atom and give information specifically about it. This is because

each atom has its own excitation energies for its electron shells. Figure 2.16 illustrates the

principles of XRD. When X-rays impinge on a crystalline material, atomic planes diffract

them.

The objective of performing XRD was to explore the possibility of any

intercalation or exfoliation in the layered silicates due to possible penetration by the

polymer into the clay layers.

This is usually determined by the shifts in low angle peaks for the clay.

According to Bragg's law:

NA = 2d sin (Equation 2.5)









Where N = order of diffraction

S= wavelength of X-rays used

d = interplanar spacing and

0 = semi-angle of diffraction.

So, as the semi angle varies, the d spacing between the clay layers also varies. If the

polymer is successful in penetrating the clay layers, then the d spacing of the clay layers

increases, thereby reducing the angle corresponding to the peak observed. Bragg's law

quantifies this. Here, N, the order of diffraction is assumed to be one.

X-Ray diffraction analysis was performed using a Philips APD 3720 instrument,

using a Cu-Ku X-Ray source (Wavelength = 1.54 A). The range of angles scanned was

0-18 degrees. Reflective mode was used and the experiment was carried out at 15 oC.

Table 2.6. Tensile moduli and tensile strengths of PP and PPCNs. Strain rate = 0.01
mm/sec., temperature of testing = 29 oC.
MATERIAL TENSILE MODULUS TENSILE STRENGTH
N/mm2 N/mm2

PP 1000 22.49


PP/Clay 95:5 968 18.9


PP/EP/Clay 90:5:5 2480 22.02


PP/EP/Clay 85.5:9.5:5 2891 23.6


PP/EP/Clay 76:19:5 1411 20.1


1144 18.9


PP/EP/Clay 47.5:47.5:5


















20 *







15
4-
E




10



-- pp (didn't fail)

-U- pp/clay(95:5) (didn't fail)
5 -- pp/ep/clay (90:5:5) didn'tt fail)

pp/ep/clay (85.5:9.5:5) didn'tt fail)

-*-pp/ep/clay (47.5:47.5:47.5)



0 0.05 0.1 0.15 0.2 0.25 0.3
Strain (absolute)


Figure 2.13. Stress versus strain plots for different PPCNs. Strain rate = 0.01 mm/sec.,
temperature of testing = 29 C.












3500






3000






2500













t 1500 -






1000
E-















500






0
0 5 10 15 20 25 30 35 40 45 50
Compatibilizer concentration (wt. %)




Figure 2.14. Dependence of tensile modulus on compatibilizer concentration. Strain rate
= 0.01 mm/sec., temperature of testing = 29 oC.

















24




23




22



C4
E 21

z


S20


C,
.w
S19
I-


0 10 20 30 40 50
Compatibilizer concentration (wt%)




Figure 2.15. Dependence of tensile strength on compatibilizer concentration. Strain rate
0.01 mm/sec., temperature of testing = 29 oC.





















d




Figure 2.16. Fundamentals of X-ray Diffraction. Here, 1= path difference, d= interplanar
spacing and 0 = semi-angle of diffraction.

The following stepwise procedure was followed:

* A 1 cm2 square was cut from the compression molded sheet of the sample, on
which XRD analysis was to be done.

* This square was mounted on a glass slide using double-sided scotch tape.

* A dummy, with the same height as the sample, was mounted on the slide to go into
the sample holder. Usually, the dummy was made out of cut pieces of glass slides
and cover slips, which were then fastened together with double-sided tape. The
purpose of the dummy was to ensure uniform level throughout the glass slide.

* The specimen was loaded on the spring clip with the glass slide extending towards
the user.

* The slide was pushed back completely.

* The door was placed with its contact down.

* Depressing "Blk Start" button on X-ray checked water.

* 20 seconds were given for the "operate" light to turn on.

* The voltage was set to 40 kV.

* The current was set to 20 mA.

* The kV was reset to 40 kV.









* The shutter control was turned to oo.

* Pressing the appropriate button opened shutter.

* On the software, using the APD menu and the sub menus within, system
preparation and system parameters were defined.

* Under the "Identify" menu, program name, scan parameters and data collection
parameters were set.

* Fl key was pressed to start testing.

* The instrument was shut down upon completion of test.

Figure 2.17 shows the entire XRD pattern for each material. Figure 2.18 shows the

low angle region of the XRD patterns shown in Figure 2.17.

2.6.4 Differential Scanning Calorimetry (DSC)

This characterization technique is used to study the response of a polymer to

thermal energy, or in other words, the behavior of a polymer is studied when it is heated

[103]. Information regarding thermal transitions of polymers, such as melting,

crystallization, and glass transition could be obtained. The basic set up of any DSC

instrument consists of two symmetrically placed pans in a silver chamber.

This chamber is heavily insulated from the atmosphere so that temperature can be

controlled from the heaters and liquid nitrogen alone. Two pans are placed on each side

of the chamber. One of them is blank, i.e., has nothing, whereas the other has the polymer

sample in it. The amount of sample required ranges from 8-15 mg. After the pans have

been placed, the chamber is closed and is taken to a starting temperature, from which it is

started to heat. This starting point depends on the temperatures at which thermal

transitions take place for the polymer. For example, if polypropylene, with a glass

transition temperature between -10 C to 0 C, is being used, the starting temperature

should be about -50 C in order to cover the entire Tg transition. It is to be kept in mind











A PP

B PPIEPICLAY (47,5:47.5:5)

C PPIEPICLAY (76,5:19.5:5)

D PPICLAY(95:5)

E MMNCLAY


0 2 4 6 8 10
2THETA (degrees)


12 14 16 18


Figure 2.17. Complete XRD patterns for PP and PPCNs in reflective mode, at 15 oC.


3000




2500




2000
0



z 1500
z


1000




500









1200

A PP

B PPIEPICLAY (47.5:47.5:5)
1000
C PPIEPICLAY (76.5:19.5:5)
B
D PPICLSY(95:5)

S800 E MMNCLAY
0
U


z 600
z
C

400 -




200
A



0 I I I I I
0 1 2 3 4 5 6 7 8 9 10

2 THETA (degrees)



Figure 2.18. Lower angle region of XRD patterns for PP and PPCNs in reflective mode,
at 15 C.









that a polymer generally does not undergo transitions at a well-defined temperature, but it

does so over a range of temperatures. After taking the polymer to the starting point, it is

heated. As mentioned earlier, one of the pans is blank while the other has extra material

in it, which is the polymer. Hence, heat requirements would be different for the two sides

of the chamber. It is this difference in heat versus temperature that we plot in order to

study the thermal transitions. Specific heat versus temperature can also be plotted.

