MIXING STUDIES AND SIMULATION OF COMPOUNDING CHOPPED FIBER AND SILICA FILLER INTO THERMOPLASTICS IN A MODULAR CO-ROTATING TWIN

SCREW EXTRUDER

A Dissertation Presented to The Graduate Faculty of The University of Akron

In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy

Sug Hun Bumm May, 2010

MIXING STUDIES AND SIMULATION OF COMPOUNDING CHOPPED FIBER AND SILICA FILLER INTO THERMOPLASTICS IN A MODULAR CO-ROTATING TWIN SCREW EXTRUDER

Sug Hun Bumm Dissertation

Approved:

Accepted:

Advisor Avraam I. Isayev Committee Member Sadhan C. Jana Committee Member Erol Sancaktar Committee Member Fred Choy Committee Member Shing-Chung Josh Wong ii

Department Chair Sadhan C. Jana Dean of the College Stephen Z. D. Cheng Dean of the Graduate School George R. Newkome Date

ABSTRACT

Mixing studies of glass fibers and silica filler into thermoplastics, two polypropylenes and polyamide 12, in co-rotating twin screw extruder were carried out. Fiber length and agglomerate sizes were determined at various positions along the screw in the twin screw extruder. The damage of glass fibers at various conditions was investigated by varying viscosity, screw speed, screw configuration and glass fiber length and diameter. Increasing screw speed, melt matrix viscosity and glass fiber concentration were found to increase the extent of fiber breakage. Based on our experimental data and Euler buckling theory the composite modular kinetic model to describe glass fiber damage was developed. Regions of major and minor fiber breakage in co-rotating twin screw

extruder were established. The simulation program based on experimental data and kinetic constants was developed. Comparisons were made between simulated results and experimental data. Silica agglomerates were characterized by measuring their mass average values to avoid subjective result due to small filler particles. Silica agglomerate sizes as effected by viscosity, screw speed and filler concentration in co-rotating twin screw extruder were studied. The composite modular kinetic model for evaluating silica agglomerate breakup was developed. The kinetic constants of breakup and re-agglomeration for various iii

conditions were calculated based on the stresses applied to agglomerates and their cohesive strength. Experimental data were compared with calculated results.

Generally, calculated results from the modified kinetic model of glass fiber and silica filler breakup showed reasonable agreement with experimental data.

iv

ACKNOWLEDGEMENTS

First, the author would like to express a deep appreciation to my loving wife, Hee Mi Na, his son, Josh Ha Ram Bumm and his daughter, Lydia Ha Eun Bumm for their love, patience and assistance. Further acknowledgement is made to the authors parents, parents-in-law, and all family members for their continuous encouragement.

The author would like to express a sincere appreciation and gratitude to his two advisors, Prof. James. L. White and Prof. Avraam I. Isayev, whose guidance, encouragement and contributed to the completion of his Ph.D. Dissertation.

The deep appreciation is extended to Dr. S.C. Jana, Dr. E. Sancaktar, Dr. F. Choy and Dr. S. Wong for their helpful advice. The author is grateful to all the facility, staff and students (especially Dr. B. J. Lee & Mr. J. Choi) for their helpful discussions.

Above of all, Thanks my Lord Jesus, my rock, my salvation and my hope.

TABLE OF CONTENTS

Page LIST OF TABLES .................................................................................................................. x LIST OF FIGURES ............................................................................................................. xii CHAPTER I. INTRODUCTION ............................................................................................................... 1 II. BACKGROUND AND LITERATURE SURVEY ............................................................ 4 2.1. Composition, Structure, and Properties of Polymer Compounds ................................ 4 2.1.1. Thermoplastic Polymers ..................................................................................... 4 2.1.2. Fillers .................................................................................................................. 5 2.2. Modular Intermeshing Co-rotating Twin Screw Extrusion.......................................... 7 2.2.1. Historical Development and Geometry for Intermeshing Co-rotating TSE ....... 7 2.3. Modeling Flow in Modular Intermeshing Co-rotating Twin Screw Extruder ........... 11 2.3.1. Isothermal Analysis of Screw and Kneading Disc Block Elements ................. 11 2.3.2. Composite Isothermal Modular Machines ........................................................ 13 2.3.3. Non-isothermal Modular Machines .................................................................. 14 2.3.4. Melting Mechanisms......................................................................................... 15 2.4. Compounding of Glass Fiber and Fiber Breakage..................................................... 17 2.4.1. Compounding of Glass Fiber ............................................................................ 18 2.4.2. Fiber Breakage in Thermoplastic Materials and Extruders .............................. 18 vi

2.5. Compounding and Breakup of Solid Fillers .............................................................. 22 2.5.1. General .............................................................................................................. 22 2.5.2. Agglomerate Dispersion Mechanism ................................................................ 23 2.5.3. Breakage Kinetic Model of Solid Particles ....................................................... 25 III. EXPERIMENTAL .......................................................................................................... 32 3.1. Materials Specification and Characterization ............................................................ 32 3.1.1. Materials specification ...................................................................................... 32 3.1.2. Thermal Properties ............................................................................................ 33 3.1.3. Rheological Characterization ............................................................................ 33 3.2. Apparatus ................................................................................................................... 36 3.2.1. Mixing in the Co-rotating Twin Screw Extruder .............................................. 36 3.2.2. Characterization of Glass Fiber and Silica Particles ......................................... 39 IV. COMPOUNDING AND BREAKAGE OF GLASS FIBERS IN POLYMER MELT MATRICES ........................................................................................................................... 45 4.1. Introduction ................................................................................................................ 45 4.2. Results ........................................................................................................................ 46 4.2.1. Comparison of different polymers in twin screw extruder ............................... 46 4.2.2. Statistical analysis of data ................................................................................. 49 4.2.3. Comparison of fiber loading ............................................................................. 49 4.2.4. Effect of different screw speeds ........................................................................ 54 4.2.5. Comparisons of different screw configurations ................................................ 54 4.2.6. Comparisons of glass initial fiber length and diameter effect for PP-1 ............ 63 4.2.7. Correlations with applied torque....................................................................... 63 4.3. Discussion and Interpretation .................................................................................... 63 4.3.1. Comparison with earlier research ..................................................................... 69 vii

4.3.2. Correlation with machine torque and power ..................................................... 70 4.3.3. Behavior of PA12 .............................................................................................. 72 4.3.4. Screw configuration .......................................................................................... 72 4.4. Conclusion ................................................................................................................. 75 V. COMPOUNDING OF THERMOPLASTIC WITH SILICA PARTICLES ..................... 76 5.1. Introduction ................................................................................................................ 76 5.2. Results ........................................................................................................................ 77 5.2.1. Characterization of silica agglomerate size ...................................................... 77 5.2.2. Comparison of different polymers in twin screw extruder ............................... 85 5.2.3. Effect of different screw speeds in polypropylene-1 ........................................ 87 5.2.4. Comparison of silica loading in polyamide 12 ................................................. 87 5.2.5. Correlations with applied torque and power ..................................................... 87 5.3. Discussion and Interpretation .................................................................................... 91 5.3.1. Comparison to glass fiber breakage study ........................................................ 91 5.3.2. Correlation with machine torque and power ..................................................... 92 5.3.3. Comparison of different processing conditions ................................................ 92 5.4. Conclusion ................................................................................................................. 95 VI. KINETIC MODEL OF GLASS FIBER BREAKUP ..................................................... 96 6.1. Introduction ................................................................................................................ 96 6.2. Model and Simulation ................................................................................................ 97 6.2.1. Euler Buckling Theory ...................................................................................... 97 6.2.2. Kinetic model of glass fiber breakage ............................................................ 100 6.2.3. Calculation of kinetic constants and critical length for glass fiber breakup ... 104 6.2.4. Simulation program for glass fiber breakage .................................................. 114 6.3. Comparison with Experiment .................................................................................. 119 viii

6.3.1. Comparison to simulation and experimental results ....................................... 119 6.4. Conclusion ............................................................................................................... 125 VII. KINETIC MODEL OF AGGLOMERATE BREAKUP OF SILICA PARTICLES .... 126 7.1. Introduction .............................................................................................................. 126 7.2. Kinetic model and calculation for silica particles .................................................... 127 7.2.1. Kinetic model of agglomerate breakup in silica compounding ...................... 127 7.2.2. Calculation of kinetic constants and discussion.............................................. 129 7.3. Comparison with experiments ................................................................................. 139 7.3.1. Comparison with calculation and discussion .................................................. 139 7.4. Conclusion ............................................................................................................... 149 VIII. CONCLUSIONS AND RECOMMENDATIONS ..................................................... 150 8.1. Conclusions .............................................................................................................. 150 8.1.1. General ............................................................................................................ 150 8.1.2. Compounding with glass fiber ........................................................................ 151 8.1.3. Mixing with silica particles ............................................................................. 152 8.2. Recommendations for Further Work........................................................................ 153 REFERENCES ................................................................................................................... 154 APPENDIX ......................................................................................................................... 165

ix

LIST OF TABLES

Table

Page

3.1 Polymers used in this study............................................................................................. 34 3.2 Fillers used in this study ................................................................................................. 34 5.1 Mass average particle silica agglomerate size after mixing with screw configuration A94 6.1 Material parameters for simulation ............................................................................... 105

6.2 Kinetic constants for polypropylene-1 for glass fiber 10% (4 mm/14 m) .................. 108

6.3 Kinetic constants for polyamide 12 for glass fiber 10% (4 mm/14 m) ...................... 109

6.4 Kinetic constants for polypropylene -2 for glass fiber 10% (4 mm/14 m) ................. 110

6.5 Critical fiber length for different polymers, screw speeds and screw configurations for glass fiber 10% (4 mm/14 m) ................................................................................... 116

7.1 Steady state and filler agglomerate size at the beginning of mixing with screw configuration A ........................................................................................................... 130 7.2 Kinetic constants of breakup and re-agglomeration in polypropylene1 with screw configuration A and silica 10% ................................................................................... 132 x

7.3 Kinetic constants of breakup and re-agglomeration in polyamide 12 with screw configuration A and 200 rpm ...................................................................................... 133 7.4 Kinetic constants of breakup and re-agglomeration in polypropylene-2 with screw configuration A and silica 10% ................................................................................... 134 7.5 Comparison of breakdown kinetic constants of PP1-CaCO 3 and PP1-silica agglomerates with screw configuration A , screw speed 200rpm and 10% concentration ............................................................................................................... 146 7.6 Comparison of agglomerates kinetic constants of PP1-CaCO 3 and PP1-silica agglomerates with screw configuration A , screw speed 200 rpm and 10% concentration ............................................................................................................... 147

xi

LIST OF FIGURES

Figure

Page

3.1 DSC traces for isotactic polypropylene and polyamide 12 at a heating rate of 20oC/min ....................................................................................................................... 35 3.2 Shear viscosity versus shear rate data for the neat polymers (temperature=210 oC) ...... 37 3.3 Screw Configurations in TEX-30 Intermeshing Twin Screw Extruder .......................... 38 3.4 Photographs of special and general elements along with their length and element number .......................................................................................................................... 40 3.5 Typical photographs of fiber length in optical microscope............................................. 41 3.6 Position along the screw length ...................................................................................... 42 4.1 Glass fiber length (L n ) along the screw configuration A in different polymers (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))........................................................... 47 4.2 Glass fiber length (L w ) along the screw configuration A in different polymers (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))........................................................... 48 4.3 Glass fiber length L n along screw configuration A for polypropylene-1 (screw speed 200 rpm, glass fiber (4 mm/14 m)) ............................................................................. 50 4.4 Glass fiber length L w along screw configuration A for polypropylene-1 (screw speed 200 rpm, glass fiber (4 mm/14 m)) ............................................................................. 51

xii

4.5 Glass fiber length L n along screw configuration A for polyamide 12 (screw speed 200 rpm, glass fiber (4 mm/14 m)) .................................................................................... 52 4.6 Glass fiber length L w along screw configuration A for polyamide 12 (screw speed 200 rpm, glass fiber (4 mm/14 m)) .................................................................................... 53 4.7 Glass fiber length L n along screw configuration A for different speeds (polypropylene-1, glass fiber 10% (4 mm/14 m)) ...................................................... 55 4.8 Glass fiber length L w along screw configuration A for different speeds (polypropylene-1, glass fiber 10% (4 mm/14 m)) ...................................................... 56 4.9 Glass fiber length L n along screw configuration A for different speeds (polyamide 12, glass fiber 10% (4 mm/14 m)) .................................................................................... 57 4.10 Glass fiber length L w along screw configuration A for different speeds (polyamide 12, glass fiber 10% (4 mm/14 m)) .............................................................................. 58 4.11 Glass fiber length L n along the different screw configurations for polypropylene-1 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m)) ............................................... 59 4.12 Glass fiber length L w along the different screw configurations for polypropylene-1 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m)) ............................................... 60 4.13 Glass fiber length L n along the different screw configurations for polyamide 12 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m)) ............................................... 61 4.14 Glass fiber length L w along the different screw configurations in polyamide 12 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m)) ............................................... 62 4.15 Glass fiber length L n along the screw configuration A in different fiber length (polypropylene -1, screw speed 200 rpm, glass fiber 10% (14 m diameter)) ............. 64 4.16 Glass fiber length L w along the screw configuration A in different fiber length (polypropylene -1, screw speed 200 rpm, glass fiber 10% (14 m diameter)) ............. 65 xiii

4.17 Glass fiber length L n along the screw configuration A in different fiber diameter ( polypropylene -1, screw speed 200 rpm, glass fiber 10% (4 mm length)) ................. 66 4.18 Glass fiber length L w along the screw configuration A in different fiber diameter ( polypropylene -1, screw speed 200 rpm, glass fiber 10% (4 mm length)) ................. 67 4.19 Glass fiber breakage relationships with torque (a) and power (b) for all screw configurations, glass fiber (4 mm/14 m), and all concentrations..68

4.20 Torque as a function of different screw speed (a) for screw configuration A, glass fiber 10% (4 mm/14 m) and polymers (b) for screw configuration A, screw speed 200 rpm, glass fiber 10% (4 mm/14 m)....71 4.21 Torque as a function of different screw configurations (a) for screw speed 200 rpm, glass fiber 10% (4 mm/14 m) and volume percents (b) for screw configuration A, screw speed 200 rpm, glass fiber (4 mm/14 m) .......................................................... 73 4.22 Glass fiber length Ln along the screw length in different screw configuration (polypropylene-1, speed 200 rpm, glass fiber 10% (4 mm/14 m)) ............................. 74 5.1 SEM observation in PP-1/silica 10% along the screw configuration A for a screw speed of 50 rpm in a co-rotating twin screw extruder. .................................................. 78 5.2 SEM observation in PP-1/silica 10% along the screw configuration A for a screw speed of 100 rpm in a co-rotating twin screw extruder. ................................................ 79 5.3 SEM observation in PP-1/silica 10% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder. ................................................ 80 5.4 SEM observation in PP-2/silica 10% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder. ................................................ 81

5.5 SEM observation in PA12/silica 1% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder. ................................................ 82 xiv

5.6 SEM observation in PA12/silica 10% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder. ................................................ 83 5.7 SEM observation in PA12/silica 20% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder ................................................ 84

5.8 Particle agglomerate size along the screw length for screw configuration A and different polymers (silica 10%, screw speed 200 rpm) with corresponding SEM micrographs................................................................................................................... 86 5.9 Particle agglomerate size along the screw length for screw configuration A and different screw speeds (polypropylene-1, silica 10%) with corresponding SEM micrographs................................................................................................................... 88 5.10 Particle agglomerate size along the screw length for screw configuration A and different concentrations (polyamide12, screw speed 200 rpm) with corresponding SEM micrographs ......................................................................................................... 89 5.11 Particle agglomerate size relationship with torque (a) and power (b) for screw configuration A, silica 10%, different screw speed ...................................................... 90 6.1 General tendency for glass fiber breakage in co-rotating twin screw extruder indicating region of minor and major breakage .......................................................... 101 6.2 SEM micrographs of glass fiber with polypropylene-1 and polyamide 12 for glass fiber 10% (4 mm/14 m), screw configuration A and screw speed 200 rpm in corotating twin screw extruder ....................................................................................... 103 6.3 Shear viscosity of PP-1 (a) and PP-2 (b) of different temperatures .............................. 106 6.4 Shear viscosity of Polyamide 12 of different temperatures .......................................... 107 6.5 Kinetic constants for different screw elements and rpm in PP-1 for screw configuration A, glass fiber 10% (4 mm/14 m) ........................................................ 111 xv

6.6 Kinetic constants for different screw elements and rpm in PA12 for screw configuration A, glass fiber 10% (4 mm/14 m) ........................................................ 112 6.7 Kinetic constants for different screw elements at 200 rpm in PP-2 for screw configuration A, glass fiber 10% (4mm/14m) .......................................................... 113 6.8 Average kinetic constant versus viscosity of polymers for screw configuration A, screw speed 200 rpm, glass fiber 10% (4 mm/14 m)................................................ 115 6.9 Simulation flow chart for glass fiber breakage program .117 6.10 Simulation results in Akro-Co-Twin Screw for residence time and pressure for polypropylene-1, screw configuration A, screw speed 200 rpm, glass fiber 10% (4 mm/14 m).................................................................................................................. 118 6.11 Comparison of glass fiber length between simulation results and experimental results for polypropylene-1 at screw speed 200 rpm of screw configuration A (a) and screw configuration C (b) for glass fiber 10% (4 mm/14 m).................................... 120 6.12 Comparison of glass fiber length between simulation results and experimental results for polypropylene-1 at screw speed 100 rpm (a) and 50 rpm (b) for screw configuration A, glass fiber 10% (4 mm/14 m) ........................................................ 121 6.13 Comparison of glass fiber length between simulation results and experimental results for polyamide 12 at screw speed 200 rpm of screw configuration A (a) and screw configuration C (b) for glass fiber 10% (4 mm/14 m).................................... 122 6.14 Comparison of glass fiber length between simulation results and experimental results for polyamide 12 at screw speed 100 rpm (a) and 50 rpm (b) for screw configuration A, glass fiber 10% (4 mm/14 m) ........................................................ 123 6.15 Comparison of glass fiber length between simulation results and experimental results for polypropylene-2 at screw speed 200 rpm of screw configuration A for glass fiber 10% (4 mm/14 m) ................................................................................... 124 xvi

7.1 Kinetic constants of breakup for different screw elements and rpm in PP-1 with screw configuration A and silica 10% ................................................................................... 135 7.2 Kinetic constants of re-agglomeration for different screw elements and rpm in PP-1 with screw configuration A and silica 10%................................................................. 136 7.3 Kinetic constants of breakup for different screw elements and concentrations in PA12 with screw configuration A and screw speed 200 rpm ............................................... 137 7.4 Kinetic constants of re-agglomeration for different screw elements and concentrations in PA12 with screw configuration A and screw speed 200 rpm.................................. 138 7.5 Kinetic constants of breakup (a) and re-agglomeration (b) for different screw element in PP-2 with screw configuration A and silica 10%.................................................... 140 7.6 Comparison of calculated and measured agglomerate particle size for PP-1 at screw speed 200 rpm (a) and 100 rpm (b) with screw configuration A and silica 10% ........ 141 7.7 Comparison of calculated and measured agglomerate particle size for PP-1 at screw speed 50 rpm with screw configuration A and silica 10% .......................................... 142 7.8 Comparison of calculated and measured agglomerate particle size for PA12 at silica concentration of 10% (a) and 20% (b) with screw configuration A and screw speed 200 rpm ....................................................................................................................... 143 7.9 Comparison of calculated and measured agglomerate particle size for PA12 at silica concentration of 1% with screw configuration A and screw speed 200 rpm .............. 144 7.10 Comparison of calculated and measured agglomerate particle size for PP-2 at silica concentration of 10% and screw speed 200 rpm with screw configuration A ............ 145

xvii

CHAPTER I I. INTRODUCTION

Mixing of various ingredients into thermoplastics is an important area in polymer processing. Mixing operations include the blending of polymeric resins, and the introduction of various solid fillers and additives and indeed reactive processing. The fillers include minerals and glass fibers. Some of the other commonly used additives are processing aids, cross-linking, foaming and slip agents, stabilizers, antioxidants, and pigments. The various mixing operations encountered in polymer processing are carried out with either batch or continuous mixers. Batch mixers are the oldest types of industrial mixer and are still widely used especially in the rubber industry. Continuous mixing is usually carried out in twin screw extruders, which are the primary mixing machines of the thermoplastics industry. Twin screw extruders are divided into three types according to the arrangement of their screws. These are non-intermeshing, tangential and intermeshing twin screw machines. They are also classified according to screw rotation directions: co-rotating twin screw extruders and counter rotating twin screw extruders. Modern twin screw extruders have modular construction and possess screw and mixing elements, barrel segments, feed

ports and vents. These individual screw elements, mixing elements and barrel segments may be configured in various ways to perform the desired process requirements. Extrusion compounding of glass fiber is the most popular method of incorporation glass fiber into thermoplastic compounds. There is little tendency of glass fibers to agglomerate and they are easily distributed in the melt. They have exhibited severe breakage. The residual fiber length has an important influence on the mechanical properties of the final product. Therefore, glass fiber length reduction during processing has been the subject of the several investigations [1-9]. In compounding small particles, there have been few basic investigations which largely involve rubber in different types of mixing equipment [10-15]. These have mostly involved carbon black but also more recently include naturally occurring calcite, clay and talc as well as synthetically prepared silica and zinc oxide. There have also been few comparisons of the relative mixing characteristics of different particles in polymer systems. Various researchers [16-18] have studied the breakup of carbon black agglomerates in rubber matrices. Rwei et al. [16, 17] have described studies on the breakup of agglomerates of carbon black in silicone oil. White et al. [19] investigated the breakup of filler agglomerates in the mixing process and compared the mixing results for an the internal mixer and a Kobe Steel NEX-T continuous mixer with various elastomers. They built kinetic models for fiber and agglomerate breakup. This was further developed by Shon et al. [7, 8]. This dissertation emphasizes the most important commercial continuous mixer, the co-rotating twin screw machine. Glass fibers as mentioned earlier are readily

distributively mixed. We investigate glass fiber breakage in the thermoplastics along the various machine conditions. Analogous to glass fiber breakage is agglomerate breakup for silica. We consider quantitative modeling of the mixing and fiber/agglomerate breakup processes in this machine including the effects of various mixing elements.

CHAPTER II II. BACKGROUND AND LITERATURE SURVEY

2.1. Composition, Structure, and Properties of Polymer Compounds

Polymer compounds generally contain thermoplastic polymers, elastomers, fillers, oils, and low molecular weight additives

2.1.1. Thermoplastic Polymers Many commercial polymers are available. We discuss here the polymers which are compounded materials relevant to this dissertation.

2.1.1.1. Isotactic Polypropylene (PP) The most widely compounded thermoplastic is polypropylene. The production of isotactic polypropylene (PP) began with the commercialization of coordination polymerization in 1957. PP can be made in isotactic, syndiotactic, atactic forms on which controlled mixed tacticity. Isotactic and syndiotactic polypropylenes were first synthesized and characterized by Natta and his coworkers [20, 21]. It is isotactic polypropylene which has become the most widely used thermoplastic in compounds. Isotactic PP is an essentially linear, highly crystalline polymer, with a crystalline melting temperature of 165 oC and glass transition temperature of -15 oC. The isotactic 4

chains crystallize in a helical conformation, giving it a relatively low density. Isotactic PP has a crystalline density of 0.9 compared to about 0.99 for polyethylene and is melt processed in the range of 180 ~240 oC. At higher temperatures it exhibits severe chemical degradation. The surface tension of molten PP is 24.8 dyne/cm at 200 oC, and its dielectric constant is 2.3 at 1KHz. PP is widely applied in making film, and fibers as well as thermoplastic elastomers. Its compounds are often injection molded [22].

2.1.1.2. Polyamides Polyamides, often referred to as nylons, were first manufactured in 1938. Many types of polyamides are today commercially available. The most popular type is polyamide 6, followed by polyamide 6/6, then polyamide 6/12, 12 and 11. Polyamides absorb more moisture from the air than most other polymers. This has an effect on process-ability, dimensional stability and physical properties. Moisture acts as a plasticizer, reducing tensile strength and stiffness and increasing elongation. Polyamides generally crystallize into extended planar zigzags joined together in hydrogen-bonded sheets. Higher polyamides (11, 12) have significantly lower stiffness and heat resistance than nylon 6 and nylon 6/6, but have improved resistance to polar solvents and lower moisture absorption [23].

2.1.2. Fillers Many commercial reinforcing types of fillers for polymer are available. We discuss the major particle reinforcements below.

2.1.2.1. Glass Fiber Continuous glass fibers were first manufactured in substantial quantities by OwensCorning in the 1930s for high temperature electrical applications. Glass fiber is used in two forms in PP. Glass mat reinforced PP(GMT-PP) is produced in small quantities for the automotive industry. Composites containing short GF are also widely used. The properties of glass fiber reinforced PP are in the range of thermoplastics engineering. Proper surface treatment of the glass fiber is crucial in glass-polymer compound in order to increase properties [24].

2.1.2.2. Silica Silica can be made with many of the morphological features of carbon blacks and two forms are widely used in elastomer technology, these are fumed or pyrolytic silica and precipitated silica. Fumed silica is made by controlled combustion of a volatile silica containing compound, such as silicon tetrachloride. This process is very similar to the carbon black techniques and it is easy to see how similar particle morphologies can arise. The products are, however, significantly more expensive than carbon blacks. For this reason, use of fumed silica in polymers is largely restricted to the special area of silicone elastomers. Precipitated silicas are less expensive and have been widely used in rubber applications for many years. The technology has become increasingly important in tire manufacturing. Precipitated silicas are generally made by acidifying solutions of sodium silicate, which can be readily obtained by methods such as digesting sand with sodium hydroxide. 6

Recent developments in precipitated silica technology include the better dispersing silica and improved balance between particle size/surface area and structure [24].

2.2. Modular Intermeshing Co-rotating Twin Screw Extrusion Twin screw extruders have become an important part of polymer processing technology especially for continuous blending, compounding, devolatilization and polymerization [25]. Twin screw extruders can be classified as co-rotating and counterrotating, on the basis of the direction of the rotation of screws. If the two screws rotate in the same direction, it is termed a co-rotating twin screw extruder, and if each screw in the twin screw extruder rotates in opposite direction they are called counter-rotating. If the two screws are fully contacted, it is called a fully intermeshing twin screw extruder. The screws are separated, it is called a non-intermeshing twin screw extruder. The barrels of twin screw extruders may be heated by hot liquids or by electricity. The latter is more common. Multiple feed ports and vents are located along the barrels. The intermeshing co-rotating twin screw extruder is the major continuous mixing devices. Roughly 60 companies around the world produce the type of machine.

2.2.1. Historical Development and Geometry for Intermeshing Co-rotating TSE The earliest patent for a co-rotating twin screw extruder is attributed to Coignet in 1869 [26]. In 1901, a German patent of Wunshe [27] described a self wiping double threaded co-rotating twin screw extruder pump. British patent of 1916 [28] and a subsequent US patent of 1920 [29] of Easton also claimed self-wiping characteristics. 7

In the 1930s Roberto Colombo and Lavorazione Materie Plastiche (LMP) of Turin, Italy developed the first commercialized co-rotating twin screw extruder. Colombo filed patents [30-33], which employ two or more intermeshing screws rotating in the same direction. A U.S. patent of 1932 by Nelson [34] of the Universal Gypsum and Lime of Chicago describes a continuous mixer consisting of a series of double tipped self-wiping co-rotating disc block elements resembling the kneading disc blocks of the modern machine. This is today considered as the origin of kneading disc block elements. A patent by Pease of 1936 [35] describes the detailed designs of this extruder. These early developments were followed by significant engineering progress in Germany in the late 1940s. This was related to both improved designs including modular machine and exploit applications such as polymerization, mixing and kneading, reactive extrusion, and devolatilization. These activities were associated with the engineering department the current Bayer AG including Erdmenger, Meskat, and co-workers. A notable achievement in a patent of 1950 by Meskat and Pawlowski [36] was a modular intermeshing co-rotating twin screw machine with both left and right handed screw elements. Erdmengers pioneering efforts in the late 1940s and 1950s led to the foundation of co-rotating twin screw mixing technology as it is known today. His patents describe a machine having barriers in screw channels and single and double tipped kneading disc block machines for mixing and mastication [37-39]. In succeeding patents [40], Erdmenger described the use of triple tipped kneading disc blocks keyed onto shafts. Erdmengers efforts later resulted in modular machines having both screw and kneading block elements [41] which are widely used in co-rotating twin screw machines today. 8

By the mid 1950s, Bayer licensed Werner & Pfleiderer to commercially manufacture their self-wiping co-rotating machines. These were modular twin screw extruder with both screw and kneading disc block elements. This was described in a paper by Fritsch and Fahr [42]. These designs also contained multiple ports for devolatilization and also for addition of secondary feed streams. Werner & Pfleiderer machines have been available commercially since the late 1950s. Werner and Pfleiderer (today Coperion Werner and Pfleiderer) remains the leading manufacturer today. In 1953, Ellerman [43] designed a self-wiping co-rotating twin screw continuous mixer with initial and final screw regions, and an intermediate rotor section on machined shafts. A distinguishing feature of this design was that at the die end screw like threads were cut into the barrel whereas screw ends were shaft-like. This was followed by a 1964 paper by Proksch [44] which described the newly commercialized Krauss-Maffei DSM which was based on this design. This machine was subsequently licensed by Japan Steel Works who still manufacture it. Around the same period Baker Perkins a then part owner of Werner and Pfleiderer also began production of modular twin screw machines with screw and kneading disc block elements. This was based upon a US patent granted to Loomans and Brennan [45]. A patent of 1975 by Loomans [46] of Baker Perkins group described a special new selfwiping profile including a radially projecting hoop. A subsequent patent by Todd [47] contains a design of an adjustable saddle like section to provide an improved mixer construction and permit venting.

With the expiration of the Erdmenger patents in the 1970s an increasing number of companies manufactured these types of machines these have been many new manufactured. Newer element designs for co-rotating twin screw extruders have also emerged from the 1970s to the present. Most manufacturers have developed special mixing elements. These include mixing gears from Berstorff, internal mixer rotor like elements from Kobe Steel, polygon mixing elements from Farrel and turbine mixing elements (screw elements with slices in their screw flights) from Werner & Pfleiderer. In some cases manufacturers have intentionally created screw elements with smaller root diameter and avoided the traditional self-wiping profile. The other focus of machine manufacturers has been to produce deeper screw channels for higher outputs, to design better gearboxes, thrust bearings and also select better materials of construction to allow high screw speed and high torque. In a 1965 patent, Zimmerman [48] described the self-wiping geometry based on kinematic principles. Booy [49, 50] in a more detailed study derived geometrical relations for the self-wiping co-rotaing elements. Acoording to Booys study the cross-section is unique for given diameter, center line distance, and number of tips. Booy also considered cross-sectional profiles both for screws with a speed ratio and for pairs of identical screws.

10

2.3. Modeling Flow in Modular Intermeshing Co-rotating Twin Screw Extruder Isothermal and non-isothermal flow studies on intermeshing co-rotating twin screw extruders are discussed in terms of flow in screw and kneading block elements as well as composite modular machines.

2.3.1. Isothermal Analysis of Screw and Kneading Disc Block Elements Analysis of flow in right handed screw elements has received much attention of researchers. Early efforts to understand flow mechanisms were made by Erdmenger [51], and Armstroff and Zettler [52]. Erdmenger reported basic experiments on the mechanisms of fluid motion. He indicated that the molten fluid flows in the screw channels and also noted that the flow in kneading disc block elements differed from this. These early studies were only qualitative. Various authors applied the classical pressure and drag flow analysis from the single screw extrusion theory to the analysis of modular intermeshing co-rotating twin screw extruders. More quantitative descriptions followed with publications by Werner and Else [53] based on a dissertation by Werner [54] at the University of Munich, Burkhardt, Herrmann and Jakopin [55], Mack and Eise [56], Curry and Nangeroni [57]. These studies clearly explained the flow mechanism as drag flow but were restricted to Newtonian fluids. Denson and Hwang [58] analyzed the flow characteristics of Newtonian fluids in the right handed screw elements of fully filled self-wiping co-rotating twin screw extruder considering the detailed geometry in a flattened screw channel of Booy [49]. They calculated velocity fields and pressure profiles using finite element methods 11

neglecting the intermeshing regions. Szydlowski and White [59] solved the same problem but used the FAN method of Tadmor et al. [60]. The first modeling studies of kneading blocks were researched by Szydlowski et al. [61-63] One of the early successful approaches for non-Newtonian fluids in screws is

the 1987 paper by Wang and White [64]. They solved the non-Newtonian problem by two methods: FAN and FEM. Similar results were presented by Wang, White and Szydlowski [65]. The material flow behavior was represented by a power law model. In 1990, Potente, Ansahl, and Wittemier [66] sought to calculate the characteristic curves for screw elements using analytical methods. Their analysis was based on a number of empirical assumptions and procedures. The first analysis of flow characteristics in left handed screw elements was simulated by White and Szydlowski [67]. The simulation method is the same with the method of right handed screw elements but the boundary conditions are different. Chen and White [68] presented dimensionless non-Newtonian calculations for throughput and pressure gradients. For kneading disc blocks, early efforts to understand flow mechanism were qualitative in nature. Quantitative efforts for simulation of flow in kneading disc blocks are however only recent in origin. Szydlowski, Brzoskowski, and White [61] simulated flow of a Newtonian fluid using a modified FAN method. The intermeshing region effects were neglected in this study but the authors computed mixing coefficients based on fractional flow fluxes. Subsequently, Szydlowski and White [62] included the effects of the intermeshing region using a piston pump model. This study was also only for Newtonian fluids. Later Szydlowski and White [63] used the modified FAN method to 12

calculate flow characteristic curves of a power law fluid in kneading disc blocks. In a subsequent study, Wang, White and Szydlowski [65] rigorously calculated the flow characteristics of a power law fluid in kneading disc block regions. Chen and White [68] calculated dimensionless pressure drop and flow rate characteristic curves for kneading disc blocks. There have been other such researches about flow in kneading disc block elements. Sebastian and Rakos [69] presented both FAN and FEM calculations using cylindrical coordinates. They modeled the flow using two region approximations (screw/barrel region and intermeshing region). Gotsis, Ji and Kalyon [70] developed a finite element model for kneading disc blocks. Cheng and Manas-Zloczower [71] presented a similar flow field analysis for kneading disc block regions. Their approach was based on selecting a number of sequential geometries to represent relative positions of kneading disc blocks at successive instances to account for the time dependent boundary conditions. Kim and White [72] presented a study of transient start-up mechanism of starved flow in a corotating twin-screw extruder.

2.3.2. Composite Isothermal Modular Machines An approach to simulate modular screws was originated by White and Szydlowski [67] for Newtonian fluids. If one knew the flow rate and boundary condition for the pressure at either end of the element the pressure at the other end could be computed. The pressure at the die end is generally known or may be computed from the die characteristics. Therefore to calculate the pressure profile in a modular machine one proceeds from the die end towards the hopper. Such pressure profiles subsequently were 13

presented by Wang, White and Szydlowski [65] in 1989, who generalized the previous calculations to a power law fluid. In practice, twin screw extruders are almost always starved fed. Therefore, depending on its conveying capacity an element may be starved or fully filled. The calculation of fill factor profiles along a screw configuration was presented by White, Montes, and Kim [73] in 1990. This was the beginning of the Akro co Twin Screw Software.

2.3.3. Non-isothermal Modular Machines In non-isothermal studies, we should consider the viscous dissipation heating and cooling and heating by the barrel. A non-isothermal analysis of co-rotating twin screw extruders was first discussed by Meijer and Elemans [74], who integrated the energy equation producing a one dimensional heat balance in which conduction at the barrel was accounted in terms of heat transfer coefficients. However, this analysis was only restricted to screw elements and very few results were presented. Further efforts to simulate developing temperature profiles in a modular selfwiping co-rotating twin screw extruder were undertaken by Chen and White[75, 76] in 1994. They developed a one dimensional integrated energy equation for both screw and kneading disc block elements. The heat conduction at the barrel and screw was accounted by heat transfer coefficients. They also presented calculations for a modular machine producing non-isothermal Akro co Twin screw (version 2). Using the output and a presumed temperature profile, a pressure profile and fill factor were calculated at each element in backward manner with knowledge of fluid mechanics. A forward energy balance was calculated using the fill factor profile and a temperature profile determined. 14

These calculations are performed iteratively owing to the fact that while the flow rate is known throughout, the temperature and pressure boundary conditions are not known at the die end of the machine. When the difference between the old and newly calculated pressure and temperature profile is small enough the calculations are completed. Kim and White [77] presented non isothermal transient startup study of flow in a starved twin screw extruder. A viscous Newtonian fluid is considered to gradually fill a modular co-rotating twin screw extruder with viscous heating and heat transfer to the barrel. White et al. [78] have modeled the heat transfer coefficients in a screw extruder machine. They developed a model to predict heat transfer coefficients and sought to predict the axial screw temperature profile.

2.3.4. Melting Mechanisms The studies of melting mechanisms in screw extruder started from the single screw extruder. In 1959, Maddock [79] first investigated the melting mechanism of single screw extruder. He used the pigmented plastic pellets in order to see melting phenomena in the extruder. The extruder was operated until steady state, and then suddenly stopped and cooled to room temperature. The screw was pulled out and the carcasses were peeled out. The state of a solid bed and a melt pool was observed. He found melt layer along the barrel and a melt pool along the leading flight. Tadmor, Duvdevani and Klein [80] observed the same results. For co-rotating twin screw extruder, Karian [81] investigated melting profiles of various polyvinyl chloride formulations along the kneading arrangements and concluded 15

that the melting or plasticizing region is a very short in length. Sakai [82] independently obtained similar result in his study. Todd [83, 84] made a more extensive study of the melting mechanism in corotating twin screw extruder in 1992. He used opened clamshell barrel to observe melting region in twin screw extruder. He concluded that the melting mechanism is attributed primarily to the heat dissipation imparted in particle to particle friction. He hypothesized that a compression/expansion effect in the intermeshing region between the kneading disk blocks played a key role in the melting. Potente [85] first reported experiments and discussed theoretical models of melting in 1993. Subsequently Potente, Ansahl and Klarholz [86] attempted to model melting based on the theory of single screw extruders in kneading disc blocks by approximating them to be a screw of equivalent pitch with allowance being made for the leakage flow across the flights from one channel to the adjacent channel. Potente and Melisch [87] studied the distribution of the solid and molten phases by image analysis in 1996. These revealed that the solid particle were dispersed in the melt and decreased in size along the length of the kneading disk block. They presented a model for the calculation of melting lengths and melting profiles. This model was based upon individual particles which are uniformly dispersed in the polymer melt. Also, Potente and his coworker combined the Potente-Melisch simulation with earlier simulation of melt flow in screw channels for a composite modular co-rotating twin screw extruder. Bawiskar and White [88-91] found from their extensive experiments the development of a melt layer along the barrel and a pellet bed at the surface of the screw and argued that this hot barrel surface plays a key rule in melting. They developed a 16

composite model simulation of solid conveying, melting and melt flow in a modular corotating twin screw extruder [89]. This was based on combining existing melt conveying models [65] with their new melting and solid conveying models [91] for the various elements of a modular twin screw extruder. In 2001, Gogos and Qian [92] developed a predictive model for melting due to the frictional and the plastic energy dissipation. Vergnes et al. [93] reported a new study of melting. They observed a thin film of molten polymer in the beginning of melting and solid pellets wetted by a thin film. In the fully developed melting step the deformed pellets are surrounded by molten polymer. They insisted on the Bawiskar and White [91] melting mechanism as initiation step and Gogos et al. [92] as a propagation step. They proposed model to simulate polymer melting that allows one to calculate the evolution of mean shear rate, pressure gradient, dissipated energy, pellet radius, and solid, liquid temperature along the screws. In the more recent research, Jung and White [94, 95] made a broad based experimental investigation of melting in modular co-rotating twin screw extruder over a range of temperature and screw speeds. They found barrel induced melting at high temperature (above T m ), plastic deformation induced bulk melting at lower temperature and screw rotation induced melting at the lowest temperature.