Specific heat can be obtained by dividing the heat supplied by the temperature difference

resulting from the supply of heat. Thus specific heat is nothing but the amount of heat

required to produce a certain temperature difference, and this obviously depends on the

characteristics of the material. Figure 2.19 shows Tg transition on a DSC thermogram.

The Figure shows that the polymer is absorbing heat and this results in a dip. For

measuring glass transition temperatures, there are different procedures, one of which is to

take the average of the starting point and end point of the transition. After glass

transition, the polymer chains have a lot of mobility. They try to get themselves ordered.

Finally when they get ordered after acquiring sufficient energy, they give off heat. This

corresponds to the crystallization transition. Figure 2.20 shows this. This peak can help

distinguishing between a crystalline and an amorphous system. Amorphous polymers do

not show this peak.

If the polymer is heated beyond its crystallization temperature, eventually a stage is

reached when the temperature of the polymer does not rise until heat is absorbed. This

stage is called melting. In other words, crystallization is "undone". Now, the furnace has

to supply additional heat because the polymer is absorbing heat, and the furnace to keep








the temperature of the chamber rising at a constant rate as well. This results in a large dip.

Figure 2.21 shows the melting transition on a DSC thermogram.





Exo


flow
heat I -

V* glass
Endo transition
temperature


temperature -




Figure 2.19. Glass transition on a DSC thermogram.





Exo

heat 4
flow

Endo c


temperature -


Figure 2.20. Crystallization transition on a DSC thermogram.


I












Exo
heat
flow

Endo Tm


temperature

Figure 2.21. Melting transition on a DSC thermogram.

The heat of melting can be obtained by measuring the area of the corresponding

peak. One very important information that can be obtained from a DSC plot, often called

a thermogram is % crystallinity of the sample. Knowing the total heat of melting Hm and

the total heat of crystallization He, Hm- He gives the heat released by the crystals in the

polymer chains that were present before the sample was heated. Dividing this by the

specific heat of melting, the grams of polymer that was crystalline before heating the

sample can be obtained. So, dividing this number by total mass of the sample and then

multiplying by 100 would yield % crystallinity.

DSC for this research was performed using a ThermoHaake DSC 220C model

instrument, whose basic make-up is just as described above. However, the procedure had

a minor difference. The instrument had to be calibrated first. This was done by doing a

blank run with alumina in the reference pan and blank in the sample pan. This was

followed by the actual experimental run with alumina in the reference pan and polymer in

the sample pan. Crimped pans were used for placing the samples. Heating rate used was

10 C/min, whereas the samples were cooled at 50 oC / min. The starting temperature

was 50 C and the maximum temperature to which the samples were heated was 250

C. Two cycles were performed. This was to ensure that during the first cycle, any







thermal history effects due to processing would be removed. Figure 2.22 shows the entire
heating thermogram.


Temperature tc)


-35 15 65
-2000-




0 -6000 B


-8000

-10000
A PPICLAY (95:5)
-12000 B PPIEPICLAY (47.5:47.5:5)
C PP
-14000 D PPIEPICLAY(90:5:5)
E PPIEPICLAY (85.5:9.5:5)


-16000 -


165


215


Figure 2.22. DSC heating thermograms for PP and PPCNs. Heating rate = 10 C/minute.
Figure 2.23 shows the Tg region of the heating thermogram for the sake of clarity.
Figure 2.24 shows the melting region alone for the same reason. Figure 2.25 shows the
cooling thermogram and the crystallization peaks.






















i t

U



A PPIEP CLAY (85.5:9.5:5)

B PPIEP CLAY(90: :5)

C PP

D PPIEP CLAY (47.5:47.5:5)

E PPICLY (95:5)

Temperature (C)

Figure 2.23. Tg region of DSC heating thermograms for PP and PPCNs. Heating rate
10 C/minute.












.2000


4000-


6000


^ 000

0
1 .10000
E

o 12000 A PP


14000 R PPIPIlY(R.55.95:5)
B
C PPICLAY 95:5)
.16000-
D PPIEPICLY (47.5:47.5:5
A
.18000

C
.20000
Temperature (C)

Figure 2.24. Tm transition for PP and PPCNs obtained from DSC heating thermogram.
Heating rate = 10 C/minute.









35000



30000




25000







E





50000
0


A PP

B PPIEP'CLAY(47.5: 475:5)

C PPCL Y(95:5)

D PPIEP'CLAY (8565 :5:6)

E PPIEP CLAY (90:5 5)


50 60 70 80 90 100 110 120 130 140 150
Temperature (C)

Figure 2.25. DSC cooling thermograms for PP and PPCNs. Cooling rate = 50 oC/minute.









2.6.5 Transmission Electron Microscopy (TEM)

TEM is an extremely valuable tool for characterizing polymer/clay

nanocomposites. This is because with this technique, the clay galleries dispersed in the

polymer can be actually seen. Greater the number of individual platelets that can be

counted on a TEM micrograph, better the dispersion of the clay.

However, TEM demands a very careful preparation of specimens. Polymers are

charged when bombarded with electrons. So, polymer specimens are coated with carbon

or gold/palladium coatings.

Fundamentally, a TEM makes use of electron optics. A high-energy beam of

electrons is directed towards a thin specimen (usually 100 nm thin slices). The electrons

that are transmitted through the specimen are collected on a screen and these give

information about the microstructure of the material. The TEM consists of an electron

gun. This could be either thermionic or a field emission gun. The filament however, is

mostly made of tungsten, and is V-shaped. LaB6 filaments can also be used, but they are

quite expensive. Other components of the TEM are condenser lens assembly, specimen

stage, objective lens assembly and the recording system. A very high quality vacuum

should be maintained at all times in order to make maximum use of the electrons emitted

by the gun.

The contrast obtained in a TEM image is atomic contrast. In our case, polymers

have elements like carbon, hydrogen and oxygen, whereas the clay has silicon, aluminum

etc., that have a higher atomic number. Thus, they scatter more and transmit fewer

electrons. So, they appear dark in the micrograph.

For preparing specimens for TEM, a few thin slices were cut from the

compression-molded sheet of the material. These were embedded in a two-part epoxy









resin in a mold, and were cured in a vacuum oven at 40 C. Next, 100 nm thin slices were

cut using an Ultracut microtoming machine. It was found that the polymer embedded in

epoxy was hard enough to be cut with a diamond knife without being cooled with liquid

nitrogen (referred to as ultracryomicrotomy). The slices were obtained in a small pool of

water that was present in a specially designed area surrounding the diamond knife. These

were picked up using hair tipped brushes and were mounted on copper grids. Carbon

coating of slices followed this. It is worthwhile mentioning that sample preparation can

introduce voids in the specimen. Figure 2.22 shows this [104].


Figure 2.26. Void formation between the folded silicate layers during the microtoming of
the bulk nanocomposite.

The prepared specimens were viewed under a JEOL 2010F TEM. Figure 2.24

shows TEM images for PP/Clay (95:5). Figure 2.25 shows TEM images for PP/EP/Clay

(85.5:9.5:5). Figure 2.26 shows TEM images for PP/EP/Clay (47.5:47.5:5).























































































Figure 2.27. TEM micrographs of PP/CLAY (95:5).


is


100 nm


_ ____ ~__


























.4*'* 1


Figure 2.28. TEM micrographs of PP/EP/CLAY (85.5:9.5:5).


; -Pk*Q






49















































.1r0 0 ,,

Figure 2.29. TEM micrographs of PP/EP/CLAY (85.59.5:5).

Figure 2.29. TEM micrographs of PP/EP/CLAY (85.5:9.5:5).









2.7 Discussion of Results

In this section, the results obtained in the form of various plots, tables and curves

from different characterization techniques are discussed and their implications are

elaborated.

2.7.1 Tensile Testing

It is evident from Figure 2.13 that with the addition of clay and compatibilizer, the

tensile properties showed remarkable improvement. Both modulus and tensile strength

for the materials designated PP/EP/CLAY (90:5:5) and PP/EP/CLAY (85.5:9.5:5) were

much better than pure PP. However, the same were inferior for PP/Clay (95:5). This

material did not have any compatibilizer. This showed the necessity for adding Epolene.

Table 2.6 shows the variation in modulus and tensile strength with variation in

compatibilizer concentration. Figure 2.14 conveys the same pictorially. It was seen that

for PP/EP/CLAY (90:5:5), the modulus was 148% greater than pure polypropylene,

whereas for PP/EP/CLAY (85.5:9.5:5), the increase was 189.1%. This means that for

these materials, the tensile moduli were more than two times that of pure PP.

Figure 2.15 shows the dependence of tensile strength on compatibilizer

concentration. The trend observed is similar to that with tensile modulus. An interesting

feature to note regarding the trends shown by Figure 2.14 and Figure 2.15 was that the

properties reached a maximum at a certain compatibilizer concentration and then leveled

off after showing a decreasing trend. However, the weight % of clay in all these materials

was constant, which was 5%. A possible hypothesis was proposed for such a behavior.

Two additional components were added to PP. First was a low molecular weight

compatibilizer, whose molecular weight was significantly lower than PP. The other

material was clay, which acts as reinforcing agent. It was seen from Figure 2.13 that









when no compatibilizer was present (i.e., for PP/CLAY (95:5)), the material still

exhibited ductile behavior. This is because the clay has been modified organically to

exhibit some compatibility with hydrophobic polymeric systems. However, the extent of

clay dispersion and distribution was not adequate at this stage to optimize the number of

load bearing clay platelets per unit volume. Hence, the modulus and tensile strength were

lower than PP.

When some compatibilizer was added (i.e., PP/EP/CLAY (90:5:5)), it was seen that

the modulus showed tremendous improvement, and the tensile strength increased as well.

However, the increase in tensile strength was not proportionate to the increase in tensile

modulus. This is because the introduction of clay tends to make PP brittle. However, at

higher stress and strain values, the small, low molecular weight compatibilizer chains

tend to flow more easily than PP. In other words, the clay increases the tensile modulus,

but the compatibilizer tends to bring it down. Hence, there is a certain amount of

compatibilizer that can be added for a given amount of clay (to be added with PP) in

order to get the optimum mechanical properties.

So, the addition of a low molecular material may adversely affect the tensile

properties. But on the other hand, the compatibilizer may also increase the spacing

between the clay galleries, thereby increasing the effective surface area available for

bonding. This could mean enhanced adhesion between the polymer matrix and the clay.

This could lead to better mechanical properties. This is supported by TEM images, which

are discussed in a later section. So there are two effects of the compatibilizer on the

system:

S Being a low molecular component, it tends to have detrimental effects on the
mechanical properties of the nanocomposite.









* It tends to increase the spacing between the clay platelets. This tends to enhance the
mechanical properties.

Now, as the percentage of compatibilizer was increased beyond 5 wt% (i.e.,

PP/EP/CLAY (85.5:9.5:5)), it was seen that the tensile properties improve further. The

modulus and tensile strength were enhanced even further. Thus, we see that factor (a) is

still prevalent over factor (b).

Upon increasing the concentration of the compatibilizer further (i.e., PP/EP/CLAY

(76:19:5)), a drastic drop in both modulus and tensile strength was observed. This

showed that the low molecular factor associated with Epolene overcame its reinforcing

capability by increasing the clay interlayer spacing. When the concentration of Epolene

was increased to 47.5 % by weight, the tensile properties not only got worse, but also the

material failed when subjected to tensile testing. This was not observed with any other

material, including pure PP. This indicated the there was excessive low molecular weight

Epolene present, and its effect on tensile properties by increment of clay interlayer

spacing was certainly overcame by its own mechanically weak character. This material

not only failed but it also did so in a brittle fashion. This is possibly due to presence of

excessive low molecular weight component, as well many load bearing clay platelets per

unit volume, which also tend to make the nanocomposite brittle.

2.7.2 X-Ray Diffraction

Figure 2.17 shows the entire range of angles covered, which is between 0 to 18 o

while Figure 2.18 shows the low angle region of the same plot. It is known that pure clay

has a diffraction peak, which corresponds to Si 001 plane, between 2 to 4 degrees. It can

be seen from the plots that some intercalation has taken place, but the shift in the peaks is

not very significant. XRD gives an overall view of the extent of clay dispersion. For









actually seeing the clay dispersion on a local scale, TEM is employed, and its results are

discussed in a later section.

2.7.3 DSC

The DSC heating thermogram is shown in Figure 2.22. It is noteworthy that the

abscissa of the plot is heat supplied by the instrument, which is directly proportional to

specific heat. Since it is hard to distinguish between individual thermograms, Tg and Tm

regions are shown separately in Figure 2.23 and Figure 2.24 respectively. From Figure

2.23, it is seen that there is not a significant shift in the Tg transition for the

nanocomposites. However, it can be said that at glass transition, the heat requirement for

PP/CLAY (95:5) is the least. This could be because the clay has a lower specific heat

capacity than the pure polymer, and hence, the heat capacity of the composite decreases.