2.4. Compounding of Glass Fiber and Fiber Breakage Many researchers studied the compounding of glass fiber and its mechanism. In this dissertation kinetic model of glass fiber breakage was discussed.

17

2.4.1. Compounding of Glass Fiber The fiber length distribution in compounded glass fiber-reinforced thermoplastics has an important influence of their mechanical properties. The residual fiber length mainly depends on the processing conditions. Many different compounding methods have been used to produce glass fiber-reinforced thermoplastic materials. Proper selection of compounding equipment and optimizing conditions can substantially increase mechanical properties of the final products. Many earlier studies [3, 96-98] of fiber breakage were based on the reaction of fibers to shear flow fields of a dilute suspension. It was found that fibers are bent, broken or aligned at high volume fractions. Another effect causing concentrated suspensions to deviate from dilute behavior was found to be the hydrodynamic interaction of the fiber with the suspending fluid. A third characteristic of concentrated suspensions is non-uniform distribution of fibers in the flow caused by fiber interactions with the machine geometry.

2.4.2. Fiber Breakage in Thermoplastic Materials and Extruders Extrusion compounding of glass fibers is the major method of incorporation glass fibers in thermoplastics composites. The residual fiber length has an important influence on their mechanical properties of the final product. Therefore, the glass fiber reduction during processing has been the subject of the several investigations. Various authors have analyzed the motion of fibers suspended in liquid beginning with the early work of Jeffery (1922). In particular, Forgacs and Mason [3] and Salinas and Pittman [98] analyzed the motion of fibers suspended in a various liquid subjected to laminar shear. A theory was developed relating the fluid shear stress () required to 18

buckle a straight fiber to the fiber aspect ratio (L/D) and modulus (E) yielding an expression of the following form.

E[ln(2 L / D) 1.75] 2( L / D) 4

(2-1)

Czarnecki and White [1] proposed a fiber breakage mechanism based on buckling during rotation in shear flow and compared different types of fiber breakage. Fiber length reduction depends on the melt viscosity, the intensity of the shear field and the period of treatment. They also developed, based on Forgacs and Masons [3] studies, expression for bending stress ( b ) at points along the filament

b f

4(2n + 1) Eb I 2n + 1 Fmax d Eb ( ) 2 2 2 2 L 16 d / 4 L d

(2-2)

where F max is the maximum force to bend and buckle fiber, E b is the bending modulus. They conclude that the mechanism of fiber breakage is Euler buckling [99]. Johnson and Lunt [100] suggested three possible mechanisms to break glass fibers during the compounding process, as follows: 1) by monofilaments bending around the high curvature surfaces of other filaments; 2) by the complex motion of the polymer melt producing sufficient amounts of stress in a filament to cause tensile fracture, and 3) by the film of sizing material between adjacent filaments breaking down under conditions of high shear, a phenomena that results in contraction of the high modulus glass surfaces and consequently to crack propagation through the filaments. 19

Lunt and Shortall [101, 102] considered that high shear stresses, generated at the interface of the melt film and solid bed, produce filamentisation of fiber bundles and fracture of the resultant monofilaments into elements of lower aspect ratio. They found that increasing screw speed caused an increase in the extent of fiber breakage and increasing processing temperature lead to a decreasing in the extent of fiber breakage. Salinas and Pittman [98] suggested critical curvature values to achieve fiber breakage based on thin rod theory for two extreme conditions of very stiff and flexible fibers. The critical radius for breaking, R break, is expressed using thin rod theory as

Rbreak E = r T

(2-3)

where r is fiber radius, E is the Youngs modulus, and T is the ultimate tensile strength of the fiber. Together with a result from the thin rod theory, these correlations may be used to predict breaking conditions for fibers of known Youngs modulus and ultimate tensile strength. Investigations by Turkovich and Erwin [9], Fisa [2] in 1983-5 focused on experimental studies of the phenomena of fiber breakage and its relationship to processing conditions. They concluded that most of the damage occurred in the screw metering zone, although when fibers are added after the melting zone, sufficient shear stress occurs in the mixing zone to break fibers.

20

Franzen et al. [4] studied fiber breakage comparing a single screw extruder, corotating twin screw extruder and Buss Kneader. They did not specify the modular screw configuration of the Buss Kneader, but they suggested that they used exceptionally mild screw configuration for their modular co-rotating twin screw extruder without kneading disc blocks. They found that the material compounded with the Buss Kneader had shorter average fiber length than that with the twin screw extruder. Stade [103, 104] has studied technique for compounding glass fiber thermoplastics in a Buss Kneader. He concluded that an increase in melt viscosity increases the proportion of the short fiber particles. Studies of damage to glass fibers in continuous mixing machines have been made by Grillo and Anderson [5]. They showed that the length of the mixing section has a most significant effect on the average fiber length and the fiber matrix bond. As the mixing length increases, the fiber length will decrease, while the fiber matrix bond will improve, rapidly at first, then leveling off. Recently, Shon and White [8] studied compounding in various mixing machines, including co-rotating twin screw, counter-rotating twin screw extruder, and Buss Kneader. They also compared different screw configurations, loading, feeding ports, and mixing elements. They concluded that downstream feeding of glass fibers and milder screw configuration favor less breakage of glass fibers. Also, they found that the most severe breakage of glass fibers was by modular intermeshing counter-rotating screws with special Leistritz elements and the least damage was with a Buss Kneader. The co-rotating twin screw extruder was intermediate.

21

Shon, Liu and White [7] later proposed a fiber breakup kinetic model.

dL = k f ( L L ) k f L dt

(2-4)

where k f is the fiber breakup rate constant and L is the fiber length at which there is no more buckling. The value of k f depends on the flow geometry, stress, initial fiber diameter, and tensile strength. It may be rewritten for each element in a composite modular mixing machine system.
Li ( L) = [ L0i Li ] exp( K i mi Lt res / Ltotal ) + Li
.

(2-5)

where K i represents the properties of fiber and the flow characteristics while is fractional fill level, and mi is shear rate in modular system. i represents the ith element and t res is a total residence time.
.

2.5. Compounding and Breakup of Solid Fillers Many researchers studied the compounding and breakup of solid fillers and they also investigated the dispersion mechanism of solid fillers.

2.5.1. General The mechanism of mixing of different materials is usually classified into two broad categories as distributive and dispersive mixing. Distributive (extensive) mixing describes two or more starting components, which are interspersed in space with one another and how they are distributed during flow. On the other hand, dispersive 22

(intensive) mixing describes a multitude of process in which the size of nonhomogeneities is reduced in scale. A description of flow fields and streamlines is adequate to predict the quality of distributive mixing. Generally in polymer- particle systems, dispersive mixing is more difficult. During dispersive mixing, agglomerates are broken up by application of high stresses. To predict the adequacy of dispersive mixing, the local stress level and an understanding of the agglomerate dispersion mechanism is required. We will discuss here dispersive mixing of solid filler. There are several reasons for making particulate-filled polymer compounds,. The first reason is obtaining specific property benefit in the final product. A second reason is that filler can reduce compound prices. Some fillers can also help to improve process ability. In discussing fillers, it is necessary to distinguish the commonly used terminology of aggregates and agglomerates. Aggregates are covalently bonded combinations of small ultimate particles formed during their manufacture. These occur notably in carbon black and silica. Agglomerates are combinations of aggregates or ultimate particles held together by van der waals or dipole induced physical bonds.

2.5.2. Agglomerate Dispersion Mechanism Dispersive mixing was first modeled by Bolen and Colwell [105]. They proposed that rupture occurs when hydrodynamic separating forces exceed cohesive forces. There will be an increase in the number of particles and a reduction in their size.

23

Subsequently, the mechanism of dispersion of the small particles in the polymer mixing process has been specially studied by various authors for rubber carbon black systems. Medalia [106] subsequently proposed that in a carbon black-rubber system, the rubber that penetrates within the aggregates is occluded and immobilized and thus acts as part of the filler rather than as part of the matrix. Tokita and Pliskin [107] suggested that there are three steps in mixing carbon black and rubber. The first step is filler wetting or induction. In this early stage, two major mixing mechanisms take place: one is a creation of new surface area for filler contact and formation of single mass of filler and rubber, and the other is a penetration of elastomer into filler voids. The second step is filler dispersion or agglomerate breakdown, and the third step is elastomer breakdown and interaction with filler. Parfitt [108] studied the dispersive process of powders in liquid media as incorporation of powder into liquid, wetting of the powder, breaking up of agglomerates and possibly aggregates, and stabilization of the resulting dispersion. Shiga and Furuta [18] proposed an Onion model based on experimental observations of carbon black dispersion in rubber compounds. In this model, aggregates are either individually or collectively scraped from the surface of the agglomerate. Rwei and Manas-Zloczower [16, 17] observed two distinct mechanisms of dispersion of carbon black agglomerate breakup in a transparent cone-and plane device. One mechanism called erosion initiates at lower shear stresses and is characterized by continuous detachment of small fragments from the outer shell of the pellet. The other mechanism called rupture was characterized by an abrupt splitting of the agglomerate into a small number of large fragments and occurs at relatively higher shear stresses. 24

In recent studies of single agglomerate dispersion in well-defined flow fields, two different modes of dispersion have been observed by Boyle, Manas-Zloczower and Feke [109]. These are cohesive and adhesive failure. They concluded that for agglomerates such as carbon black, calcium carbonate, and silica where fluid infiltration is minimal, dispersion occurs by cohesive failure.

2.5.3. Breakage Kinetic Model of Solid Particles Bolen and Colwell [105] were the first to propose equation to relate the particle creation rate to shearing stress and time.
1 dn = k1 ( 0 )[1 e k2t ] dt

(2-6) is the average

where k 1 is the particle creation rate, n is the number of particles,

shear stress, 0 is the minimum shear stress to cause particle rupture, k 2 is the rate constant. They also expressed the degree of mixing as a function of the number of particles produced. This theoretical analysis has been further developed by a McKelvey [110]. He considered a system in which the minor component exists as two-particle agglomerate suspended in a viscous liquid. A force balance across the stress field acting on the two particles, leads to the equation: dx 1 + x[k ] = ky, dy y

6R k= Fa

(2-7)

where x and y are the position of the center of particle, is the viscosity of medium, R is the radius of the particles, and F a is the inter-particle cohesive force. He concluded that 25

high shear stresses prompt dispersion and if the flow in the mixer is completely unidirectional, agglomerates will be ruptured, but if they simply aligned, there is no further dispersion. Dizon et al. [111] extended McKelveys theory to fillers that exhibit considerable interactions with the polymer matrix. In this case, the inter-particle cohesive force includes not only the affinity of the filler particles for each other but also their affinity for the matrix. The effective radius of the aggregates R e should be substituted for the particle radius R and the inter-particle force C and the filler-rubber adhesion forces A should be substituted for the F a term. Equation (2-7) is then transformed to: dx 1 + x[k ] = ky dy y 6R A k= C
.

(2-8)

In the mixing stage when the agglomerate radius is large compared to inter-particle force, the hydrodynamic drag force overwhelms the inter-particle force, and dispersion proceeds effectively. As agglomerate radius gets smaller, the force balance becomes less favorable for dispersion. The process of agglomerate breakdown continues until a certain equilibrium is reached between the two opposing forces, and further dispersion is no longer possible. Tadmor [112] analyzed dispersive mixing in polymer processing quantitatively by modeling agglomerates as dumbbells consisting of two unequal beads connected by a rigid connector. He calculated the force in the connector, when the dumbbell is placed in a general homogeneous velocity field of a Newtonian fluid. In simple shear flow, the maximum force in the connector was obtained as 26

Fmax = 3 ( )r1r2 In steady elongational flow, the maxium force in the connector was obtained as Fmax = 6 ( k )r1r2

(2-9)

(2-10)

where is shear rate, r 1 r 2 are radii of dumbbell and k is the rate of elongation. These models predicted that maximum forces in extensional flows are twice those in shear flows at the same deformation rate and the maximum force acting on a clump or dumbbell is proportional to the shear stress and the product r 1 r 2 . Manas-Zloczower et al [113] proposed a mathematical model of the dispersive mixing process in internal mixers. They calculated the agglomerate size distribution and the fraction of undispersed agglomerates as a function of mixing time. This model was based on the assumption that dispersive mixing is by agglomerate rupture in the narrow gap where high shear flow field occurs. The cohesive force on agglomerates was determined to be
9 1 C0 Fc = [ ] S d 8

(2-11)

where is the void volume fraction, d is the diameter of spherical particles forming the agglomerate, S is the cross sectional contact area at the rupture plane, and C o is in the range 4.06 10-11 to 4.78 10-11 N/nm. The hydrodynamic forces in shear flow were argued to be:
Fh = c 2 sin 2 sin cos

(2-12)

where is a numerical constant which depends on particle shape, is the viscosity of the liquid, is the local shear rate, c is a volume characterizing the size of the particle and and are instantaneous orientation Euler angles. The agglomerate will rupture when 27

the hydrodynamic separating forces exceed the cohesive force (F h /F c 1). By the equation for F h /F c , they concluded that agglomerate rupture is independent of agglomerate size and F h /F c is proportional to d. Therefore, the smaller the aggregates clustered in the agglomerate, the more difficult it is to break the latter. Manas-Zloczower et al [114] subsequently proposed an agglomerate size distribution and its dependencies on a number of variables with a theoretical model of the dispersive mixing process in roll mills. The volume fraction of agglomerates which are considered undispersed, is given by

D ( Xt * ) j Xt * D0 e , ( n+1) / 3 Dcr n /03 j! 2 2 j =0

n

(2-13)

where X is the fraction of broken agglomerate during one pass through the high shear zone, j is the number of ruptures corresponding to size D j, t* is dimensionless mixing time (t/t ave ), n is set by given in Eq (2-13) inequality, D o is the initial agglomerate size,

and D cr is the critical agglomerate size. Powell and Mason [115] developed a model for the dispersion of homogeneous cohesion less particle clusters. In their derivation, the rate at which particles erode from the cluster is assumed to be proportional to the surface area of the agglomerate and the applied shear rate:
d R N (t ) R 2 [ ] 2 dt a

(2-14)

where R is the radius of the cluster, N is the number of fragments erodes per unit surface area, a is the volume average radius of the fragments and is the applied shear rate.

28

Shiga and Furuta [18] proposed a model to calculate particle size distribution functions based on the assumption that each pass of an agglomerate through a high shear zone region will reduce its weight by quantity M, proportional to the hydrodynamic stress, , exerted on the surface of the agglomerate, the agglomerate size, R, and the residence time, t, in the high shear field ( -M R2t). Rwei and Manas-Zloczower [16] revised Powell and Masons model based on their observations. The size of the eroded fragments is assumed to be proportional to the size of the parent cluster: R0 R(t ) = Kt * R0 (2-15)

where R is the radius of the cluster, K is the rate constant and t*=t is a dimensionless erosion time. K is believed to depend on the flow geometry, the applied shear stress, and the cohesive strength of the agglomerate. Recently, Potente et al. [116] proposed a theoretical model which describes the three distinct mechanisms of dispersion: erosion, agglomerate rupture, and reagglomeration. In this model, they connected dispersion process with process characteristics, particularly with the melting process and the residence time. d d d d = ( ) Clusterting ( ) Rupture ( ) Erosion t t t t (2-16)

Berzin and Vergnes [117] devised a theoretical model to predict the evolution of dispersion of a inorganic filler in a polymer matrix along a twin screw extruder as a function of the screw geometry and processing conditions. They developed a general kinetic model of filler agglomerate breakup, based on chemical-like equations. 29

k i = Ci ai

(2-17)

In this approach, kinetic constants, k i are considered as a function of shear rate, represented by a power law equation with subscript i describing agglomeration and breakup possibility. Lozano et al. [118] developed a new model to predict agglomerate size distribution in a twin screw extruder. The model considers the break-up and erosion process and it uses agglomerate size population balance in its mathematical formulation. The model parameters were evaluated in simple flow.
f (v, t ) = ( f (v)V (v, f ) + ( f (v)W (v, f )) t v v

(2-18)

The term V(v,f) represent the contribution of the erosion and W(v, f) the contribution of the breakup and agglomeration process. Where v is agglomerate volume and f is the distribution function. Shon, Liu and White [7] developed models of agglomerate breakdown and fiber damage through breakage in various experimental conditions. They studied the mixing of various particulates into synthetic elastomers and polypropylene in a batch mixer and continuous mixer. They also compared the results with a Buss Kneader, co-rotating twin screw extruder and an intermeshing counter-rotating twin screw extruder with different modular screw configurations. Their model presumes that stages of agglomerate breakup can re-combine to the following form: d(d)/dt = -kd + k(1/d2) (2-19)

where agglomerate breakup rate is taken to be proportional to size d and reagglomeration to (1/d)2 (i.e. associated with small surface area). k is the agglomerate 30

breakup rate constant, and k is the agglomerate re- agglomeration rate constant. k and k are the functions of stress, filler concentration, type of particle, particle size or BET surface area of the particle.

31

CHAPTER III III. EXPERIMENTAL

3.1. Materials Specification and Characterization In this chapter, we discuss the materials and characterization and experimental procedures.

3.1.1. Materials specification We need to choose polymers for this study which reflect differences in viscosity and physical-chemical character. Three polymers chosen for this investigation are summarized in Table 3.1 Polypropylene is the commercially most widely used thermoplastic that is used for compounding. We choose two isotactic polypropylenes, an aliphatic hydrocarbon polymer, of different viscosity but both with a density of 0.90 g/cm3 and a melting temperature of 163oC (Equistar, PP31KK01, PP41BW01). In addition, we choose polyamide 12 a highly polar polymer with a density of 1.01g/cm3 and a melting point of 177.2oC (EMS, Grilamid L25). These are both available in the form of pellets. The polyamide and one of the polypropylenes have very different polarities and the viscosity of the polyamide and the polypropylenes are similar in the low shear region. Using the polymers, we can investigate the effects of both viscosity level and polarity on the dispersion of filler agglomerates and glass fiber breakage. 32

The glass fibers used in this experiment had average lengths of 4 mm (4000 m) and 13 mm and were obtained from Owens-Corning Corporation. The diameters of glass fibers used are 14 and 17 microns. The small particle used in this study is silica (Silene 7320). They are summarized in Table 3.2

3.1.2. Thermal Properties Polymer thermal characteristics were studied by Differential Scanning Calorimetry (DSC). The melting and crystallization temperature of polymers were measured by Perkin-Elmer DSC-7 at 20 ml/min nitrogen gas flow. Each sample of a weight between 5 mg to 8 mg was placed in DSC pans. The sample was first heated to 220 at 20/min and held for 5 min, then cooled down to 20 at 20/min. Melting and crystallization points were determined from the peak position, respectively. DSC traces of these polymers are given in Figure 3.1. The PP and PA12 possess melting point at 164.2 and 177.2.

3.1.3. Rheological Characterization The shear viscosity of the pure polymers and compounds is important to the compounding process. The shear viscosity of homo polymers and composites at high

shear rate was measured by a capillary rheomenter (Instron 3211).