Upon adding Epolene (90:5:5), the heat capacity is slightly increased. However, the heat

capacity of Epolene is lower than PP. Hence, some chain confinement has possibly

taken place. The addition of Epolene facilitates the penetration of PP chains into clay

galleries as well as bonding between the clay and the matrix PP, thereby increasing the

heat requirement for Tg. Increment in thermal requirement is observed for PP/EP/Clay

(85.5:9.5:5) also, for the same reason. Both the nanocomposites also show a slightly

higher Tg than PP. But the heat capacity of the system PP/EP/Clay (47.5:47.5:5) is found

to be lower than PP. This could be because the low molecular weight (and hence lower

energy required to move the chains) factor associated with Epolene has overcome its

ability to aid chain intercalation. Also, the weight fraction of PP has decreased drastically

in this nanocomposite.

From Figure 2.24, it is seen that there are considerable shifts in Tm values. The Tm

of PP is 171.4 C. The Tm of PP/Clay (95:5) is 166.5 C, about 5 C lower than PP. This









could be because the clay may be acting as a nucleating agent. So, there are numerous

sites for heterogeneous nucleation per unit volume of the material. As a result, unlike PP,

where there are fewer, but larger crystals, in the nanocomposite, there are numerous, but

smaller crystals. The Tm values for all the nanocomposites are lower than PP, due to the

possible explanation provided above.

Figure 2.23 shows the cooling thermogram. Here also, the abscissa of the plot is

heat supplied by the instrument. The large peaks between ca. 100 C and ca. 150 C

represent crystallization phenomena. The most striking feature of the plot is the

significant shift in the Tc (crystallization temperature) for the nanocomposites, ranging

from about 4-12 degrees. This means that crystallization phenomenon begins much

earlier for the nanocomposites. This also indicates that the clay might be acting as a

nucleating agent. It is also seen from the figure that crystallization begins earliest for

PP/EP/CLAY (90:5:5), which is very close to the onset of crystallization of PP/EP/CLAY

(85.5:9.5:5). However, for the material PP/EP/CLAY (47.5.47.5:5), crystallization

temperature is lower than the other nanocomposites. This is an interesting result. This is

because PP/EP/CLAY (47.5.47.5:5) is expected to disperse the clay best and hence, the

number of nucleating sites available per unit volume of the material is expected to be the

highest for this material. Then why does the onset of crystallization occur much later than

PP/EP/CLAY (85.5:9.5:5)? In a work by Potzgay et al. [105] the authors have proposed

that crystallization is actually caused by those clay-platelets that are least separated by the

penetration of polymer chains. This could explain the results obtained in this research. It

offers an explanation for the earlier crystallization of PP/EP/CLAY (90:5:5) than

PP/EP/CLAY (85.5:9.5:5), and also that the crystallization temperature of PP/EP/CLAY









(47.5:475:5) is the least among the nanocomposites containing Epolene, because Epolene

facilitates increase in clay-interlayer spacing. However, PP/Clay (95:5) does not follow

this trend. This is possibly due to excessive stacked tactoids with virtually no polymer are

present. So the number of nucleation sites per unit volume is drastically lower than the

other nanocomposites. In summary, the following things should be kept in mind, while

addressing crystallization behavior of nanocomposites:

* Epolene is more compatible with clay than PP and plays an important role at the
PP/Clay interface.

* Epolene melts and crystallizes at temperatures much lower than PP.

* The molecular weight of Epolene is much lower than PP, so it exhibits higher
mobility than PP at any temperature above its glass transition.

* Increase in Epolene concentration means more liquid material at elevated
temperatures, but also better dispersion of clay in the polymeric matrix.

These reasons also help to explain as to why be the crystallization temperature of

PP/CLAY (95:5) greater than PP/EP/CLAY (47.5:47.5:5), besides the explanation

provided by Potzgay et al.

2.7.4 TEM

TEM micrographs shown in Figures 2.25 through 2.27 enable us to view to

dispersion of clay on a local scale. It can be seen that clay is poorly dispersed in

PP/CLAY (95:5) (Figure 2.25). There are quite big and distinct stacks of platelets in this

material. The marker for the image taken at 10 kX gives a rough estimate of the size of

these domains. The domains are approximately 2-3 microns large. The image taken at a

higher magnification, 100 kX, shows that there is a significant amount of tactoids

formation with little or no penetration by the polymer. This is evident from the big dark

region that can be seen in the image. This can be explained by the fact that the









organophilic polymer is still not very compatible with the clay, which is even though

modified with organic substances. However, there are numerous platelets that are

expanded by the penetration of polymer chains. In other words there is some

intercalation. For PP/EP/Clay (85.5:19:5) (Figure 2.26), we observe that the dispersion is

much better than PP/CLAY (95:5), and that the stacks of platelets that contain very less

polymer are smaller and fewer.

For PP/CLAY (47.5:47.5:5) (Figure 2.27), we see that the dispersion is even better.

Even at low magnifications, such as 30 kX, the size of the stacked tactoids does not

exceed 600 nm, as seen from the image.

It should be noted however, that these images do not represent the entire sample,

with respect to dispersion and distribution of the clay. But the images prove a

fundamental concept, which is the necessity of a compatibilizer for enhanced dispersion

and distribution of clay platelets.

2.8 Conclusions

The following can be concluded from the following research:

* Compatibilizers are necessary ingredients for enhanced dispersion and adhesion of
silicates in organophilic polymer systems, especially with non-polar polymers such
as PP.

* Better dispersion and distribution of clay platelets gave rise to better mechanical
properties of nanocomposites. This was explained by the increase in number of
load bearing clay platelets per unit volume of the material and also the uniformity
of distribution of the platelets.

* However, when added beyond a certain concentration, the compatibilizer had
deleterious effects on the mechanical properties of the nanocomposites.

* Addition of compatibilizer, besides affecting the extent of clay dispersion and
mechanical properties, also influenced the thermal behavior of the nanocomposites.

* Compatibilizer also played a role in crystallization of the nanocomposites.














CHAPTER 3
IMPACT MODIFICATION OF POLYPROPYLENE/MONTMORILONITE CLAY
NANOCOMPOSITES

3.1 Introduction

Numerous papers have been published on polymer/clay nanocomposites, but very

few address one of the key issues associated with them, which is their impact properties.

In spite of the fact that tensile modulus, tensile strength, barrier properties etc. show a

significant increase upon the addition of clay, the impact properties remain either close to

the original polymer matrix or they are inferior.

The aim of the present work was to investigate and improve the impact properties

of polymer/montmorillonite clay nanocomposites. The proposed strategy was to add

elastomeric species. This has been a proven technique for improving the impact

properties of many materials. Other objectives were:

3. To study the effects of introducing the elastomer on the extent of
intercalation/exfoliation of the clay.

4. The effect of introducing the elastomer on other properties such as tensile
properties and thermal behavior.

5. To determine the effects of method of preparation of the rubber modified polymer
clay nanocomposite on the above mentioned aspects.

If we succeed in improving the impact properties on these novel class of materials,

without sacrificing other assets ot these materials, then polymer clay nanocomposites

would be more complete materials with respect to improved properties in a balanced

fashion that could be used for a variety of applications.









Figure 3.1 [12] shows a typical trend in the Izod impact strength of

montmorillonite-modified polymer, which was Nylon-6 in this case. It was observed that

the pure polymer was superior in comparison to the nanocomposites.


0 5 10 15 20 25
Organoclay Content (wt.%)

Figure 3.1. Notched Izod impact strength of nylon 6 and 95/05 composites as a function
of clay loading.

This is because the large surface area of the clay provides greater space for the

polymeric matrix to adhere to it, but at the same time, it also increases the possibility of

formation of regions where the polymer does not adhere to the surface of the clay. This

could result in microvoids. These really impair the impact properties.

This is because they act as stress concentrators and initiators for crack formation.

Further, it is also believed that addition of clay also alters local chain dynamics [15].









Michler and coworkers [106] suggested that depending on their orientation with respect

to the axis of tension, a role could be attributed to the silicate layers with respect to

formation of micro voids. They showed that intercalated morphology showed more

cavitation than the exfoliated morphology.

Thus, morphological considerations are of great importance in addressing the

impact properties of polymer clay nanocomposites. In spite of the fact that the inorganic

clays are modified with many additives such alkyl ammonium chloride, that also

facilitate improved adhesion between the filler and the matrix, the impact properties do

not show significant increase. In fact, in many cases, deterioration has been observed [14,

39, 43, 47, 60,107].

As stated earlier, it has been shown that intercalated polymer clay nanocomposites

tend to show extensive cavitation. Figure 3.2 [15] shows this. In this work, it was

revealed that at room temperature, the polyamide/clay nanocomposite was quite fragile.

Further, the volume strain evolution upon drawing revealed that pristine polymer

deformed with little volume variation, whereas the nanocomposite showed cavitation.

These observations corroborated the above mentioned reason for describing the stagnant

or deteriorating nature of the impact properties.

The impact modification of polymer/clay nanocomposites calls for a slightly

different approach than for traditional fiber reinforced composites. This is because the

way in which the nanocomposite is formed is different. The clay has a layered structure,

with the distance between the layers being a few nanometers in size. The polymer chains

have to penetrate into these galleries and increase the separation. This also disperses and

distributes the clay platelets uniformly throughout the matrix.




















































Figure 3.2. SEM observation: (a) Cavitated nanocomposite; (b) Fibrillated
nanocomposite and polymer/clay interaction.










In doing so, they also have to bond to the surface of the clay platelets. On the other

hand, there is no such penetration of polymer chains in case of traditional fiber reinforced

composites.

Cho et al. reported that for a given loading of clay, the Izod impact strength

increased with increasing temperature. But still, the pure polymer showed better impact

properties at any given temperature than the montmorillonite-modified nanocomposites

[12]. Figure 3.3 [12] shows this.

Nylon 6 Composites
1200


S1000


800

SNylon a6 garclay
S600


E 400
"5%
N I nlmorillonli e
200



20 30 40 50 60 70 80 90 100
Temperature ({C )

Figure 3.3. Notched Izod impact strength of nylon 6 and 95/05 composites as a function
of temperature.

The rationale of Cho et al. was the following:

Upon increasing the temperature, the softness of the material is increased, and so

are the motions between the polymer chains. This indicates that the volume occupied by

the voids decreases and hence, impact properties improve. However, increased









temperature has adverse effects on other properties such as storage modulus and tensile

strength, which are very important engineering properties for material selection.

So, it is seen that improving the impact properties of polymer clay nanocomposites

is not an easy task. It is however, envisioned that there are certain strategies, which will

be discussed in the next section, that could possibly overcome this problem.

3.2 Research Strategies

Blending or reactive blending with elastomeric materials seemed to be an

interesting possibility. This was because imparting rubbery domains would greatly

enhance energy dissipation during fracture. Figure 3.4 illustrates this.
















Figure 3.4. Effect of addition of elastomer on craze crack structure. (a) Propagating crack
along the matrix material, along with craze fibrils. (b) Propagating crack in a
material with rubbery domains. Here, the rubbery domains absorb the energy
due to their extremely large size of plastic zone so that fracture process is
retarded. Also there is little crazing upon introducing elastomers. Elastomers
undergo tearing phenomena due to their large plastic zone.

This method for improving the impact properties of a wide variety of materials has

been employed since 1960s [110-117], and is being used till date [118-124].

However, due to dearth of publications regarding rubber toughening of polymer

clay nanocomposites, nothing definite could be stated about the outcomes of this method









prior to performing experiments. But the organically modified clays were not as

hydrophilic as glass fibers were. So the issues related to compatibilization of the interface

between the matrix polymer, clay and the elastomer were alleviated to a considerable

extent. This was corroborated by the fact that elastomers being liquids at room

temperature possessed better wetting characteristics. However, it is well known that the

elastomers also tend to reduce the tensile modulus because of their liquid like behavior.

Figure 3.5 illustrates this.

Hence, attempts were made towards improving the impact properties of the

nanocomposites, without sacrificing the tensile properties significantly.

3.3 Materials

Montell (now Basell) supplied PP used for this study. Table 3.1 enlists its

properties. The compatibilizer used was Epolene G-3003, supplied by Eastman

Chemical Company. Table 3.2 lists some of its properties.

The clay used for this study was Nanomer I.34TCN, supplied by Nanocor Inc.

Table 3.3 describes some of its properties.

Two different elastomers were used for this research. DuPont- Dow Elastomers

supplied the first, a polyolefin elastomer, under the trade name Engage (grade 8842).

Table 3.4 shows some of its properties.

The other elastomer was an oligomeric polybutadiene whose ends are

functionalized with epoxy and hydroxyl groups. Aldrich chemicals supplied this. Table

3.5 shows some of its properties.

Sigma Aldrich supplied Glycidyl methacrylate used for this research. Table 3.6

enlists some of its properties.























(I


Figure 3.5. Stress strain curves for different types of materials.