33

Table 3.1 Polymers used in this study Melting Material Temp. () Density (g/cm3) Melt Index (g/10min) 5.0 163.0 0.90 (230/5KG) 30.0 163.0 0.90 (230/5KG) 20 Polyamide 12 178.0 1.01 (275/5KG) Supplier & Product name Equistar chemicals PP31KK01 Equistar chemicals PP41BW01 EMS GRILAMID L25

Isotactic Polypropylene-1 Isotactic Polypropylene-2

Table 3.2 Fillers used in this study Particle Material Product name Size () 0.075 BET Surface (m2/g) 35 14/17 Owens-Corning (Length) (diameter) Supplier

Silica

Siliene 7320

PPG

4mm/13mm Glass Fiber 147A

34

PP-1 PA12

Heat Flow Endo Up

120

140

160

180

200

Temperature (oC)

Figure 3.1 DSC traces for isotactic polypropylene and polyamide 12 at a heating rate of 20oC/min

35

At low shear rates, the shear viscosity of sample was determined using the Advanced Rheometrics Expansion System (ARES) at shear rate less than 10 s-1. We also measured the steady state shear viscosity using a capillary rheometer. Dies of varying diameters and varying lengths were used in the capillary instrument. Bagley die end corrections [119] were made in determining the shear stress. The shear rate was determined by the Weissenberg-Mooney method [120, 121]:

w =

32Q 3 (ln Q) [ + ] 3 D 4 4 (ln P)

(3-1)

where Q is the flow rate. Dies with varying diameter can be used to determine slippage if it is suspected [121]. The shear viscosities of the neat polymers determined at 210oC are shown in Figure 3.2.

3.2. Apparatus In this dissertation, we used the co-rotating twin screw extruder for mixing and we used various instruments for analysis.

3.2.1. Mixing in the Co-rotating Twin Screw Extruder These experiments were carried out in a Japan Steel Works Tex 30 modular co-rotating twin screw extruder. It has 30 mm diameter screws with 26 mm centerline spacing distance and 975 mm screw length. Four different screw configurations were specially chosen for these experiments. They are shown in Figure 3.3 Screw configuration A, has the mildest screw configuration through the entire screw length.

36

105

Shear Viscosity (Pa.s)

104

PP-1 PP-2 PA12

103

102
Cone-Plate Test Capiliary Test

101 10-2

10-1

100

101
-1

102

103

104

Shear rate (s-1 )

Figure 3.2 Shear viscosity versus shear rate data for the neat polymers (temperature=210 oC)

37

(a) Screw A ( No kneading disc blocks in mixing region )

(b) Screw B ( One left kneading disc blocks in mixing region)

(c) Screw C ( One left kneading disc blocks and one neutral block in mixing region)

(d) Screw D ( One left kneading disc blocks in mixing region at different position)

Figure 3.3 Screw Configurations in TEX-30 Intermeshing Twin Screw Extruder

38

Screw configuration C, has the most severe configuration. Screw configurations B and D are intermediate. Photographs of special and general elements of a twin screw extruder are shown in Figure 3.4. The polymer matrix (polypropylene, polyamide) were added in the first feed port and the glass fiber and solid particles were fed in the second feeding position for four different twin screw extruders. The polymers are melted by the screw between the first and second feed ports. The feed rate was 5 kg/hr and the fractions of glass fiber and solid particle concentration was 10 and 20 volume %. The screw rotational speed was 50 rpm, 100 rpm, and 200 rpm. The preheating barrel temperature of the mixing machines was 210oC. After the machine reached steady state, it was stopped and rapidly cooled down below the melting temperature of polymer material. Then, by slowly increasing the barrel temperature, the screw was removed from the barrel. Samples were collected at high temperature to avoid additional damage of glass fiber and solid particle agglomerates in the polymer matrix. Agglomerates and fiber dimensions were determined at various positions along the screws.

3.2.2. Characterization of Glass Fiber and Silica Particles Measurements of the damaged glass fiber were made with an Optical Microscope (Leitz Laborlux 12Pol) with 4 times magnification lens. Typical photographs of fiber length are shown in Figure 3.5 and Figure 3.6 shows the position of screw length where samples were removed. The matrix polymer was removed by burning it off in a muffle furnace maintained at 800oF for 5hr. The recovered glass fibers were dispersed on the slide plate and then the length of at least 300 fibers were measured. 39

Kneading

Neutral

45mm #32 37.5 mm # 35

30mm #33

22.5mm # 34

Figure 3.4 Photographs of special and general elements along with their length and element number

40

Figure 3.5 Typical photographs of fiber length in optical microscope

41

A : 90 mm,

B : 202.5mm,

C : 292.5 mm F : 495 mm

D : 382.5 mm, E : 450 mm,

G : 510 mm (Outside of Extruder)

Figure 3.6 Position along the screw length

42

The fiber length distribution was also evaluated using the method of moments [1]. From the fiber length, the number average (Ln) and weight average (Lw) fiber lengths was determined by the following equations: Ln =

N L N
i i

(3-2)

Lw

N L = N L
i i i

(3-3)

The polydispersity index was calculated to quantity the scatter or broadness of the fiber length distribution.

P=

Lw Ln

(3-4)

In case of small silica particles, A Hitachi S-2150 Scanning Electron Microscope (SEM) was used to characterize the filler agglomerate size. The average filler agglomerate sizes were calculated with an Image Analyzer. The average agglomerate size was generally represented in terms of higher order average of individual agglomerate size. We determined various possible averages. In case of number average value, the problem of evaluating the size of small aggregates comes into question. The results are very subjective with small particles which are usually erratically included or rejected. Large agglomerates, however, play a dominant role in the product quality of the compounds. In this study we emphasize mass average values d defined by

43

d =

N d d N d
i 3 i i 3 i

(3-5)

which is less subjective and is dominated by large particles. Here d is the mass average size of agglomerates. The d i is the individual agglomerate size and N i is the amount of agglomerates with a size of d i .

44

CHAPTER IV IV. COMPOUNDING AND BREAKAGE OF GLASS FIBERS IN POLYMER MELT MATRICES

4.1. Introduction The fiber length distribution of compounded fiber-reinforced thermoplastics has a major influence on the mechanical properties of their molded products. The residual fiber length in fabricated products mainly depends on the compounding conditions and the materials. Many different compounding methods have been used to produce glass fiberreinforced thermoplastic materials. Proper selection of compounding equipment and optimizing conditions can substantially increase mechanical properties of the final products. Twin screw extrusion compounding of glass fiber is the major method of incorporation glass fibers in thermoplastic composites. The variation of fiber length distribution during processing has been the subject of several investigations [1-3, 5, 7-9, 98-104]. However, many questions still exist because most experimental studies are not extensive enough with regard to operating conditions, range of materials, etc. In this chapter we consider this problem. We investigate the mixing of glass fiber into three different polymers of varying polarity and viscosity under various processing conditions. These are two polypropylenes (PP1, PP2) and a polyamide 12 (PA12). We give attention to how different mixing conditions such as screw rotation speed, screw 45

configurations induce breakage of the glass fiber for the various polymer matrices studied. The experimental procedures used were described in Chapter 3. The number of fibers measured and subsequently averaged for each sample was 300. The three polymers, PP1, PP2 and PA12 used in our study were characterized in Chapter 3.

4.2. Results

In this section, we will discuss experiments results for various conditions such polymer, screw speed and concentration effects.

4.2.1. Comparison of different polymers in twin screw extruder We found on studying screws removed from the twin screw extruder that after passing the first kneading block, the polymer was well melted. We fed the glass fiber into the second feeding port into the melt stream. The glass fiber we found seemed rapidly wetted by the molten polymer. For screw configuration A, there are only screw elements in mixing section of the screw. Figure 4.1 and Figure 4.2 show the number and weight average fiber lengths for the three polymers in the co-rotating twin screw extruder. In this study, 10% glass fiber, and the same speed 200 rpm were used. These figures show the general tendency that the major part of glass fiber length reduction occurs immediately after their introduction and reaches a limiting value for each compounding condition. In the case of low viscosity resin PP-2, the final limiting fiber length is significantly higher than for the higher viscosity PP1 and PA12 for both Ln and L w . The ratio L w /L n of the final fibers was in the 46

PP-1 PP-2 PA 12

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.1 Glass fiber length (L n ) along the screw configuration A in different polymers (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))

47

PP-1 PP-2 PA 12

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.2 Glass fiber length (L w ) along the screw configuration A in different polymers (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))

48

range 1.20~1.53. We observed that the fibers in the PA12 polymer more rapidly reached the lower limiting length than either of the two PPs.

4.2.2. Statistical analysis of data In this study, fiber length measurements were done using about 300 fibers. Wide variation of lengths was found. The average fiber length using the number average (L n ) and weight average (L w ) fiber lengths and associated error bars were determined. The weight average value is larger than number average value. In the following figures, error bars were used to present the standard deviations. The error bars were determined using the following equation: STD = 1 N

(x
i =1

x)2

( 4.1 )

From the error bar, we found that the fiber length data scatter to a large extent near the position of fiber entry and then decreased with increasing position along screw length. We used the standard variation values for 50% medium size fiber lengths.

4.2.3. Comparison of fiber loading Figure 4.3 to Figure 4.6 show the number and weight average fiber length for different fiber concentrations in the same all right handed screw elements co-rotating twin screw extruder configuration. In this study, we used the same screw configuration A, and same speed 200 rpm. These figures show that in compounds with higher concentrations, the glass fibers are more severely damaged than the low fiber content composition. We can see that reduction of glass fiber length for PA12 appears to be more rapid than PP-1. The ratios of L w /L n are 1.20~1.53. 49

1% 10% 20%

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.3 Glass fiber length L n along screw configuration A for polypropylene-1 (screw speed 200 rpm, glass fiber (4 mm/14 m))

50

1% 10% 20%

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.4 Glass fiber length L w along screw configuration A for polypropylene-1 (screw speed 200 rpm, glass fiber (4 mm/14 m))

51

Fiber Length (mm)

1% 10%

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.5 Glass fiber length L n along screw configuration A for polyamide 12 (screw speed 200 rpm, glass fiber (4 mm/14 m))

52

Fiber Length (mm)

1% 10%

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.6 Glass fiber length L w along screw configuration A for polyamide 12 (screw speed 200 rpm, glass fiber (4 mm/14 m))

53

4.2.4. Effect of different screw speeds Figure 4.7 to Figure 4.10 show the fiber length decrease along the screw axis for different screw speeds. As shown in the figures, the higher the screw speed the more severe the fiber breakage. In the case of PP-1, we see that the final limiting value was achieved after about 300 mm along the screw axis. For PA12, we observed that the final value was reached about after 200 mm of screw axis. Also, we found that the glass fibers were more damaged for PA12 in the higher screw speed region than for PP-1.

4.2.5. Comparisons of different screw configurations Figure 4.11 to Figure 4.14 show the fiber length distribution along the screw axis for co-rotating twin screw extruder with screw configurations A, B, C, and D for PP-1 and with screw configurations A, C, D for PA12. Screw configuration A represents a mild condition which has no kneading disc blocks. Screw B has one kneading disc block element at positions of 232 mm. Screw C has two kneading disc blocks. These are located at positions of 232 mm and 352 mm from the second hopper. Screw configuration D has one kneading disc block which is located at a position of 90 mm from the second hopper. We used the same 4 mm 10% glass fiber at a speed of 200 rpm. From these figures, we see that the number and weight average values seem to differ little along the screw length for different screw configurations except for screw D with the early kneading disc block which exhibits a more rapid initial deterioration of fiber length.

54

RPM

Fiber Length (mm)

50 100 200

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.7 Glass fiber length L n along screw configuration A for different speeds (polypropylene-1, glass fiber 10% (4 mm/14 m))

55

RPM

Fiber Length (mm)

50 100 200

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.8 Glass fiber length L w along screw configuration A for different speeds (polypropylene-1, glass fiber 10% (4 mm/14 m))

56

Fiber Length (mm)

RPM 50 100 200

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.9 Glass fiber length L n along screw configuration A for different speeds (polyamide 12, glass fiber 10% (4 mm/14 m))

57

Fiber Length (mm)

RPM 50 100 200

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.10 Glass fiber length L w along screw configuration A for different speeds (polyamide 12, glass fiber 10% (4 mm/14 m))

58

Fiber Length (mm)

Screw A Screw B Screw C Screw D

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.11 Glass fiber length Ln along the different screw configurations for polypropylene-1 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))

59

Fiber Length (mm)

Screw A Screw B Screw C Screw D

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.12 Glass fiber length L w along the different screw configurations for polypropylene-1 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))

60

Screw A Screw C Screw D

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.13 Glass fiber length Ln along the different screw configurations for polyamide 12 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))

61

Screw A Screw C Screw D

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.14 Glass fiber length L w along the different screw configurations in polyamide 12 (screw speed 200 rpm, glass fiber 10% (4 mm/14 m))

62

4.2.6. Comparisons of glass initial fiber length and diameter effect for PP-1 Figure 4.15 to Figure 4.18 show the fiber length distribution along the screw axis for different initial fiber lengths of 4 mm and 13 mm. In this study, we used the same 10% glass fiber, screw configuration A, and screw speed 200 rpm. We found that the general tendency of fiber breakage at the beginning of mixing was similar. However, both initial fiber lengths eventually decreased to the same limiting value. We also studied different fiber diameters of 14 m and 17 m. We use different L/D of glass fibers. These were 285.7 and 235.3. The result was that the large fiber diameter compounds had greater fiber lengths at the end of the mixing process. In the beginning of feeding, the glass fiber breakage tendency was same with different diameters. Along the screw axis, the glass fiber breakage was different for different diameter.

4.2.7. Correlations with applied torque As fiber breakage must be related to applied stresses, we should be able to look to the machine torque as a measure of these stresses. In Figure 4.19 we report the reduced final fiber length =Li/Lo( Li : final length, Lo : initial length) as a function of machine torque. We see that breakage increases with torque.

4.3. Discussion and Interpretation In this section, we describe comparisons with machine variables and discuss the effects of various conditions in the twin screw extruder. 63

12
4 mm 13 mm

10

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.15 Glass fiber length Ln along the screw configuration A in different fiber length (polypropylene -1, screw speed 200 rpm, glass fiber 10% (14 m diameter))

64

12
4 mm 13 mm

10

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.16 Glass fiber length L w along the screw configuration A in different fiber length (polypropylene -1, screw speed 200 rpm, glass fiber 10% (14 m diameter))

65

14 micron 17 micron

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.17 Glass fiber length Ln along the screw configuration A in different fiber diameter ( polypropylene -1, screw speed 200 rpm, glass fiber 10% (4 mm length))

66

14 micron 17 micron

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.18 Glass fiber length L w along the screw configuration A in different fiber diameter ( polypropylene -1, screw speed 200 rpm, glass fiber 10% (4 mm length))

67

0.4

(a)
PP-1 PP-2 PA 12

0.3

0.2

0.1

0.0 0 5 10 15 20 25

Torque (N.m)

0.4

(b)
PP-1 PP-2 PA 12

0.3

0.2

0.1

0.0 0 10 20 30 40 50 60 70 80

Power (Torque rpm)

Figure 4.19 Glass fiber breakage relationships with torque (a) and power (b) for all screw configurations, glass fiber (4 mm/14 m), and all concentrations

68

4.3.1. Comparison with earlier research We have sought to compare our experimental data with the extensive literature on fiber breakage in compounding cited earlier [1, 2, 4, 5, 7-9, 122-127]. Our observations [123] involve more extensive experiments than those by earlier researchers. Turkovich and Erwin [9] found that initial fiber length had little effect on the final length, and increasing the melt temperature which reduces viscosity and decreasing screw speed resulted in slightly longer fibers. We agree with their results and exhibited similar data in Figure 4.1, Figure 4.7 and Figure 4.9. Fisa [2, 122] found that the length breakage is most severe during the very first stage of the process and concluded that the matrix viscosity affects the fiber length significantly. We also found that the beginning of mixing was the major location of glass fiber breakage and very a important factor was polymer viscosity (see Figure 4.1). A higher viscosity led to a greater fiber breakage than a low viscosity polymer. Franzen et al. [4] investigated compounding of three different fibers using the Buss and co-rotating twin screw extruder. They found that high melt viscosity aids fiber breakage. Shorter fibers are in general obtained at higher screw speeds and higher fiber volume fractions. They used high loading volume fractions. In our experiments, we used 1, 10 and 20 volume percent and found similar behavior as shown in Figure 4.3 and Figure 4.5. Thieltges and Michaeli [124] found that high stress in material leads to pronounced fiber breakage. We also compared results of fiber breakage with torque data and found fiber breakage increases with torque. Grillo and

Andersen [5] concluded that mild mixing condition reduces fiber breakage. Ramani and Bank [125] found that the residence time and the intensity of mixing during extrusion compounding have a predominant effect on fiber length degradation. They also found that 69

most of the length reduction in the fibers occurs in the mixing section of the extruder and longer fibers continue to get reduced in length after the mixing section through the rest of the screw. They only focused on the effects of the mixing section. In the present study of different screw configurations effect, we also found that mixing elements were important factor for reduction of glass fiber length, as shown in Figure 4.12 and Figure 4.14. However, a more important correlation is with polymer viscosity, as shown in our experiments. Shimizu and Arai [126] investigated co-rotating twin screw extruder and found that the fiber length depended upon the shear stress and the total number of screw rotations. We also have found a correlation between screw speed and torque. We found that at the screw speed above 100 rpm there is a little effect on the breakage. Yilmazer and Canserver [127] investigated the effects of processing conditions on fiber length degradation in a co-rotating twin screw extruder. They found that when the shear rate is increased through the alteration of the screw speed and the feed rate, the average fiber length decreases. Our experiments have the same tendency. It can be seen that there is general qualitative agreement with our observations.

4.3.2. Correlation with machine torque and power Figure 4.20 shows glass fiber breakage as a function of machine torque. This torque is measured by machine. It is of interest to consider torque comparison with variables such as screw speed, melt viscosity, fiber concentration etc. The PA12 polymer shows higher torque than the two polypropylenes as shown in Figure 4.20. This is presumably due to its high shear rate viscosity as shown in Figure 3.2.

70

25

(a)
PP-1 PA 12

20

Torque (N.m)

15

10

0 50rpm 100rpm 200rpm

RPM

25

(b)
20

Torque (N.m)

15

10

0 PP-1 PP-2 PA12

Different Polymers

Figure 4.20 Torque as a function of different screw speed (a) for screw configuration A, glass fiber 10% (4 mm/14 m) and polymers (b) for screw configuration A, screw speed 200 rpm, glass fiber 10% (4 mm/14 m) 71

Level of viscosity in high shear rate region led to more fiber breakage than that in lower shear rate region. We found increasing screw rpm increases torque. Thus, low screw speed produces low torque and less fiber breakage (Figure 4.20). Screw configurations seem to have a relatively small effect on torque as shown in Figure 4.21. Screw configuration C gives slightly higher values of torque than the other screw configurations. The torque value remains unchanged despite increasing fiber concentrations within the same polymer.

4.3.3. Behavior of PA12 It is found, as shown in Figure 4.1 and Figure 4.2, that fiber breakage occurs more rapidly with PA12 than with PP-1 and PP-2. A possible explanation for this is that the high polar PA12 wets the polar-silicate glass more rapidly than the non-polar polypropylene and breaks up fiber bundles more rapidly.

4.3.4. Screw configuration Results show that PP-1 generated for torque is lower than that of PA12. Also, screw configurations C and D generate a higher torque. Regarding glass fiber breakage, we found that screw configuration is one of the major causes of breakage. Higher torque causes of more of breakage of glass fiber. Figure 4.22 shows the different screw position effects for PP-1. We found that the kneading block in the beginning of the mixing region has more effect on the glass fiber length reductions.

72

25

(a)
20

Torque (N.m)

15

10

PP-1 PA 12

0 Screw A Screw B Screw C Screw D

Different Screw Cofigurations

25

(b)
20

Torque (N.m)

15

10

PP-1 PA 12

0 1% 10% 20%

Concentrations (%)

Figure 4.21 Torque as a function of different screw configurations (a) for screw speed 200 rpm, glass fiber 10% (4 mm/14 m) and volume percents (b) for screw configuration A, screw speed 200 rpm, glass fiber (4 mm/14 m)

73

Screw B Screw D

Fiber Length (mm)

Kneading Element

Kneading Element

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 4.22 Glass fiber length Ln along the screw length in different screw configuration (polypropylene-1, speed 200 rpm, glass fiber 10% (4 mm/14 m))

74

4.4. Conclusion We found in our experimental studies that increasing screw speed, increasing the melt matrix viscosity and increasing glass fiber concentrations all increase the extent of fiber breakage under the conditions of our studies. Initial fiber length was found to have no effect on final fiber length at the same diameter. However, increasing fiber diameter reduces fiber breakage based on our experimental data and other researchers. We conclude that influences on fiber length reduction can be ordered as Polymer viscosity fiber concentration >screw rpm>screw configuration residence time A strong correlation is found between fiber breakage and torque or power for fiber of same diameter.