Fiber/Reinforcing
agent


Elastomer/Rubbery
material









Table 3.1. Properties of Basell Profax 6523 Polypropylene used for the research.
PROPERTY VALUE TEST METHOD

PHYSICAL


Specific Gravity
Melt Flow Rate (230 C)


0.9
4.00 g/10 min


ASTM D792
ASTM D1238


MECHANICAL


Tensile Strength @ Yield
Tensile Elongation @ Yield
Flexural Modulus (Procedure A)
Notched Izod Impact (73 F)
Rockwell Hardness (R-Scale)
THERMAL
DTUL (Z66si Unannealed


4900 psi
12%
1% Secant: 200000 psi
0.7 ft-lb/in
86

199 F


ASTM D638
ASTM D638
ASTM D790
ASTM D256
ASTM D785

ASTM D648


Table 3.2. Properties of Epolene
PROPERTY

Ring & Ball Softening Point
(oC)
Penetration Hardness
Density @ 25 C
Acid Number
Viscosity, cP (mPa.s) @ 190 C
Melt Index @ 190C
Color (Gardner)
Molecular Weight
Manufacturer


G-3003.
VALUE


158"

<1
0.912
8
60,000
12.7
25
27,200
Eastman Chemical
Company


Table 3.3. Physical properties of Nanomer 1.34 TCN.
PROPERTY VALUE


Appearance White Powder
Mean Dry Particle Size 16-22
(Microns)
+ 325 Mesh Residue (%) 0.1
Specific Gravity 2.0
Moisture (%) 3.0
Bulk Density (gms/cc) 0.30-0.36

Purity (% min) 98.5
Manufacturer Nanocor


"











Table 3.4. Properties of Engage" 8842.
PROPERTY VALUE

Co monomer Content (wt%) by 1C NMR/FTIR 45

Density (g/cm3), ASTM D-792 0.857

Mooney Viscosity ASTM D-1646 ML at 121 OC 26

Melt Index (dg/min) ASTM D-1238 190 C, 2.16kg 1.0

Durometer Hardness, Shore A ASTM D-2240 50

DSC Melting Peak (C) Rate 10 OC/min 33

Ultimate Tensile Strength, MPa ASTM D-638, 508 mm/min 2.1

Ultimate Elongation (%) ASTM D-638, 508 mm/min 975

Manufacturer DuPont Dow
Elastomers.

Table 3.5. Properties of oligomeric, epoxy and hydroxyl end functionalized
polybutadiene.
PROPERTY VALUE

Mn 1,300

Mw 2,600

Microstructure 55% 1,4-trans; 15% 1,4-cis;

vinyl 30%

Viscosity 250 poise

Fp >230 F

Density 1.01 g/mL

Manufacturer Aldrich Chemicals.









Table 3.6. Properties of Glycidyl methacrylate
PROPERTY VALUE
Molecular Formula C7 Hio 03
Weight % epichlorohydrin 0.2%
Weight % R-glycidol 1
Boiling point 189 C/760 mm Hg
Freezing point 169 F
Density 1.042 g/mL
Structural formula

II
H2C:C-C-O CH2\/

CH3 O
Manufacturer Aldrich Chemicals.

3.4 Processing

The main equipment used for processing the nanocomposites was a 30mm APV co-

rotating reactive twin-screw extruder. This extruder had eight temperature zones from

feed zone to die zone. Hence, the processing temperature ranged from 200 oC (feed zone)

to 234 oC (die zone). The screw L/D was 40. PP and Epolene pellets were dried in an

air-circulating oven at 80 OC for 24 hrs.

Different processing protocols were employed. The following protocol was used in

preparing the functionalized oligomer impact-modified polymer nanocomposite.

This was labeled as protocol A. First, the compatibilizer (Epolene) and end-

functionalized oligomeric elastomer were blended together in a batch mixer (150 C, for

2 hours) in the weight ratio of (4.75: 0.25). The elastomer was dissolved in xylene. Figure

3.6 shows the details of this operation.

This product was designated as Comp/F-olig. The resulting product was crushed

and dried for 24 hours in an air-circulating oven at 80 OC.









Next, PP and Comp/F-olig, mixed in the weight ratio (90:5) were blended in the

twin-screw extruder. The resulting strands were pelletized and dried for 30 hours under

conditions described above. Subsequently, the PP+Comp/F-olig pellets were melt-

compounded with 5-wt % clay.

To ensure good mixing, the clay was also dispersed in xylene, before being added

to the molten PP/Comp/F-Olig mixture at the feed zone along the screw channel. The

resulting strands were pelletized and dried as described above. This product was

designated as PP/Comp/F-Olig /Clay. The feed rate of PP, PP/Comp and other blends

described earlier was 40 grams/min., whereas the feed rate of clay was 2 grams/min. In

order to verify that the characteristics of the compounded materials were not significantly

influenced by the sequence of the preparation, two other impact-modified

nanocomposites were prepared. The polymeric elastomer was used for this purpose. For

the first sample, designated PP/Comp/F-POE/Clay, protocol B was used.

Here, the polyolefin elastomer (POE) was first functionalized with Glycidyl

methacrylate (GMA) in the reactive twin-screw extruder. Next, PP and Epolene were

blended in the extruder in the weight ratio 90:4.75. The functionalized elastomer was

then added to the PP/Compatibilizer blend in the weight ratio of 94.75:0.25. Finally, clay

(dispersed in xylene) was added to the above blend. Xylene: clay used was 5:1 by weight.

The weight ratio of PP, Epolene, polyolefin elastomer and Clay now became

90:4.75:0.25:5.

For the second sample, designated PP/Comp/Clay/F-POE, protocol C was

employed.










Elastomer/xylene in




Water out c



Condenser

Reactor












Figure 3.6. Schematic representation showing mixing of Epolene with oligomeric
polybutadiene.

Here, the sequence from functionalized POE and clay was reversed, that is, the clay

was added to PP/Compatibilizer mixture before the functionalized POE. The weight

percentage of each component remained the same. The reference material used for

comparing the properties of the impact-modified nanocomposites was PP/Comp/Clay

(90:5:5).

Table 3.7 summarizes the designations of different nanocomposites and their
method of preparation. Table 3.8 summarizes the weight percentage of different

components in various nanocomposites processed. Figure 3.7 shows the operation in the

form of a block diagram.