75

CHAPTER V V. COMPOUNDING OF THERMOPLASTIC WITH SILICA PARTICLES

5.1. Introduction Mixing of different materials is usually classified into two categories as distributive and dispersive mixing. Distributive mixing describes two or more starting components, which are interspersed in space with one another and how they are distributed during flow. On the other hand, dispersive mixing describes a multitude of processes in which the size of non-homogeneities is reduced in scale. We will consider the dispersive mixing of silica particle system. Some particles are used for reinforcing fillers in elastomers and thermoplastics. These include naturally occurring calcite, clay and talc and synthetically carbon black, silica. Tire industry in its early years used carbon black as a reinforcing filler. Recently, silica particles are used for tire reinforcement because of rolling resistance and fuel consumption. There have been few researches of the silica mixing analysis with thermoplastics in twin screw extruder. We deal in this chapter with the mixing of silica into two polypropylenes and polyamide 12 for various processing conditions. These are screw speed effect and polymer effect and silica concentration effect.

76

5.2. Results

In this section, we will discuss the silica agglomerate result for various conditions such as polymer and screw speed and concentration effect in twin screw extruder. 5.2.1. Characterization of silica agglomerate size A description of the dispersed mixed state in samples can be represented by the size of dispersed particles. Agglomerate sizes were determined from SEM photomicrographs. The silica particles seen on SEM photomicrographs prepared in this study are found to be similar to those observed by other researches [128-130]. An image analyzer system was used to measure the agglomerate particle size. The polymer was fed into the first feeding port and the silica was fed into the second feeding port. After machine had reached steady state, the screw then removed from the barrel and samples were collected at room temperature to avoid additional changes of the particle morphology. The mixing of silica into polypropylene and polyamide 12 was studied by characterizing samples taken at various locations along the screw. Figures 5.1-5.3 shows micrographs of the polypropylene-1 with silica. Figure 5.4 shows micrographs of polypropylene-2 with silica. In case of polyamide 12, Figures 5.5-5.8 shows the agglomerate particle along the screw axis. A, B, C, D and G on micrograph indicates positions of the screw as given in Figure 3.6 Figures show SEM observations of silica agglomerates in polymers (PP-1, PP-2, PA12) matrix along the screw axis for screw configuration A which only has screw elements after the second feeding port. After passing the first kneading disc block, the polymer was well melted. Following feeding silica from the second feeding port, silica 77

Figure 5.1 SEM observation in PP-1/silica 10% along the screw configuration A for a screw speed of 50 rpm in a co-rotating twin screw extruder.

78

Figure 5.2 SEM observation in PP-1/silica 10% along the screw configuration A for a screw speed of 100 rpm in a co-rotating twin screw extruder.

79

Figure 5.3 SEM observation in PP-1/silica 10% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder.

80

Figure 5.4 SEM observation in PP-2/silica 10% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder.

81

Figure 5.5 SEM observation in PA12/silica 1% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder.

82

Figure 5.6 SEM observation in PA12/silica 10% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder.

83

Figure 5.7 SEM observation in PA12/silica 20% along the screw configuration A for a screw speed of 200 rpm in a co-rotating twin screw extruder

84

was wetted by the molten polymer. We found that these SEM shows the gradually reduced the particle agglomerate size.

5.2.2. Comparison of different polymers in twin screw extruder After passing the first kneading block, the polymer was well melted. We fed the silica particles the second feeding port into the melt stream. We used the screw configuration A which is only screw elements in the mixing section of the screw. Figure 5.8 shows the mass average agglomerate size for the three polymers. In this study, 10% silica concentration, and same speed 200 rpm were used. The figure shows the general tendency of the particle agglomerate size reduction. The agglomerate size reaches a state steady size along the screw axis. In case of two different viscosity polypropylenes, there are similar changes for agglomerate size tendency. However, polyamide 12 shows the more rapid break-up and small particle agglomerate size than either of the two PPs. The reason is that there is no chemical interaction between silica particle and polypropylene which is a non-polar polymer. However, polyamide 12 is polar so there are chemical interactions such as hydrogen bonding, between silica and polyamide 12. The final average agglomerate size reached 0.696 m, 0.742 m and 0.503 m for PP-1, PP-2 and PA12, respectively. In figures, error bars were used to present the standard deviations like same method for glass fiber error bar as mentioned Chapter 4.

85

2.0
RPM PP-1 (200) PP-2 (200) PA12 (200)

Particle Agglomerate Size (m)

1.5

1.0

0.5

0.0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

PP-2

A: 1.252m

G: 0.742m

PA12

A: 0.803m

G: 0.503m

Figure 5.8 Particle agglomerate size along the screw length for screw configuration A and different polymers (silica 10%, screw speed 200 rpm) with corresponding SEM micrographs 86

5.2.3. Effect of different screw speeds in polypropylene-1 Figure 5.9 shows the particle agglomerate sizes along the screw axis for different screw speeds. As shown in the figure, the lower the screw speed the more severe change for average particle size. In the beginning of feeding, we observed that the particle agglomerate size is quite different at different speeds. At the 90 mm screw point, the agglomerate size is 4.658 m and 1.154 m for 50 rpm and 200 rpm, respectively. Therefore, initial particle agglomerate size is affected by screw speed change. Also, we found that the final agglomerate size is different with changing speed. The value of agglomerate size is 0.917 m and 0.696 m for 50 rpm and 200 rpm, respectively.

5.2.4. Comparison of silica loading in polyamide 12 Figure 5.10 shows the particle agglomerate size at different silica concentrations for PA12 in the same all right handed screw elements co-rotating twin screw extruder configuration. In this study, we used the same screw configuration A, and same speed 200 rpm. The figure shows that in the compounds with higher concentration, the silica agglomerate size is larger than that with the low silica concentration. We can see that the steady state of agglomerate size for 20% concentration appears to be achieved earlier than either of the two other concentrations. The final average agglomerate size reached 0.187 m and 0.972 m for 1% PA12 and 20% PA12, respectively.

5.2.5. Correlations with applied torque and power As agglomerate breakup must be related to applied stresses, we should be able to look to machine torque and power as measure for these stresses. In Figure 5.11, we 87

6
RPM PP-1 (50) PP-1 (100) PP-1 (200)

Particle Agglomerate Size (m)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

50 rpm

A: 4.658m

G: 0.917m

200 rpm

A: 1.154m

G: 0.696m

Figure 5.9 Particle agglomerate size along the screw length for screw configuration A and different screw speeds (polypropylene-1, silica 10%) with corresponding SEM micrographs 88

2.0
PA 12 ( 1%) PA 12 (10%) PA 12 (20%)

Particle Agglomerate Size (m)

1.5

1.0

0.5

0.0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

1% P A12

C: 0.339 m

G: 0.187 m

20% P A12

C: 0.986 m

G: 0.972m

Figure 5.10 Particle agglomerate size along the screw length for screw configuration A and different concentrations (polyamide12, screw speed 200 rpm) with corresponding SEM micrographs 89

1.0
PP-1 PP-2 PA 12

(a)

Particle Agglomerate Size (m)

0.8

0.6

0.4

0.2

0.0 0 5 10 15 20 25

Torque (N.m)

1.0

(b)

Particle Agglomerate Size (m)

0.8

0.6

0.4
PP-1 PP-2 PA 12

0.2

0.0 0 1000 2000 3000 4000 5000

Power (Torque RPM)

Figure 5.11 Particle agglomerate size relationship with torque (a) and power (b) for screw configuration A, silica 10%, different screw speed

90

reported the particle agglomerate size as a function of machine torque and power. We see that particle agglomerate size decreases with power and torque. We observed that power tendency is clearer than torque for agglomerate particle size.

5.3. Discussion and Interpretation In this section, we will discuss and interpretation for comparing to glass fiber breakage and various conditions.

5.3.1. Comparison to glass fiber breakage study As we already explained in chapter 4, the glass fiber breakup mechanism includes the interaction of fiber-fiber, fiber-machine element, and fiber-matrix polymer interface. The initial fiber length decreases quickly in the early stage of mixing and then reaches its limiting length. There seems to be a basic similarity of the breakage of the glass fibers to the breakup of silica particles. In the mixing process, the agglomerates of silica particles are initially incorporated in a molten polymer matrix. Subsequently there is a wetting stage of the particulate component by the melt and then the wetted agglomerates are continuously ruptured and their sizes are decreased by applied shear stress in the twin screw extruder. When the agglomerate breaks into smaller sizes, the particles produced may subsequently coalesce to larger agglomerates. Medalia [131] has pointed out that breaking and reformation of agglomerates of carbon-black in a rubber matrix occurs during a deformation cycle at all amplitudes of strain. Kraus[132] suggested the agglomerate sizes achieve steady state 91

values, with some oscillations around this values. Furthermore, de-agglomeration and reagglomeration rates were found to be related to strain amplitude dependence of carbonblack filled rubber. Silica particles should also be expected to similarly re-agglomerate.

5.3.2. Correlation with machine torque and power Figure 5.11 shows silica agglomerate particle size as a function of torque and power measured by the machine. It is of interest to consider torque and power comparison with variables such as screw speed, melt viscosity, silica concentration etc. During compounding of silica, the polyamide 12 shows higher torque than the two polypropylenes, as shown Figure 5.11. This is similar to a fiber breakage during compounding in twin screw extruder. This is due to its high shear rate viscosity. We found increasing power (torque* rpm) produces small agglomerate particle size. Therefore, the silica particle breakup effect correlates with the power.

5.3.3. Comparison of different processing conditions Table 5.1 shows mass average particle agglomerate size with polymers for various conditions. It is found as shown Figure 5.8 that PA12 polymer shows the more rapid break-up and small agglomerate size than either of the two PPs. The reason is that the high polar polyamide 12 wets the silica particles more rapidly than the non-polar polypropylenes. In case of different concentrations, the final average agglomerate size in PA12 reached 0.187 m and 0.972 m for 1% and 20%, respectively. The agglomerate size has the maximum and minimum values in our experiments. In Figure 5.10, we found that the steady state of agglomerate size for 20% silica is achieved earlier than for two 92

other concentrations. Generally, it is possible that agglomerate size decrease is proportional to hydrodynamic force which re-agglomeration is proportional to the total surface area of agglomerate. Therefore, the increasing silica concentrations can give more effects to the agglomerate size. Concentration has largest effects on the silica agglomerate sizes in our experiments.

93

Table 5.1 Mass average particle silica agglomerate size after mixing with screw configuration A Polymer RPM 50 Polypropylene-1 100 200 Polypropylene-2 200 200 Polyamide 12 200 200 Concentration (%) 10% 10% 10% 10% 1% 10% 20% Agglomerate size (m) 0.917 0.715 0.696 0.742 0.187 0.503 0.972

94

Figure 5.9 shows the screw rpm effect on agglomerate size changes. We found that at the beginning of mixing, the silica agglomerate size exhibits quite big difference with screw speeds. Final particle agglomerate size seems to show a relatively small variation with screw speed than at the beginning of mixing section. In case of 200 rpm, the agglomerate size is achieved a steady state value of distances close to the feeding point. Therefore, we found that screw speed is one of the important factors for quick reduction agglomerate particle size.

5.4. Conclusion We found in our experimental studies that increasing screw speed, increasing the melt matrix viscosity and increasing silica concentration all increase the silica agglomerate breakage under the conditions of our studies. We conclude that influences on particle breakup can be ranked as such: Silica concentration > polymer viscosity screw rpm However, after particles feeding, in agglomerate sizes in twin screw extruder is more effected by screw rpm. A correlation is also found between agglomerate size breakage and power input.

95

CHAPTER VI VI. KINETIC MODEL OF GLASS FIBER BREAKUP

6.1. Introduction In this dissertation we seek to develop a kinetic model of glass fiber breakage in a modular co-rotating twin screw extruder. Various authors beginning with Forgacs and Mason [3] in 1959 and Czarnecki and White [1] in a 1980 paper proposed a fiber breakage mechanism based on buckling. These authors considered the melt viscosity, the intensity of shear field and the period of treatment. Salinas and Pittman [98] in 1981 analyzed the motion of fibers suspended in a liquid subjected to laminar shear. They modeled the fluid shear stress required to buckle a straight fiber as a function of aspect ratio and modulus. They also developed critical curvature values based on thin rod theory. Johnson and Lunt [100] suggested the possible mechanism to break glass fiber. Recently, Shon, Lin and White [7, 8] proposed an empirical kinetic model to represent fiber breakage in various mixing machines including the co-rotating twin screw, counter-rotating twin screw extruder and Buss Kneader. In this chapter, we will develop a new kinetic model of fiber breakage which we will compare with the experimental data we described in Chapter IV. We have further developed a simulation program from this model and determined the kinetic constants.

96

6.2. Model and Simulation

In this section, I will discuss the theoretical model for fiber and compare with simulation and experimental results.

6.2.1. Euler Buckling Theory As we have just indicated, the behavior of fibers in a suspension and their tendency to undergo rotation and experience both compression and tensile forces was first considered by Forgacs and Mason [3]. Subsequent authors, notably Czarnecki and White [1] proposed fiber buckling as a breakage mechanism for rigid fibers and presented evidence using glass, aramid and cellulose fiber that this was related to the Euler buckling model based on a pin ended column to which a compressive force is applied. There are other possible effects for glass fiber breakage such as rotation, bending and friction. In this theory, we only consider buckling through compressive force. We will briefly summarize the Euler model. If x is the direction along the column and y(x) is the lateral deflection, a balance on moments leads to M = EI with boundary conditions y(0)=0, y(L)=0 (6.2) d2y = Fy dx 2 (6.1)

where E is the Youngs modulus and I the cross-sectional moment of inertia. For a cylinder this is I=

d 4
64 97

(6.3)

The s olution of E q ( 6.1) i s y = C1 sin This becomes multi valued when F x EI (6.4)

F L= EI 2
suggesting buckling force is F= For glass fibers E is about 72 GPa.

(6.5)

2 EI
4 L2

(6.6)

One may create variants on the buckling configuration [99]. These generally lead to solutions of form F= EI L2 (6.7)

where may be greater or smaller than 2/4 When glass fibers are added to extruder, they will generally be in bundles of m fibers. These will have cross-sectional moments of inertia, I b , of roughly Ib =

(md ) 4
64

(6.8)

because the packing of the fiber is unclear. The polymer melt will eventually wet the individual fibers and reduce the crosssectional moment of inertia to the value given in Eq (6.3), i.e. d4/64.

98

The compressive force, F, on the fiber bundles should be related to the melt flow induced shear stresses f on the surfaces of the fiber bundles ie
F = (md ) L f

(6.9)

The shear stress acts along the fiber length in non-uniform fashion. We assumed that the shear stress is uniform along the glass fiber length. The shear stress will itself be the product of the melt viscosity and the local shear rates, i.e.

f = f

(6.10)

Presumably in a self wiping co-rotating twin screw extruder, the shear rate will be near to

f =

DN
H

(6.11)

wherd D is the screw diameter, N is screw speed and H is the screw channel depth, will be unity under starved flow conditions and greater than unity when the screw element is fully filled and pressurized. Thus for individual bundles
F = (md ) L

DN
H

(6.12)

Breakage of a fiber bundle would thus seen to occur when

(md ) L

DN
H

EI L2

or

E (md ) 4 (md ) L 2 H 64 L

DN

(6.13)

For an individual fiber (m=1) this would be

DN
H

E d3 L3 64

(6.14)

99

6.2.2. Kinetic model of glass fiber breakage The breakage of fibers along the twin screw extruder axis is shown in Figure 6.1. It is reasonable to suggest that the rate of fiber breakage is
dL crew configuration) = f ( , fiber properties, , N, s dt

(6. 15)

where t is the residence time corresponding to position along axis, is the fiber volume fraction, N is the screw speed, is the polymer matrix viscosity. In our experiments, the

main breakage region was located at position of 0 mm~250 mm after the second hopper. From Figure 6.1 it is reasonable to suggest that the rate of breakage is proportional to the fiber length or the difference between its length and a length Lcrit below which there is no breakage. dL = k ( L Lcrit ) dt (6.16)

Lcrit is ambiguous because we are probably dealing with bundles of m fibers rather than individual fibers where the cross-sectional moment of inertia is I =

(md ) 4
64

(6.17)

Eventually, glass fibers are seprated therefore m=1. Lcrit gradually reduces towards the individual fiber. The constant k depends on the melt viscosity , screw speed N, fiber diameter d, etc. Clearly k in Eq (6.16) depends on the drag force F which is F drag = m d L f where f is the shear stress on the fiber surface. f is (6.18)

f = ( fiber surface)
100

(6.19)

Severe Medium Mild

Fiber Length (mm)

2
Minor Breakage Region

Major Breakage Region

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 6.1 General tendency for glass fiber breakage in co-rotating twin screw extruder indicating region of minor and major breakage

101

The compressive force F =cA c corresponds to a principal axis value associated with f From Eq (6.14), we can get average critical length for different polymers and different screw speeds. From Figure 6.2, we observe that the glass fibers are not seen as bundles. Therefore, we can use in Eq (6.14) in glass fiber m=1. Lcri = [ E 2 (d ) 3 3 E 2 (d ) 3 3 ] =[ ] 256 f 256
1 1

(6. 20)

(6.21)

It would seem reasonable to have the shear rate that polymer melt matrix experiences in a twin screw extruder as

DN cos
H

(6.22)

where H is the distance from the screw root to the barrel, D the barrel diameter, and the helix angle for each screw. It should be noted that for screw configurations A, B, C the screws are largely starved in this region and Eq (6.22) should be valid. Solving Eq (6.16) leads to L(t ) Lcrit = e kt L(0) Lcrit where (6.23a)

k = C[

(md ) L
EI 2 L

DN
H ]

(6.23b)

102

PP-1 Glass fiber (10%)

PA12- Glass Fiber (10%)

Figure 6.2 SEM micrographs of glass fiber with polypropylene-1 and polyamide 12 for glass fiber 10% (4 mm/14 m), screw configuration A and screw speed 200 rpm 103

where I=d4/64, C is the coefficient associated with the approximate nature of the analysis. Eq (6.23a) may be rewritten for a module in a composite modular mixing machine system as Li (t ) = [ Li (0) Lcrit ] exp(k Li t resi ) + Lcrit Ltotal (6.24)

6.2.3. Calculation of kinetic constants and critical length for glass fiber breakup Quantitatively, we calculated the kinetic constants for screw elements and different polymer materials using Eq (6.23). We used the coefficient C=0.001 s-1 and calculated the shear rates and viscosity for each element and polymer from Eq (6.22) with =1 in the case of starved region. In this simulation, we use the rheological parameters obtained from viscosity data (Figure 6.3 and Figure 6.4). Table 6.1 summarized the value of material parameters for equation of viscosityshear rate-temperature relation. We calculated the shear rate for fully filled region using the Newtonian fluid expression as follows.

DN cos
H

x H p ( )[1 2 2 ] 2 x1 H

(6.25)

Table 6.2, 6.3 and 6.4 summarized the value of kinetic constants obtained using Eq (6.23b). Figure 6.5, Figure 6.6 and Figure 6.7 show the kinetic constants tendency along the screw length for different speeds and screw elements for PP-1, PA12 and PP-2. The result shows that kinetic constants are not much changed for different screw elements. However, with increasing screw rpm, the kinetic constants were increased.

104

Table 6.1 Material parameters for simulation

Parameter Reference Temp.(T o ) Power law coefficient at the reference temp. (k o ) Temperature sensitive of viscosity (b) Power law Index (n)

Polypropylene-1 160oC

Polypropylene-2 160oC

Polyamide 12 180oC

8438.8 Pa.sn

1338.3 Pa.sn

8962.5 Pa.sn

0.0158 C-1

0.0195 C-1

0.0467 C-1

0.537

0.764

0.796

Viscosity-shear rate-temperature relation =k o e-b(T-To)n-1 Viscosity-shear rate-temperature relation : =k o e-b(T-To)n-1 PP-1 : =8438.8 e-0.0158 (T-160) -0.467 PP-2 : =1338.3 e-0.0195 (T-160) -0.236 PA12 : =8962.5 e-0.0467 (T-180) -0.204

105

104

(a)
180oC 210oC 240oC

Shear Viscosity (Pa.s)

103

102

101 10-1

100

101

102
-1

103

104

Shear rate (s )

-1

104

(b)
180oC 210oC 240oC

Shear Viscosity (Pa.s)

103

102

101 10-1

100

101

102
-1

103

104

Shear rate (s-1 )

Figure 6.3 Shear viscosity of PP-1 (a) and PP-2 (b) of different temperatures

106

104
210oC 230oC 250oC

Shear Viscosity (Pa.s)

103

102

101 100

101

102
-1

103

104

Shear rate (s-1 )

Figure 6.4 Shear viscosity of Polyamide 12 of different temperatures

107

Table 6.2 Kinetic constants for polypropylene-1 for glass fiber 10% (4 mm/14 m) 200 rpm Screw A # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** m 1 1 1 1 1 Viscosity (Pa.s) 729.3 691.6 664.1 644.5 253.4 Viscosity (Pa.s) 292.3 611.7 309.8 Viscosity (Pa.s) 1005.0 953.0 915.1 888.1 299.7 Viscosity (Pa.s) 1385.0 1313.2 1261.0 1223.9 352.6 Shear rate (s-1) 36.00 40.40 44.10 47.10 354.12 Shear rate (s-1) 260.20 52.71 229.36 Shear rate (s-1) 18 20.2 22.1 23.5 246.36 Shear rate (s-1) 9 10.1 11.0 11.8 173.46 Initial Length Lo (mm) 4 4 4 4 4 Initial Length Lo (mm) 4 4 4 Initial Length Lo (mm) 4 4 4 4 4 Initial Length Lo (mm) 4 4 4 4 4 Kinetic Constant k (s-1) 0.22 0.23 0.25 0.26 0.75 200 rpm Screw C Kneading Neutral # 34 ( Fill 1) ** m 1 1 1 Kinetic Constant k (s-1) 0.64 0.27 0.60 100 rpm Screw A # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** m 1 1 1 1 1 Kinetic Constant k (s-1) 0.15 0.16 0.17 0.18 0.62 50 rpm Screw A # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** m 1 1 1 1 1 Kinetic Constant k (s-1) 0.10 0.11 0.12 0.12 0.51

* Screw element number as indicated by stamp of Japan Steel Works, LTD on elements used. ** Fill factor in co-rotating twin screw extruder 108

Table 6.3 Kinetic constants for polyamide 12 for glass fiber 10% (4 mm/14 m) 200 rpm Screw A # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** m 1 1 1 1 1 Viscosity (Pa.s) 1063.8 1039.1 1020.8 1007.4 692.6 Viscosity (Pa.s) 745.8 987.0 805.5 Viscosity (Pa.s) 1225.0 1196.6 1175.5 1160.1 723.0 Viscosity (Pa.s) 1410.7 1378.0 1353.6 1335.9 750.5 Shear rate (s-1) 36 40.4 44.1 47.1 296.56 Shear rate (s-1) 206.15 52.06 141.23 Shear rate (s-1) 18 20.2 22.1 23.5 240.19 Shear rate (s-1) 9 10.1 11.0 11.8 199.9 Initial Length Lo (mm) 4 4 4 4 4 Initial Length Lo (mm) 4 4 4 Initial Length Lo (mm) 4 4 4 4 4 Initial Length Lo (mm) 4 4 4 4 4 Kinetic Constant k (s-1) 0.32 0.35 0.38 0.40 1.73 200 rpm Screw C Kneading Neutral # 34 ( Fill 1) ** m 1 1 1 Kinetic Constant k (s-1) 1.29 0.43 0.96 100 rpm Screw A # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** m 1 1 1 1 1 Kinetic Constant k (s-1) 0.19 0.20 0.22 0.23 1.46 50 rpm Screw A # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** m 1 1 1 1 1 Kinetic Constant k (s-1) 0.11 0.12 0.13 0.13 1.26

* Screw element number as indicated by stamp of Japan Steel Works, LTD on elements used. ** Fill factor in co-rotating twin screw extruder 109

Table 6.4 Kinetic constants for polypropylene -2 for glass fiber 10% (4 mm/14 m) 200 rpm Screw A # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** m 1 1 1 1 1 Viscosity (Pa.s) 216.0 210.2 205.9 202.8 115.6 Shear rate (s-1) 36 40.4 44.1 47.1 507.8 Initial Length Lo (mm) 4 4 4 4 4 Kinetic Constant k (s-1) 0.07 0.07 0.08 0.08 0.49

* Screw element number as indicated by stamp of Japan Steel Works, LTD on elements used. ** Fill factor in co-rotating twin screw extruder

110

0.4
RPM 50 100 200

0.3

Kinetic Constant (s )

-1

0.2

0.1

0.0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 6.5 Kinetic constants for different screw elements and rpm in PP-1 for screw configuration A, glass fiber 10% (4 mm/14 m)

111

0.5
RPM 50 100 200

0.4

Kinetic Constant (s )

-1

0.3

0.2

0.1

0.0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 6.6 Kinetic constants for different screw elements and rpm in PA12 for screw configuration A, glass fiber 10% (4 mm/14 m)

112

0.10
200 rpm

0.08

Kinetic Constant (s )

-1

0.06

0.04

0.02

0.00 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 6.7 Kinetic constants for different screw elements at 200 rpm in PP-2 for screw configuration A, glass fiber 10% (4mm/14m)

113

Figure 6.8 shows values of average kinetic constants and average viscosity of polymer for screw configuration A, screw speed 200 rpm and 10% glass fiber. These average values were obtained by averaging data for kinetic constant and viscosity for given in Table 6.2 to 6.4 of configuration A at 200 rpm. We observed that the kinetic constants increased with increasing viscosity of polymers. For simulation, we calculated the critical length for different polymer and screw speeds using Eq (6.21). We applied the value of bundle m=1 for polypropylene and polyamide, based on SEM micrographs shown in Figure 6.2. Also, from SEM micrograph, we observed that glass fibers were preferentially oriented along the flow direction. Table 6.5 summarized the critical length for different screw speeds and polymers. We determined these constants from our theory. However, we used experimental data for polymer rheological property and extruder screw configuration.

6.2.4. Simulation program for glass fiber breakage We developed the simulation program with Compaq Visual Fortran 6. (Appendix) Figure 6.9 shows the flow chart for glass fiber breakage program. To carry out simulation, we need material properties of polymer such as power law index (n) and consistency (K) (see Table 6.1). We can calculate these properties using the rheological data at three different temperatures. We used the Eq (6.24) and the kinetic constants given by Eq (6.23) for each element and different polymers (see Table 6.2~4). Also, we need to know, residence time and pressure gradient for each element in twin screw extruder for simulation. To get these data, we use the Akro-Co-Twin Screw software which was developed by White and his research group. 114

0.6

Average Kinetic Constant (s )

-1

0.4

0.2

0.0 190 (PP-2) 596 (PP-1) 964 (PA12)

Shear Viscosity ( Pa. s)

Figure 6.8 Average kinetic constant versus viscosity of polymers for screw configuration A, screw speed 200 rpm, glass fiber 10% (4 mm/14 m)

115

Table 6.5 Critical fiber length for different polymers, screw speeds and screw configurations for glass fiber 10% (4 mm/14 m)

Screw A Screw rpm (200) PP-1 PP-2 PA12 Number of fiber bundle (m) 1 1 1 Critical fiber length (mm) 0.44 0.51 0.34

Screw rpm (100) PP-1 PA12

Number of fiber bundle (m) 1 1

Critical fiber length (mm) 0.4 0.36

Screw rpm (50) PP-1 PA12

Number of fiber bundle (m) 1 1

Critical fiber length (mm) 0.50 0.37 Screw C

Screw rpm (50) PP-1 PA12

Number of fiber bundle (m) 1 1

Critical fiber length (mm) 0.44 0.34

116

Figure 6.9 Simulation flow chart for glass fiber breakage program

117

Figure 6.10 Simulation results in Akro-Co-Twin Screw for residence time and pressure for polypropylene-1, screw configuration A, screw speed 200 rpm, glass fiber 10% (4 mm/14 m) 118

Figure 6.10 shows the simulation results from software for the residence time and pressure values along the each element. After obtaining these data, we can get the shear rate and viscosity for each element. Then, we can calculate the kinetic constants and

critical lengths for polymers and processing conditions. Finally, we can simulate the final glass fiber length along the screw axis.

6.3. Comparison with Experiment In this section, we show simulation results and compare them with experimental data. We will discuss this comparison for various conditions in twin screw extruder.

6.3.1. Comparison to simulation and experimental results We compare experimental and simulation results for three different polymers, different screw configurations, and screw speeds based on simulation software program. Figure 6.11 and Figure 6.12 show the simulation results with experimental data for polypropylene-1 at 200 rpm, 100 rpm, 50 rpm of screw A and screw C of 200 rpm. We observed that the simulation data of fiber length were slightly lower than experimental results. However, the final residual length has a reasonable value compared to actual length. Glass fiber breakage tendency in beginning of mixing region is in good agreement with experimental data for 100 rpm and 50 rpm. But in cases of 200 rpm and screw C, they show somewhat different tendency. Figure 6.13 and Figure 6.14 show comparison of experimental data and simulation for fiber length in polyamide 12 at 200 rpm, 100 rpm, and 50 rpm of screw A and screw C. 119

(a)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

(b)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 6.11 Comparison of glass fiber length between simulation results and experimental results for polypropylene-1 at screw speed 200 rpm of screw configuration A (a) and screw configuration C (b) for glass fiber 10% (4 mm/14 m)

120

(a)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

(b)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 6.12 Comparison of glass fiber length between simulation results and experimental results for polypropylene-1 at screw speed 100 rpm (a) and 50 rpm (b) for screw configuration A, glass fiber 10% (4 mm/14 m)

121

(a)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

(b)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 6.13 Comparison of glass fiber length between simulation results and experimental results for polyamide 12 at screw speed 200 rpm of screw configuration A (a) and screw configuration C (b) for glass fiber 10% (4 mm/14 m)

122

(a)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

(b)
Experiment Simulation

Fiber Length (mm)

0 0 100 200 300 400 500 600

Screw Axis Distance (mm)

Figure 6.14 Comparison of glass fiber length between simulation results and experimental results for polyamide 12 at screw speed 100 rpm (a) and 50 rpm (b) for screw configuration A, glass fiber 10% (4 mm/14 m)

123

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 100 200 300 400 500 600

Experiment Simulation

Fiber Length (mm)

Screw Axis Distance (mm)

Figure 6.15 Comparison of glass fiber length between simulation results and experimental results for polypropylene-2 at screw speed 200 rpm of screw configuration A for glass fiber 10% (4 mm/14 m)

124

Simulation results of PA12 have a slightly lower value than that obtained in experiment for 100rpm and 50rpm. We found that simulations are in good agreement with experiments for 200 rpm and screw configuration A and C. Also, we found that simulated curves show a discontinuity in case of screw configuration C. The reason is that screw configuration C has two special elements which have high values of kinetic constants. Figure 6.15 shows comparison of the simulation results with experimental data for fiber length in PP-2 at 200 rpm of screw A. We can see that the final glass fiber length for PP-2 was quite reasonable in comparison with experimental results.

6.4. Conclusion Based on our experimental data and Euler bucking theory we developed the kinetic model that describes glass fiber breakup in a co-rotating twin screw extruder. We found two regions for fiber break up for melt flow in co-rotating twin screw extruder. In major break up region, three possible breakage mechanisms occur: fiber-fiber, fiber-barrel and fiber-polymer. We developed the composite modular mixing kinetic model that included the effect of the presence of bundles and critical fiber length. Based on this kinetic model, we calculated the kinetic constants for different screws, screw speeds and polymers. Also, we developed the simulation program using Compaq Visual Fortran 6 based on experimental data and use by kinetic constants. We compared simulation and experimental results. Generally, simulation of composite modular extruder kinetic model for glass fiber breakage shows quite reasonable results for various polymers, screw speeds, and screw configurations. 125

CHAPTER VII VII. KINETIC MODEL OF AGGLOMERATE BREAKUP OF SILICA PARTICLES

7.1. Introduction There are several reasons for making particulate-filled polymer compounds. The first is obtaining specific property benefit in the final product. A second reason is to reduce the material cost. The last is that some filler can help to improve process ability. It is necessary to distinguish between the commonly used terminology of aggregates and agglomerates. Aggregates are covalently bonded combinations of small ultimate particles formed during their manufacture. These occur notably in carbon black and silica. Agglomerates are combinations of aggregates or ultimate particles held together by van der Waals or dipole induced physical bonds. Breakage kinetic model of solid particles was first modeled by Bolen and Colwell [105]. In 1958, they proposed the equation to relate the particle creation rate to shearing stress and time. Dizon et al. [111] extended McKelveys [110] theory to fillers that exhibit considerable interactions with the polymer matrix. Manas-Zloczower et al. [113] proposed a mathematical model of dispersive mixing process in internal mixers. Rwei and Manas-Zloczower [16] modified the Powell and Masons [115] model based on their experimental observation indicating that the size of the eroded fragments is assumed proportional to the size of the parent cluster. 126

Recently, Bumm, Shon, Lin and White [7, 19, 133] proposed an empirical kinetic model to represent agglomerate breakup of solid particles at various mixing conditions in co-rotating twin screw extruder. In this Chapter, we investigate the breakup of silica agglomerates and have sought to model their breakage. We will determine the kinetic constants for breakup and reagglomeration. We have evaluated the influence of polymers and processing conditions.

7.2. Kinetic model and calculation for silica particles

In this section, I will discuss kinetic model for silica particles and compare with calculation and experiment data.

7.2.1. Kinetic model of agglomerate breakup in silica compounding To model this we suggest that the agglomerate breakup rate is proportional to the hydrodynamic forces acting on the agglomerates. According to Stokes law [134, 135] for Newtonian fluids, this force is proportional to the agglomerate diameter. So the agglomerate breakup rate can be assumed to be proportional to the agglomerate size. On the other hand, we consider that re-agglomeration occurs when two agglomerates contact each other. This effect is greater for smaller particles. We take the re-agglomeration rate to be proportional to the total surface area of the agglomerates. This leads to:

1 dD = k b D + k re 2 dt D

(7-1)

127

Similar to the Bernoulli equation, these nonlinear differential equations can be reduced to linear form and solved. [136]. When t approaches infinity, the agglomerate size will reach a steady state size of D*. From Equation (7-1), this is:
k D* = ( re ) 3 kb
1

(7-2)

Substituting Equation (7-2) into Equation (7-1), and integrating gives

D(t ) = [(( D0 ) 3 ( D*) 3 ) exp(3k b t ) + ( D*) 3 ]1 / 3

(7-3)

where D o is the filler agglomerate size at the beginning of mixing, and k b is the agglomerate breakup rate constant, and k re is the agglomerate re- agglomeration rate constant. k b and k re are the functions of stress, filler concentration, type of particle, particle size or BET surface area of the particle. These kinetic constants will depend primary on the applied shear stresses, and the cohesive strength of the agglomerate. Equation (7-3) may be rewritten for a composite modular continuous mixing system. Di (t ) = [(( D0i ) 3 ( Di *) 3 ) exp(3k bi t ) + ( Di *) 3 ]1 / 3 (7-4)

where i represents the ith element and t is the residence time in ith element. The relation of the residence time and position in an element can be expressed by
t= L Ltotal t res

(7-5)

Substituting equation (7-5) into (7-4), the agglomerate size decreases with position in an element i in a mixing machine as
Di (t ) = [(( D0i ) 3 ( Di *) 3 ) exp(3k bi Lt res / Ltotal ) + ( Di *) 3 ]1 / 3

(7-6)

128

We now express the k bi as a function that is proportional to the fractional fill level and shear rate in a modular system: k bi = K ii mi Substituting equation (7-7) into (7-6), we can get
Di (t ) = [(( D0i ) 3 ( Di *) 3 ) exp(3K ii m Lt res / Ltotal ) + ( Di *) 3 ]1 / 3

(7-7)

(7-8)

If the average shear rate, fractional fill level, and residence time in elements are known the kinetic parameter for each element can be determined.

7.2.2. Calculation of kinetic constants and discussion We now introduce the average shear rate of the drag flow, fractional fill level, and residence time in each element to the kinetic equation 7-8, to determine agglomerate size breakdown in a co-rotating twin screw extruder. The values of kinetic constants can be determined by the curve fit to the experimental data with various k b values. In this calculation, we determined from the experimental data that the agglomerate size will reach a steady state size of D*. The filler agglomerate size at the beginning of mixing, D o which was calculated from SEM micrographs with EDPM, NBR, SBR for 10% and 20% silica is 13 m [6]. The results are shown in Table 7.1 for different conditions. To use equation 7-8, we should know the residence time and fill factor for each element. To get these data, we use the Akro-Co-Twin Screw software which was developed by White and his research group. Appendix shows the results from software for the residence time and fill factor.