3.5 Characterization

The following characterization are used to obtain an understanding of the structure

property relationships in the nanocomposites processed:

* Tensile testing
* X-Ray Diffraction
* Izod impact testing
* Differential Scanning Calorimetry
* Transmission electron microscopy

Table 3.7. Preparation of Impact modified nanocomposites.
MATERIAL METHOD OF PREPARATION

PP/EP/F-OLIG /CLAY Epolene is blended with functionalized oligomeric
(PROTOCOL A) polybutadiene (95% Epolene and 5% F-olig PB by weight).

The matrix is prepared by taking 90 parts of pure PP and 5
parts of (epolene+f-oligomeric PB).

95 parts of this matrix are added to 5 parts of clay (by
weight). Hence in 100 parts of the nanocomposite, there is 90
% PP, 4.75%Epolene, 0.25% F-olig PB, 5% clay.

PP/EP/F-POE/CLAY PP is blended with Epolene.
(PROTOCOL B)
F-POE is added to this. Thus the matrix material is prepared,
which is PP/Epolene/F-POE.

To this, clay is added to make the nanocomposite.


PP/EP/CLAY/F-POE The nanocomposite is prepared first by blending PP, Epolene
(PROTOCOL C) and clay.

F-POE is then added to this nanocomposite.

PP/EP/CLAY (90:5:5) 90 parts of PP (by weight) are blended with 5 parts of
(REFERENCE Epolene.
MATERIAL)
5 parts by wt. of the montmorillonite clay is added to make the
nanocomposite.









Table 3.8. Percent composition of different nanocomposites by weight (dry basis).
SAMPLE WT. WT. % WT. % WT. WT. % F-
DESIGNATION % PP EPOLENE CLAY % OLIGOMER
POE
PP/COMP/CLAY 90 5 5 0 0
PP/COMP/F/OLIG/CLAY 90 4.75 5 0 0.25
PP/COMP/CLAY/F-POE 90 4.75 5 0.25 0
PP/COMP/F-POE/CLAY 90 4.75 5 0.25 0

Introduction of POLYMER

M in.[ rr rni' Io I







Die Zoe 7 LZone 6 Zone 5 Zone 4 e 3 Zone 2 ne 1
234C 227T C 223 C 2180C 214C 208C 204(C 2WC





Extrudate
to pelleizer




Figure 3.7. Synthesis of impact modified nanocomposites using a reactive twin-screw
extruder.

3.5.1 Specimen Preparation

Specimens for the listed techniques were prepared using compression molding. The

temperature used was 205 C, and the pressure used was 10, 000 psi. Sheets were

prepared for pure PP, and the nanocomposites.

In order to prepare the specimens, the press was first heated to 420 F. The mold

used was square in shape, with dimensions of 70 mm X 70 mm X 0.8 mm. The mold was

placed on a metal plate covered with Teflon coated aluminum foil. The mold was then









filled with dried pellets. This plate with mold and the pellets was placed on the bottom

plate of the press. Another Teflon coated aluminum foil covered metal plate was placed

on top of the mold bearing plate, to give a sandwiched assembly. The bottom plate of the

press was raised until the assembly just touched the top plate of the press. The pellets

were then allowed to convert into a liquid state by heat transfer from the press. This took

about 5-6 minutes. After that the pressure of the system was raised to 10, 000 psi.

Initially, due to resistance offered by the liquid polymer as well relatively incomplete

conversion to liquid, the pressure dropped below 10,000 psi. Under these circumstances,

it was necessary again to raise the pressure to 10,000 psi. This was repeated until the

pressure attained a steady value of 10,000 psi. The pressure could be measured using a

gauge attached to the press. A pressure of 10, 000 psi. on the gauge corresponded to 9302

psi. on the sample. This was calculated using the formula:

Ps x As = Pg x Ag (Equation 3.1)

Where, Ps = Pressure on the sample

As = Cross sectional area of the sample

Pg = Gauge pressure

Ag = Cross sectional area of the piston of the press.

As =70 X 70mm2

Ag =3.14 X (32)/4

Pg = 10, 000 psi.

After the gauge pressure became steady at 10, 000 psi., the mold was allowed to

rest at the abovementioned temperature and pressure for 10 minutes. After that, the heat

supply to the press was turned off. Immediately after this, the pressure-release screw was









turned. The hot plate assembly containing the mold between the two metal plates was

removed and was immersed in a cold-water reservoir and kept for 3 minutes. Then, the

entire assembly was flipped over and was replaced in the reservoir for 3 more minutes.

After the mold cooled down, the solidified sheet was then taken out of the mold. Sheets

were prepared in this way for pure PP, and the various nanocomposites.

These sheets served as specimens for all the characterization techniques.

3.5.2 Tensile Testing

The aim of performing tensile testing was to evaluate the mechanical response of

the materials to a known strain or deformation rate. This gives us a plot of stress versus

strain from which we can obtain a wealth of information such as the brittle or ductile

behavior, tensile modulus or an indication of stiffness of the material, tensile strength etc.

Tensile testing was carried out using an EnduraTEC ELF 3200 series machine. It

consisted of the following components:

* The linear motor assembly: Had a patented high-bandwidth, low-distortion actuator
from Bose Corporation.

* Testing Chamber: Had facilities for introducing hot air, for increasing temperature
as well as introducing liquid nitrogen. A bulb for viewing the test in case liquid
nitrogen made the chamber cloudy was also provided. The door had a transparent
section for enabling to view testing while in progress. There were two sets of grips.
The bottom grip was stationary and was connected to the load cell. The upper grip
was mobile and its motion was regulated by the Wi ntest' software, and ultimately,
the linear motor.

* Temperature Control: With the help of the software, temperature could be varied
between -50 C to 150 oC.

* Controller box, that acts as an interface between the computer and the machine
itself.

Strain rate used was 0.01 mm/sec and temperature of testing was 28 C. Figure 3.8

presents the results obtained from tensile testing.











































-*- PP


-U-PP/COMP/F-OLIG/CLAY
(90:4.75:0.25:5)
-A-PP/COMP/CLAY/F-POE
(85.72:4.76:4.76:4.76)
PP/COMP/CLAY (90:5:5)

- PP/COMP/F-POE/CLAY
(85.72:4.76:4.76:4.76)


0.05 0.1 0.15 0.2 0.25


Strain (absolute)




Figure 3.8. Tensile behavior of PP and impact modified PP/Clay nanocomposites at 0.01
mm/sec., 28 oC.