129

Table 7.1 Steady state and filler agglomerate size at the beginning of mixing with screw configuration A Polymer RPM-% 50-10% Polypropylene-1 100-10% 200-10% Polypropylene-2 200-10% 200-1% Polyamide 12 200-10% 200-20% D o (m) 13 13 13 13 13 13 13 D*, Steady state size (m) 1.051 0.883 0.799 0.841 0.184 0.597 0.970

130

Then, we calculated the K i , k b (the agglomerate size breakup rate constant) and k re (the re-agglomeration rate constants) for each element. Tables 7.2, 7.3 and 7.4 show the results for kinetic constants of breakup and re-agglomeration for various polymers and processing conditions. Figures 7.1 - 7.5 show the kinetic constants for breakup and re-agglomeration along the screw elements at different concentrations and polymers. We observed that with increasing screw rpm, the kinetic constants of breakup were increased, as seen in Figure 7.1. Also, the values of kinetic constants changed significantly with decreasing screw element length. The kinetic constants of re-agglomeration rate generally lower than that of breakup, as shown in Figure 7.2. In case of 50 rpm, the kinetic constants of reagglomeration have almost similar values compared to the values of breakup. This is reasonable since the values of kinetic constant of 50 rpm screw speed represent largest agglomerate particle size. Figures 7.3 and 7.4 show that the kinetic constants of breakup and reagglomeration decreases with increasing concentration of silica particles. The agglomerate particle size was larger for 20% compound as was indicated in Figure 5.10. Presumably, the number of collisions between agglomerates at a high volume loading in the co-rotating twin screw extruder was higher than those at a low volume loading. Generally, the value of kinetic constants of breakup in polyamide 12 is higher than those for two polypropylene materials as shown in Tables 7.2 to 7.4. This maybe due to high viscosity of PA12 compared to the polypropylene. In case of 1% compound,

131

Table 7.2 Kinetic constants of breakup and re-agglomeration in polypropylene1 with screw configuration A and silica 10% 200 rpm Shear stress Screw # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** (KPa) 26.3 27.9 29.3 30.4 89.7 Fill factor 0.05 0.06 0.07 0.09 1.00 k b (sec-1) 1.280 2.720 3.174 4.095 45.503 k re (m3.sec-1) 0.653 1.387 1.619 2.089 23.210 100 rpm Shear stress Screw # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** (KPa) 18.1 19.2 20.2 20.8 73.8 Fill factor 0.10 0.11 0.13 0.17 1.00 k b (sec-1) 0.391 0.762 1.248 1.335 7.854 k re (m3.sec-1) 0.269 0.525 0.859 0.919 5.407 50 rpm Shear stress Screw # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** (KPa) 12.5 13.3 13.9 14.4 61.2 Fill factor 0.20 0.23 0.27 0.37 1.00 k b (sec-1) 0.153 0.316 0.513 0.692 1.869 k re (m3.sec-1) 0.178 0.367 0.596 0.803 2.170

* Screw element number indicating by stamp of Japan Steel Works, LTD on elements used. ** Fill factor in co-rotating twin screw extruder

132

Table 7.3 Kinetic constants of breakup and re-agglomeration in polyamide 12 with screw configuration A and 200 rpm PA12 (20%) Shear stress Screw # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** (KPa) 38.3 42.0 45.0 47.5 205.4 Fill factor 0.04 0.05 0.06 0.07 1.00 k b (sec-1) 1.599 3.214 4.080 5.678 81.118 k re (m3.sec-1) 1.459 2.933 3.724 5.182 74.035 PA12 (10%) Shear stress Screw # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** (KPa) 38.3 42.0 45.0 47.5 205.4 Fill factor 0.04 0.05 0.06 0.07 1.00 k b (sec-1) 1.879 3.166 4.065 5.634 80.49 k re (m3.sec-1) 0.400 0.674 0.865 1.199 17.126 PA12 (1%) Shear stress Screw # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** (KPa) 38.3 42.0 45.0 47.5 205.4 Fill factor 0.04 0.05 0.06 0.07 1.00 k b (sec-1) 2.206 3.983 5.013 7.136 101.943 k re (m3.sec-1) 0.014 0.025 0.031 0.044 0.635

* Screw element number indicating by stamp of Japan Steel Works, LTD on elements used. ** Fill factor in co-rotating twin screw extruder 133

Table 7.4 Kinetic constants of breakup and re-agglomeration in polypropylene-2 with screw configuration A and silica 10% 200 rpm Shear stress Screw # 32 * (45 mm) # 35 (37.5 mm) # 33 (30 mm) # 34 ( 22.5 mm) # 34 ( Fill 1) ** (KPa) 7.8 8.5 9.1 9.5 58.7 Fill factor 0.05 0.06 0.07 0.09 1.00 k b (sec-1) 1.607 2,886 3.385 3.944 43.827 k re (m3.sec-1) 0.956 1.717 2.013 2.346 26.070

* Screw element number indicating by stamp of Japan Steel Works, LTD on elements used. ** Fill factor in co-rotating twin screw extruder

134

RPM 50 100 200

Kinetic Constant, kb (s )

-1

0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 7.1 Kinetic constants of breakup for different screw elements and rpm in PP-1 with screw configuration A and silica 10%

135

2.5
RPM 50 100 200

Kinetic Constant, kre (m .s )

3 -1

2.0

1.5

1.0

0.5

0.0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 7.2 Kinetic constants of re-agglomeration for different screw elements and rpm in PP-1 with screw configuration A and silica 10%

136

8
1% 10 % 20 %

Kinetic Constant, kb (s )

-1

0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 7.3 Kinetic constants of breakup for different screw elements and concentrations in PA12 with screw configuration A and screw speed 200 rpm

137

6
1% 10 % 20 %

Kinetic Constant, kre (m .s )

3 -1

0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 7.4 Kinetic constants of re-agglomeration for different screw elements and concentrations in PA12 with screw configuration A and screw speed 200 rpm

138

the value of kinetic constants of re-agglomeration is lowest among all the concentrations. The final value of measured agglomerate sizes was also lowest for 1% compound. Figure 7.5 shows the kinetic constants of breakup and re-agglomeration for PP-2. We observed that the value shows similar tendency with PP-1.

7.3. Comparison with experiments In this section, we show calculated results and compare them with experimental data. We will discuss this comparison for various conditions and compare with results obtained by previous researchers.

7.3.1. Comparison with calculation and discussion We compare experimental and calculated results for three different polymers and various processing conditions in a co-rotating twin screw extruder. Figures 7.6 and 7.7 show the comparison of calculated and measured agglomerate particle sizes of PP-1 compounds at three different rpms. We found that calculated results are in good agreement with experimental data for 200 rpm. However, in case of 100 rpm and 50rpm, calculated and measured agglomerate size at location A, close to port are different with the measured agglomerate size being significantly lower than calculated one. Figures 7.8 and Figure 7.9 show the behavior of calculated and measured agglomerate particle size along screw length at three different concentrations for PA12. We observe that experimental results reach steady state earlier than calculated results. Generally, the calculations are in quite reasonable agreement with experiments.

139

(a)
6
200 rpm

Kinetic Constant, kb (s )

-1

0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

2.5

(b)
200 rpm

Kinetic Constant, kre (m .s )

3 -1

2.0

1.5

1.0

0.5

0.0 45mm(#32) 37.5mm(#35) 30mm(#33) 22.5mm(#34)

Screw Element Length

Figure 7.5 Kinetic constants of breakup (a) and re-agglomeration (b) for different screw element in PP-2 with screw configuration A and silica 10%

140

14

(a)
12

Pariticle Agglomerate Size (m)

10 8 6 4 2 0

Experiment Calculation

100

200

300

400

500

600

Screw Axis Distance (mm)

14

(b)
Pariticle Agglomerate Size (m)
12 10 8 6 4 2 0 0 100 200 300 400 500 600
Experiment Calculation

Screw Axis Distance (mm)

Figure 7.6 Comparison of calculated and measured agglomerate particle size for PP-1 at screw speed 200 rpm (a) and 100 rpm (b) with screw configuration A and silica 10%

141

14 12

Pariticle Agglomerate Size (m)

10 8 6 4 2 0

Experiment Calculation

100

200

300

400

500

600

Screw Axis Distance (mm)

Figure 7.7 Comparison of calculated and measured agglomerate particle size for PP-1 at screw speed 50 rpm with screw configuration A and silica 10%

142

14

(a)
12

Pariticle Agglomerate Size (m)

10 8 6 4 2 0

Experiment Calculation

100

200

300

400

500

600

Screw Axis Distance (mm)

14

(b)
12

Pariticle Agglomerate Size (m)

10 8 6 4 2 0

Experiment Calculation

100

200

300

400

500

600

Screw Axis Distance (mm)

Figure 7.8 Comparison of calculated and measured agglomerate particle size for PA12 at silica concentration of 10% (a) and 20% (b) with screw configuration A and screw speed 200 rpm

143

14 12

Pariticle Agglomerate Size (m)

10 8 6 4 2 0

Experiment Calculation

100

200

300

400

500

600

Screw Axis Distance (mm)

Figure 7.9 Comparison of calculated and measured agglomerate particle size for PA12 at silica concentration of 1% with screw configuration A and screw speed 200 rpm

144

14 12

Pariticle Agglomerate Size (m)

10 8 6 4 2 0

Experiment Calculation

100

200

300

400

500

600

Screw Axis Distance (mm)

Figure 7.10 Comparison of calculated and measured agglomerate particle size for PP-2 at silica concentration of 10% and screw speed 200 rpm with screw configuration A

145

Table 7.5 Comparison of breakdown kinetic constants of PP1-CaCO 3 and PP1-silica agglomerates with screw configuration A , screw speed 200rpm and 10% concentration Screw Co-rotating twin screw extruder #32 (45mm) #33 (30mm) #34 (22.5mm) #35 (37.5mm) PP-CaCO 3 agglomerates k b (s-1) 0.41 0.55 0.72 0.47 PP-Silica agglomerates k b (s-1) 1.28 3.17 4.10 2.72

146

Table 7.6 Comparison of agglomerates kinetic constants of PP1-CaCO 3 and PP1-silica agglomerates with screw configuration A , screw speed 200 rpm and 10% concentration PP-CaCO 3 agglomerates k re (m3.sec-1) 25.58 34.96 45.42 29.44 PP-Silica agglomerates k re (m3.sec-1) 0.65 1.62 2.09 1.39

Screw Co-rotating twin screw extruder #32 (45mm) #33 (30mm) #34 (22.5mm) #35 (37.5mm)

147

The behavior of calculated and experimental agglomerate particle sizes along the screw configuration A for the PP-2 and 10% silica is shown in Figure 7.10. We found that the calculated results are quite reasonable in comparison with experimental data. It is of interest to compare the value of breakup and re-agglomerates kinetic constants of silica with values obtained for breakup of PP-CaCO 3 agglomerates in the same modular machine. This is shown in Table 7.5 and Table 7.6 where we provide results of comparisons to Shon et al. [7, 133] for final average agglomerates size of calcium carbonate. This value was 10.1 m. Our comparisons are for fully filled modular elements at the same screw speed of 200 rpm. We see that agglomerate breakup kinetic constants of silica are larger than those of calcium carbonate by 300% to 600%. We also observed that re-agglomeration kinetic constants of calcium carbonate are larger than those of silica. They are higher by 2100% to 3900%. In our study, we found that the final agglomerate size of silica reached 0.7 m. From these results, we can conclude that final agglomerates size of calcium carbonate is mainly affected by re-agglomeration. However, in silica particles agglomerate, the main effect is breakup kinetic value because the re-agglomeration kinetic value is lower than the breakup kinetic value.

148

7.4. Conclusion Based on our experimental data and dispersion process we developed the kinetic model for particulate agglomerate size in a co-rotating twin screw extruder. We also developed the composite modular kinetic model for evaluating silica agglomerate breakup during compounding with polymers of various processing conditions. Based on this kinetic model, we calculated the kinetic constants of breakup and re-agglomeration. Kinetic constants of breakup and re-agglomeration of silica compound are not much different. In contrast, based on experimental data available in literature on compounding of calcium carbonate with polypropylene-1, we found that re-agglomeration kinetic constants of calcium carbonate play a major role in agglomerate breakup. We compared calculated results with experimental data for a composite modular system. Generally, the calculation is quite reasonably compared with experiments.

149

CHAPTER VIII VIII. CONCLUSIONS AND RECOMMENDATIONS

8.1. Conclusions

In this section, I will discuss the glass fiber breakage and silica particle agglomerate results for various conditions in twin screw extruder. 8.1.1. General In this dissertation, we have made mixing studies of glass fiber and silica filler into thermoplastics in a co-rotating twin screw extruder. The purpose of these studies is to understand effects of glass fiber breakup and silica filler agglomerate breakup and reagglomeration of particles and develop the kinetic model for these processes. The compounding of glass fiber in two polypropylenes of different viscosity and polyamide 12 was carried out to trace brittle breakup of glass fibers. We investigated the damage of glass fibers by varying processing conditions such as screw rpm and screw configuration, filler concentration and different polymers. We developed the new modified kinetic model and simulation program using the mechanism describing fiber damage. Silica filler was added as solid agglomerated particles into a co-rotating twin screw extruder at various processing conditions. A difference in this mixing process from glass fiber is that there is a re-agglomeration mechanism of silica. 150

We calculated the kinetic constants of breakup and re-agglomeration and compared the results with those of previous research.

8.1.2. Compounding with glass fiber Chopped glass fibers of a length of 4 mm were mixed with polypropylenes and polyamide 12 in a co-rotating twin screw extruder. The breakage of initial length of glass fibers investigated at the several positions along the screw axis and at various processing conditions. We found that increasing screw speed, increasing the melt matrix viscosity and increasing glass fiber concentration all increase the extent of fiber breakage under the conditions of our studies. The initial fiber length was found to have no effect on the final fiber length at the same diameter. However, increasing fiber diameter reduces fiber breakage based on our experimental data and those of other researchers. We conclude that fiber length reduction can be ranked as Polymer viscosity fiber concentration >screw rpm>screw configuration residence time. Also, we found that there is a strong correlation between fiber breakage and torque or power for fiber of the same diameter. Based on our experimental data and Euler bucking theory we developed a modified kinetic model for glass fiber breakup in a co-rotating twin screw extruder. We found two regions for fiber breakup during melt flow in a co-rotating twin screw extruder namely, major and minor breakup regions. In the major breakup region, three possible mechanisms occur: fiber-fiber, fiber-barrel and fiber-polymer. In the minor region occurs the only fiber-polymer. We also developed the composite modular mixing 151

kinetic model that includes bundle and critical length effects. Based on this kinetic model, we calculated the kinetic constants for different screws, screw speeds and polymers. Also, we developed the simulation program with Compaq Visual Fortran 6.l. We compared simulated and experimental results. Generally, simulation based on the proposed model for glass fiber breakage is in a reasonable agreement with experimental data obtained on various polymers, screw speeds, and screw configurations.

8.1.3. Mixing with silica particles Silica was used as a filler to investigate compounding of solid particles into a polymer matrix in a co-rotating twin screw extruder. In the characterization of silica agglomerates, mass average values were applied to avoid subjective results due to small filler particles. We found in our experimental studies that increasing screw speed, melt matrix viscosity and silica concentration all increase the silica agglomerate breakage under the conditions of our studies. We conclude that influences of these variables on particle breakup can be ranked as Silica concentration > polymer viscosity screw rpm However, after particles feeding section, the most effect on agglomerate sizes in twin screw extruder is screw rpm. We also developed the composite modular kinetic model for silica compounding at various processing conditions. Based on this kinetic model, we calculated the kinetic constants of breakup and re-agglomeration. We compared re-agglomeration kinetic constants of silica and calcium carbonate. 152

We found that re-agglomeration in calcium carbonate plays a more important role in determing agglomerate particle size. We compared calculated and experimental results for composite modular system. Generally, the calculated results are in a reasonable agreement with experimental data.

8.2. Recommendations for Further Work There is long history of studies of mixing solid additives into viscous liquids and polymers. During the polymer processing, morphological changes in the dispersed phase is important since they determine the final product properties. This study has been limited to the mixing of glass fibers, silica fillers with polypropylenes and polyamide 12 in a co-rotating twin screw extruder. It can be extended to mixing of others ingredients with different primary particle sizes and surface treatment of fillers into other polymer system. Screw configuration and machines may also be varied. The modeling of glass fiber and silica agglomerate size is still incomplete due to the absence of the detailed mechanisms and experimental evidences. This can be improved by developing proper dispersion mechanism with a more realistic flow analysis in a corotating twin screw extruder.[53] Also, we need to further develop the simulation program for compounding of silica agglomerates using the kinetic model. More comprehensive results can improve the modeling and simulation efforts.

153

REFERENCES

1.

Czarnecki, L. and J.L. White, "Shear Flow Rheological Propertise, Fiber Damage, and Mastication Characteristics of Aramid-, Glass-, and Cellulose-FiberReinforced Polystyrene Melts". J. Appl. Polym. Sci., 1980. 25: p. 1217-1244. Fisa, B., "Impact Fracture of Glass-Flake Reinforced Polypropylene". Polymer Composites 1986. 7(5): p. 375-382. Forgacs, O.L. and S.G. Mason, "Particle Motions in Sheared Suspensions X. Orbits of Flexible Threadlike Particles". J. Colloid Sci., 1959. 14: p. 453-491. Franzen, B., C. Klason, and J. Kubat, "Fibre Degradation During Processing of Short Fibre Reinforced Thermoplastics" Composites., 1989. 20: p. 65-76. Grillo, J., P. Anderson, and E. Papazoglou, "Optimization of Screw and Die Design for Compounding Fiberglass Strand on the Co-Rotating Twin Screw Extruder". SPE Antec Tech. Papers, 1992. 38: p. 20-30. Liu, D., MS. Thesis in Polymer Engineering, The University of Akron, 2000. Shon, K., D. Liu, and J.L. White, "Experimental Studies and Modeling of Development of Dipersion and Fiber Damage in Continuous Compounding". Int. Polym. Process, 2005. XX: p. 322-331. Shon, K. and J.L. White, "A Comparative Study of Fiber Breakage in Compounding Glass Fiber-Reinforced Thermoplastics in a Buss Kneader, Modular Co-Rotating and Counter-Rotating Twin Screw Extruders". Polym. Eng. Sci., 1999. 38: p. 1757-1768. Turkovich, R.V. and L. Erwin, "Fiber Fracture in Reinforced Thermoplastic Processing". Polym. Eng. Sci., 1983. 23: p. 743-749. Buskirk, P.R. Van, and S.B. Turetzky, "Practical Parameters for Mixing" Rubber Chem. Technology, 1975. 28: p. 577-591. Cho, J.W., L. Pomini, and J.L. White, "Flow Visualization in an Internal Mixer using New Experimental Rotors including Different Rotor Speed Ratios". Kautsch Gummi Kunsts, 1997. 50(10): p. 728-732. 154

2.

3.

4.

5.

6. 7.

8.

9.

10.

11.

12.

Kim, K.J. and J.L. White, "Particle Orientation in Talc Filled Thermoplastics Extruded Through Cylindrical, Rectangular and Annular Dies". J Non-Newt. Fluid Mech 1996. 66: p. 257-270. Kim, P.S. and J.L. White, "Flow Visualization of Intermeshing and Separated Counter Rotating Rotor Internal Mixers". Rubber Chem. Technology, 1994. 67: p. 871-880. Kim, P.S. and J.L. White, "Comparison of Black Incorporation Development of Dispersion in Intermeshing and Separated Counter Rotating Rotor Internal Mixers". Kautsch Gummi Kunstst, 1996. 49: p. 10. Min, K. and J.L. White, "Flow Visualization Investigations of the Addition of Carbon Black and Oil to Elastomers in an Internal Mixer". Rubber Chem. Technology, 1987. 60: p. 361-380. Rwei, S.P., I. Manas-Zloczower, and D.L. FEKE, " Characterization of Agglomerate Dispersion by Erosion in Simple Shear Flows". Polym. Eng. Sci., 1991. 31: p. 558-562. Rwei, S.P., I. Manas-Zloczower, and D.L. Feke, "Observation of Carbon Black Agglomerate Dispersion in Simple Shear Flows". Polym. Eng. Sci., 1990. 30: p. 701-706. Shiga, S. and M. Furuta, "Processability of EPR in an Internal Mixer (II)Morphological Changes of Carbon Black Agglomerates During Mxing". Rubber Chem. Technology, 1985. 58: p. 1-22. White, J.L., D. Liu, and S.H. Bumm, "Development of Dispersion in RubberParticle Compounds in Internal and Continuous Mixers". J. Appl. Polym. Sci., 2006. 102: p. 3940-3943. Natta, G. and P. Corradini, "The Structure of Crystalline 1,2-Polybutadiene and of Other Syndyotactic Polymers". J. Polym. Sci., 1956: p. 251-266. Natta, G. and F. Danusso, "Nomenclature Relating to Polymers having Sterically Ordered Structure. J. Polym. Sci., 1959. 34: p. 3-11. White, J.L. and D. Choi, eds. "Polyolefin: Processing, Structure Development and Properties" 2005, Hanser: Munich Ahn, S., Ph. D Dissertation in Polymer Engineering, University of Akron (2003). Karger-Kocsis, J., ed. "Polypropylene: An A-Z Publishers: Dordrecht. 155 Reference" 1999, Kluwer

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23. 24.

25.

White, J.L. " Twin Screw Extrusion Techonology ; Principles" 1990, Munich: Hanser. Munich. Coignet, F., " Improvement in Grain-Binders". U.S. Patent. 93,035, 1869. Wunsche, A., German Patent 131, 392, 1901. Easton, R.W., "Improvements in Presses and Pumps. British Patent (filed Sept., 25, 1916) 1,109,663, 1917. Easton, R.W., " Screw Conveyer". US Patent (filed June 2, 1920) 1,468,379, 1923. Colombo, R., Italian Patent (filed Feb. 6, 1939) 370,578, 1939. Colombo, R., British Patent (filed May 2, 1946) 629,109, 1949. Colombo, R., " Method and Apparatus for Manufacturing by Extrusion Structural Members from Thermoplastic Systhetic Resins". U.S. Patent (filed Aug. 7, 1947) 2,563,396, 1951. Colombo, R., " Extrusion Press more Particularly for Thermoplastic". Canadian Patent (filed Dec. 27, 1949) 517,911, 1955. Nelson, W.K., " Method and Apparatus for making Gypsum Board". U.S. Patent (Filed June 4, 1931) 1,868,671, 1932. Pease, F.F., " Apparatus for Treating Plastic materials". U.S. Patent ( filed Aug. 17, 1933) 2,048,286, 1936. Meskat, W. and J. Pawlowski, " Schnecken-Misch-und-Knetwerk". German Patent (filed Dec. 10, 1950) 949,162, 1956. Erdmenger, R., "Misch-und Knetvorrichtung". German Patent (filed Sept. 24, 1949) 813,154 1951. Erdmenger, R., "Vorrichtung Zum Kontinuierlichen Mischen". German Patent (filed Sept. 29, 1949) 815,641, 1951. Erdmenger, R., " Mixing and Kneading Machine". U.S. Patent (filed Sept. 20, 1950) 2,670,188, 1954. Erdmenger, R., "Misch-und Knetvorrichtung". German Patent ( filed July 28, 1953) 940,109, 1956.