Table 3.9. Tensile properties of PP and impact modified PPCNs.
MATERIAL MODULUS TENSILE STRENGTH
(N/mm2) N/mm2
PP 949.25 22.3

PP/COMP/CLAY (90:5:5) 1892.1 21.68

PP/COMP/CLAY/F-POE 1023.1 19.89

PP/COMP/F-POE/CLAY 1185.3 21.7

PP/COMP/CLAY/F-OLIG 1307.6 22.67



3.5.3 X-Ray Diffraction

The objective of performing XRD was to explore the possibility of any

intercalation or exfoliation in the layered silicates due to possible penetration by the

polymer into the clay layers. This is usually determined by the shifts in low angle peaks

for the clay. This is because according to Bragg's law:

d = nA (2d sin 0) (Equation 3.2)

d = interplanar spacing,

n = order of diffraction

= wavelength of X-Ray source, and

o = semi-angle of diffraction

So, as the semi angle varies, the d spacing between the clay layers varies. If the

polymer is successful in penetrating the clay layers, then the d spacing of the clay layers

increases, thereby reducing the angle corresponding to the peak observed.

XRD was performed using a Philips APD 3720 instrument using a Cu-Ku X-Ray

source (Wavelength = 1.54 A). The range of angles swept was 0-75 degrees. Reflective









mode was used and temperature was 15 C. Figure 3.9 and Figure 3.10 present the results

obtained from XRD.

3000
A PP

A B MONTMORILLONITE

2500 C PP/COMP/CLAY/F.POE
D PP/COMP/CLAY/F.OLIG


S 2000
0



z 1500-
U



Z


1000




500


0 5 10 15 20 25

2 THETA (degrees)


Figure 3.9. XRD patterns for PP and impact modified PP clay nanocomposites in
reflective mode, at 15 C.










800


700 --------
A MMN CLAY

B PPICOMPICLAYIF.POE
600 -
SI C PPICOMPl -OLIGICLAY

u 600
I C

Z 400


300










0 1 2 3 4 5 7 8
2THETA (degrees)





3.5.4 Izod Impact Testing

In this method to determine impact strength, a metallic pendulum swings on its

track and strikes a notched, cantilevered plastic sample. The energy lost (required to

break the sample) as the pendulum continues on its path is measured from the distance of
200 l. l I '_i_" 'l i




100- --------- % '^ ^





2THETA (degrees)









its follow through. Figure angle region ofXRD plot shown in figure 3.9 in reflective mode, using at 15
TMI #41869 model machine.
3.5.4 Izod Impact Testing

In this method to determine impact strength, a metallic pendulum swings on its

track and strikes a notched, cantilevered plastic sample. The energy lost (required to

break the sample) as the pendulum continues on its path is measured from the distance of

its follow through. Figure 3.11 shows the instrument. Impact testing was carried using a

TMI #41869 model machine.






























Figure 3.11. Izod impact testing apparatus.

In this research while making impact testing bars as per as ASTM D-256,

formation of air bubbles could not be avoided, even after repeated trials. Hence, impact

testing was carried out with a specimen that had lesser thickness and width than the

prescribed standard. For the same reason, it could not be notched as well. Hence, the

impact testing was performed in the un-notched mode. Table 3.10 summarizes the results

obtained.

Table 3.10. Impact strengths of impact modified PP/clay nanocomposites at 25 C.
MATERIAL IMPACT STRENGTH IN ft. lb / sq. in

PP 15.91

PP/COMP/CLAY 14.85

PP/COMP/CLAY/F-POE 16.98

PP/COMP/CLAY/F-OLIG 26.52


Point of
Impact


IZOd
Test
App aratus









3.5.5 Differential Scanning Calorimetry

DSC describes the behavior of a material when subjected to heat at a controlled

rate. This enables us to determine different transitions associated with the polymer such

as glass transition, melting transition, besides crystallization behavior etc.

DSC on the samples was performed using a ThermoHaake DSC 220 C model

instrument. Heating rate used was 10 "C/minute, while cooling rate was 50 C/min. Two

sweeps of this thermal treatment were performed.

The output of the instrument is a plot between heat supplied in microwatts versus

temperature. The heat supplied is directly proportional to the specific heat of the material

being tested. Figure 3.12 shows the heating thermogram. Figures 3.13 and 3.14 show the

Tg and Tm transitions separately for the purpose of clarity. Figure 3.15 shows the cooling

thermogram.

3.5.6 Transmission Electron Microscopy

TEM images usually complement XRD data and also enable us to see details at a

nanometer scale. However, it should be noted that this technique gives image of a very

small section of the material.

Transmission electron microscopy was performed on PP/COMP/F-POE/CLAY

using a JEOL 2010 Field emission TEM instrument. For PP/COMP/F-OLIG/CLAY, a

JEOL 200 CX instrument was used. It has a tungsten based thermionic gun. Figure 3.16

shows the TEM image for the oligomer-modified nanocomposite. Figures 3.17 and

Figure 3.18 present the TEM images for polyolefin-modified elastomer. Use of two

different instruments for the samples may result in difficulty in comparing the details

with respect to intercalation of clay platelets.










A PP

B PPICOMPICLAYIF-POE

------ C PP I CO i0- P I F, -mOLUIGfi CLAY





1)0 4 5) 10 o 10 2(0 21
(1)





0

10000











Temperature (t)


Figure 3.12. DSC heating thermogram for PP and impact modified PP/clay
nanocomposites. Heating rate = 10 C/min., cooling rate = 50 C/min.









Ennn


4UUU




2000 Temperattre (




0
0 .O 20 40 60 83 1(

---m / 200 f-m__ -_.---'-^ ---_
A






A PP

B PPICOMPICLA IF.POE

C PPICOMPICLA IF.OLIG
--- ~ ~ ~-m8---------


Figure 3.13.Tg region of DSC heating thermograms presented in Figure 3.12. Heating
rate = 10 C/min., cooling rate = 50 C/min.








0
1i0 15 1!0 1i5 160 1;5 170 1 5 11 15

.2000


4000





ao


8000
U
I .1000 /



.12000


14000 A
A PP I

14000 B PPOMPICLAYIF.POE
B
C PP COMPIF.01IGICLAY
.16000


.18000
Temperature (%)

Figure 3.14. Tm region of DSC heating thermograms presented in Figure 3.12. Heating
rate = 10 C/min., cooling rate = 50 C/min.















B


A PP

B PPICOMPICLAYIF-POE

o C PPICOMPIF-OLIG.LAY
,1.




A











0 50 100 150 200 250
Temperature (0C)

Figure 3.15. DSC cooling thermogram for PP and impact modified PP/clay
nanocomposites. Heating rate = 10 C/min., cooling rate = 50 C/min.





































250 nm


Figure 3.16. TEM micrograph of PP/COMP/F-OLIG/CLAY.


4


200 nm


Figure 3.17. TEM micrographs of PP/COMP/F-POE/CLAY