26. 27. 28.

29. 30. 31. 32.

33.

34.

35.

36.

37.

38.

39.

40.

156

41.

Erdmenger, R., " Mixing and Kneading Machine". U.S. Patent (filed July 27, 1954) 2,814,472, 1957. Fritsch, R. and G. Fahr, Kunststoffe, 1959. 43: p. 543. Ellermann, W., "Kontinuierlich Arbeitende Schnecken Presse Fur Plastische Massen". German Patent(filed July 31, 1953) 953,634, 1955. Proksch, W., Kunststoffe und Gummi, 1964. 3: p. 426. Loomans, B.A. and A.K. Brennen, " Continuous Mixer". U.S. Patent (filed March 21, 1962) 3,198,491 , 3,195,868, 1965. Loomans, B.A., "Continous Mixing and /or Kneaing Machine with Co-wiping Single Lead Screws". U.S. Patent (filed Oct. 24, 1973) 3,900,187, 1975. Todd, D.B., "Multi-screw, continuous, material processing systems". U.S. Patent (filed July 27, 1977) 4,136,968, 1979. Zimmermann, H.G., " Screw Conveyer or Like Screw Machine". U. S. Patent, 3,170,566, 1965. Booy, M.L., " Geometry of Fully Wiped Twin-Screw Equipment". Polym Eng Sci., 1978. 18: p. 973-983. Booy, M.L., " Isothermal Flow of Viscous Liguids in Corotating Twin Screw Devices". Polym Eng Sci., 1980. 20: p. 1220-1228. Erdmenger, R., "Mehrwellen-Schnecken in der Verfahrenstechnik" Chem Ing Tech, 1964. 36: p. 175-185. Armstroff, O. and H.D. Zettler, Kunststoff Technik, 1973. 12: p. 240. Werner, H. and K. Eise, " An Analysis of the Conveying Characteristics of TwinScrew Co-Rotating Extruders". SPE Antec Tech Papers, 1979. 25: p. 181. Werner, H., Doctorate Dissertation, University of Munich, 1976. Burkhardt, U., H.Herrmann, and S. Jakopin, SPE Antec Tech Papers, 1978. 24: p. 498. Mack, W.A. and K. Eise, "Science ; Technology of Polymer Processing". 1979, Cambridge: MIT.

42. 43.

44. 45.

46.

47.

48.

49.

50.

51.

52. 53.

54. 55.

56.

157

57.

Eise, K., J. Curry, and J.F. Nangeroni, "Compounding Extruders for Improved Polyblends" Polym Eng Sci., 1983. 23: p. 642-646. Denson, C.D. and B.K. Hwang, "The Influence of the Axial Pressure Gradient on Flow Rate for Newtonian Liquids in a Self Wiping, Co-Rotating Twin Screw Extruder ". Polym Eng Sci., 1980. 20: p. 965-971. Szydlowski, W. and J.L. White, "An Improved Theory of Metering in an Intermeshing Corotating Twin-Screw Extruder ". Adv Polym Tech, 1987. 7: p. 177-183. Tadmor, Z., E. Broyer, and C. Gutfinger, "Flow Analysis Network (FAN) - A Method for Solving Flow Problems in Polymer Processing ". Polym Eng Sci., 1974. 14: p. 660-665. Szydlowski, W., R. Brzoskowski, and J.L. White, "Modelling Flow in an Intermeshing Co-rotating Twin Screw Extruder: Flow in Kneading Discs". Int Polym Process, 1987. 1: p. 207-214. Szydlowski, W. and J.L. White, "Improved Model of Flow in the Kneading Disc Region of an Intermeshing Co-Rotating Twin Screw Extruder". Int Polym Process, 1988. 2: p. 142-150. Szydlowski, W. and J.L. White, " A Non-Newtonian Model of Flow in a Kneading Disc Region of A Modular Intermeshing Corotating Twin Screw Extruder". J. Non-Newtonian Fluid Mech, 1988. 28: p. 29-46. Wang, Y. and J.L. White, "Non-Newtonian Flow Modeling in the Screw Regions of an Intermeshing Corotating Twin Screw Extruder". J. Non Newt Fluid Mech, 1989. 32: p. 19-38. Wang, Y., J.L. White, and W. Szydlowski, "Flow in a Modular Intermeshing Corotating Twin Screw Extruder". Int Polym Process, 1989. 4: p. 262-269. Potente, H., J. Ansahl, and R. Wittemeier, "Throughput characteristics of Tightly Intermeshing Co-rotating Twin Screw Extruders". Int Polym Process, 1990. 5: p. 208-216. White, J.L. and W. Szydlowski, "Composite Models of Modular Intermeshing Corotating and Tangential Counter-Rotating Twin Screw Extruders ". Adv Polym Tech, 1987. 7: p. 419-426. Chen, Z. and J.L. White, "Dimensionless Non-Newtonian Isothermal Simulation and Scale-up Considerations for Modular Intermeshing Corotating Twin Screw Extruders". Int Polym Process, 1991. 6: p. 304-309. 158

58.

59.

60.

61.

62.

63.

64.

65.

66.

67.

68.

69.

Sebastian, D.H. and R. Rakos, " Determination of the Residence Time Distribution in a Plasticating Extruder Using an Ionomer Tracer". SPE Antec Tech Papers, 1985. 31: p. 42. Gotsis, A.D., Z. Ji, and D.M. Kalyon, " 3D Analysis of the Flow in Co-Rotating Twin Screw Extruders". SPE Antec Tech Papers, 1990. 36: p. 136. Cheng, H. and I. Manas-Zloczower, "Study of Mixing Efficiency in Kneading Discs of Co-Rotating Twin-Screw Extruders". Polym Eng Sci., 1997. 37: p. 10821090. Kim, E.K. and J.L. White, "Isothermal Transient Startup of a Starved Flow Modular Co-Rotating Twin Screw Extruder ". Polym Eng Sci., 2000. 40: p. 543553. White, J.L., S. Montes, and J.K. Kim, " Experimental Study and Pratical Engineering Analsis of Flow Mechanisms and Starvation in a Modular CoRotating Twin Screw Extruder". Kaut Gummi Kunst, 1990. 43: p. 20-32. Meijer, H.E.H. and P.H.M. Elemans, "The Mdeling of Continuous Mixers. Part I: The Corotating Twin-Screw Extruder ". Polym Eng Sci., 1988. 28: p. 275-290. Chen, Z. and J.L. White, "Simulation of Non-Isothermal Flow in Modular CoRotating Twin Screw Extrusion". Polym. Eng. Sci., 1994. 34: p. 229-237. Chen, Z. and J.L. White, "Simulation of Non-isothermal Flow in Twin Screw Extrusion". Int. Polym. Process, 1994. 9: p. 310-318. Kim, E.K. and J.L.White, "Non-Isothermal Transient Startup of A Starved Flow Modular Co-Rotating Twin Screw Extruder". Int Polym Process, 2000. 15: p. 233241. White, J.L., E.K. Kim, and J.M. Keum, "Modeling Heat Transfer in Screw Extrusion with Special Application to Modular Self-Wiping Co-Rotating TwinScrew Extrusion" Polym Eng Sci., 2001. 41: p. 1448-1455. Maddock, B.H., SPE Journal, 1959: p. 383. Tadmor, Z., I.J. Duvdevani, and I. Klein, "Melting in Plasticating Extuders Theory and Experiments ". Polym Eng Sci., 1967. 7: p. 198-217. Karian, H.G., "Co-Rotating Twin Screw Compounding Studies of PVC Formulations" Journal of Vinyl Additive Technology, 1985. 7: p. 154-159.

70.

71.

72.

73.

74.

75.

76.

77.

78.

79. 80.

81.

159

82.

Sakai, T., N. Hashimoto, and N. Kobayashi, "Experimental Comparison between Counter-Rotating and Co-Rotating on the Twin Screw Extrusion Performance". SPE Antec Tech Papers, 1987. 33: p. 146. Todd, D.B., " Heat Transfer in Twin Screw Extruders". SPE Antec Tech Papers, 1988. 46: p. 54. Todd, D.B., "Melting of Plastics in Kneading Blocks". SPE Antec Tech Papers, 1992. 38: p. 2528-2536. Potente, H., "Single and Twin-Screw Extrusion: Problems Solved and Unsolved" Journal of Polymer Engineering, 1993. 12(4): p. 297-330. Potente, H., J. Ansahl, and B. Klarholz, "Design of Tightly Intermeshing CoRotating Twin Screw Extruders". Int Polym Process, 1994. 9: p. 11-25. Potente, H. and U. Melisch, "Theoretical and experimental investigations of the melting of pellets in co-rotating twin-screw extruders". Int. Polym. Process, 1996. 11(2): p. 101-108. Bawiskar, S. and J.L. White, "Solids Conveying and Melting in a Starve Fed Selfwiping Co-rotating Twin Screw Extruder". Int. Polym. Process, 1995. 10: p. 105110. Bawiskar, S. and J.L. White, "A Composite Model for Solid Conveying, Melting, Pressure and Fill Factor Profiles in Modular Co-Rotating Twin Screw Extruders". Int. Polym. Process, 1997. 12: p. 331-340. Bawiskar, S. and J.L. White, " Determination of Material Properties & Specifying Working Conditions for Akro-Co Twin Screw". SPE Antec Tech Papers, 1998: p. 65-70. Bawiskar, S. and J.L. White, "Melting Model for Modular Self Wiping CoRotating Twin Screw Extruders" Polym Eng Sci., 1998. 38: p. 727-740. Gogos, C.G. and B. Qian, "A predictive melting model for polymer particulates in co-rotating twin screw extruders". SPE Antec Tech Papers, 2001. 59(1): p. 134138. Vergnes, B., G. Souveton, and A. Ainser, "Experimental and Theoretical Study of polymer melting in a Co-rotating Twin Screw Extruder". Int. Polym. Process, 2001. 16: p. 351-362. Jung, H. and J.L. White, "Investigation of Melting Penomena in Modular CoRotating Twin Screw Extrusion". Int Polym Process, 2003.18(2): p. 127-132. 160

83.

84.

85.

86.

87.

88.

89.

90.

91.

92.

93.

94.

95.

Jung, H. and J.L. White, "Modeling and Simulation of the Mechanisms of Melting in a Modular Co-Rotating Twin Screw Extruder". Int Polym Process, 2 008. 23(3): p. 242-251. Harris, J.B. and J.F.T. Pittman, Trans. Ins. Chem. Engrs., 1976. 54: p. 73. Salariya, A.K. and J.F.T. Pittman, "Preparation of Aligned Discontinuous Fiber Pre-pregs by Deposition from a Suspension" Polym Eng Sci., 1980. 20: p. 787797. Salinas, A. and J.F.T. Pittman, "Bending and Breaking Fibers in Sheared Suspensions" Polym Eng Sci., 1981. 21: p. 23-31. Timoshenko, S. and J.M. Gere, "Theory of Elastic Stability " 2nd Ed. . 1961: McGraw-Hill. Johnson, A.E. and J.M. Lunt, "New Coupling Concept for Glass-Reinforced Nylon Resin Composites". Modern Plastics, 1976. 53(7): p. 58-60. Lunt, J.M. and J.B. Shortall, "The Effect of Extrusion Compounding on Fiber Degradation and Strength Properties in Short Glass-Fiber-Reinforced Nylon 6.6" Plastics Rubber Process, 1979. 4(3): p. 108-111. Lunt, J.M. and J.B. Shortall, " Extrusion Compounding of Short-Glass-FiberFilled Nylon 6.6 Blends". Plastics Rubber Process, 1980. 5(2): p. 37-44. Stade, K., " Techniques for Compounding Glass Fiber-Reinforced Thermoplastics". Polym Eng Sci., 1977. 17: p. 50-57. Stade, K., "The Production of Glass Fiber-Reinforced Poly(butylene terephthalate) on a Continuous Kneader". Polym Eng Sci., 1978. 18: p. 107-113. Bolen, W.R. and R.E. Colwell, " Intensive Mixing". Soc Plastics Eng. J., 1958. 14(8): p. 24-28. Medalia, A., "Morphology of aggregates. VI. Effective volume of aggregates of carbon black from electron microscopy; application to vehicle absorption and to die swell of filled rubber" Colloid Interface Sci., 1970. 32(1): p. 115-131. Tokita, N. and I. Pliskin, " The Dependence of Processability on Molecular Weight Distrubution of Elastomers". Rubber Chemistry Technology, 1973. 46: p. 1166-1187. Parfitt, G.D., "Dispersion of Powders in Liquids". 1981, London: Applied Science Publishers. 161

96. 97.

98.

99.

100.

101.

102.

103.

104.

105.

106.

107.

108.

109.

Boyle, J.F., I. Manas-Zloczower, and D.L. Feke, " Hydrodynamic Analysis of the Mechanisms of Agglomerate Dispersion". Powder Tech., 2005. 153(2): p. 127-133. McKelvey, J.M., "Polymer Processing". . 1962, New York: Wiley. Dizon, E.S., E.Y. Micek, and C.E. Scott, Performance Characteristics of Presentday Tread Blacks. Journal of Elastomers & Plastics 1976. 8(4): p. 414-430. Tadmor, Z., "Forces in Dispersive Mixing". Ind. Eng. Chem. Fund, 1976. 15(4): p. 346-348. Manas-Zloczower, I., A. Nir, and Z. Tadmor, "Dispersive Mixing in Internal Mixers-A Theoretical Model Based on Agglomerate Rupture". Rubber Chem. Technol., 1982. 55: p. 1250-1285. Manas-Zloczower, I., A. Nir, and Z. Tadmor, "Dispersive Mixing in Roll-Mills" Polym Compos., 1985. 6(4): p. 222-231. Powell, R.L. and S.G. Mason, "Dispersion by Laminar Flow". Amer. Inst. Chem. Eng. J., 1982. 28(2): p. 286-293. Potente, H., K. Kretschme, and J. Flecke, "A Physical-Mathematical Model for the Dispersion Process in Continuous Mixers" Polym Eng Sci., 2002. 42: p. 19-32. Berzin, F. and B.Vergnes, " A Theoretical Approach to Solid Filler Dispersion in a Twin-Screw Extruder" Polym Eng Sci., 2002. 42(3): p. 473-481. Lozano, T., P.G. Lafleur, and M. Grmela, "Modeling Filler Dispersion along a Twin-Screw Extruder". Int Polym Process, 200 3. XVIII: p. 12-19. Bagley, E.B., "End Corrections in the Capillary Flow of Polyethylene". J. Appl. Phys., 1957. 28: p. 624-627. Eisenschitz, R., B. Rabinowithsch, and K. Weissenberg, Mitt. Der. Mat., 1929. 9: p. 91. Mooney, M., "Explicit Formulas for Slip and Fluidity". J. Rheology, 1931. 2: p. 210-222. Fisa, B., " Mechanical Degradation of Glass Fibers During Compounding with Polypropylene". Polymer Composites, 1985. 6: p. 232-241. Gupta, V.B., R.K. Mittal, and P.K. Sharma, "Some Studies on Glass FiberReinforced Polypropylene. Part I: Reduction in Fiber Length during Processing ". Polymer Composites, 1989. 10: p. 8-15. 162

110. 111.

112.

113.

114.

115.

116.

117.

118.

119.

120.

121.

122.

123.

124.

Thieltges, H.P. and W. Michaeli, " Effects on Fiber Length During Processing". SPE ANTEC Tech Paper, 1991. 37: p. 1991-1993. Ramani, K., D. Bank, and N. Kraemer, "Effect of Screw Design on Fiber Damage in Extrusion Compounding and Composite Properties" Polym. Composites, 1995. 16: p. 258-266. Shimizu, Y., S. Arai, and H. Kawamoto, " Experimental Analysis of the Kneading Disk Region in a Co-Rotating Twin Screw Extruder: Part 2. Glass Fiber Degradation During Compounding". Adv. Polym. Technol, 1997(16): p. 25-32. Yilmazer, U. and M. Cansever, "Effects of Processing Conditions on the Fiber Length Distribution and Mechanical Properties of Glass Fiber Reinforced Nylon6". Polym. Composites, 2002. 23: p. 61-71. Garcia, M., W.E.V. Zyl, and G. Weickert, " Novel Preparation of Hybrid Polypropylene/Silica Nanocomposites in a Slurry-Phase Polymerization Reactor. Ind. Eng. Chem. Res., 2003. 42: p. 3750-3757. Lin, O.H., Z.A.M. Ishak, and H.M. Akil, " Preparation and properties of nanosilica-filled polypropylene composites with PP-methyl POSS as compatibiliser". Materials and Design, 2009. 30: p. 748-751. Yang, H., B. Li, and X. Dong, " Rheology and Phase Structure of PP/EPDM/SiO 2 Ternary Composutes". European Polymer Journal, 2008. 44: p. 113-123. Medalia, A., "Carbon Black Aggregate Morphology and its Effect on the Rheology of Dispersions". Journal of Powder & Bulk Solids Technology 1978. 2(3): p. 1923. Kraus, G., "Mechanical Losses in Carbon Black-Filled Rubbers". Journal of Applied Polymer Science: Applied Polymer Symposium 1984. 39: p. 75-92. K.Shon, S.H. Bumm, and J.L. White, "A Comparative Study of Dispersing a Polyamide 6 into a Polypropylene Melt in a Buss Kneader, Continuous Mixer, and Modular Intermeshing Corotating and Counter-Rotating Twin Screw Extruders" Polym Eng Sci, 2008: p. 756-766. Lamb, H., "Hydrodynamics". 6th ed. 1932, New York: Cambridge University Press. Stokes, G.G., "On the Effect of the Internal Friction of Fluids on the Motion of Pendulums". Trans. Camb. Phil. Soc., 1851. 9: p. 8-106.

125.

126.

127.

128.

129.

130.

131.

132.

133.

134.

135.

163

136.

Kreyszig, E., " Advanced Engineering Mathematics", ed. 7th. 1993, Canada: John Wiley & Sons.

164

APPENDIX
SIMULATION PROGRAM FOR GALSS FIBER IN TWIN SCREW EXTRUDER ************ PLEASE READ THIS FIRST *************************** ********************************************************************** REAL D, H, RPM, n, C, dp, maxstress, LACL, E, nb, fd, LO, k REAL ssrate, sfrate, stress, eta1, eta2, eta, L, sl1 REAL theta, sl, tr, ff, sstress, fstress PARAMETER (PI=3.14159,elemnum=16) DIMENSION theta(elemnum),sl(elemnum),Tr(elemnum),ff(elemnum) DIMENSION k(elemnum),dp(elemnum),L(elemnum), pitch(elemnum) DIMENSION ssrate(elemnum),sfrate(elemnum),stress(elemnum) DIMENSION eta1(elemnum),eta2(elemnum),eta(elemnum) DIMENSION sstress(elemnum), fstress(elemnum), sl1(elemnum) * COMMON /ARRAYS/ssrate(16), fsrate(16), stress(16), eta1(16), eta2(16) * COMMON / SCREWINFO/theta, s l, Tr, f , k OPEN(UNIT=10, NAME='output.txt', STATUS='UNknown', $ ACCESS='SEQUENTIAL') READ(5,*)D, RPM, H, C, n, E, nb, fd, LO write(10,*) 'parameters' write(10,*)D, RPM, H, C, n, E, nb, fd, LO write(10,*) write(10,*) 'Screw info' DO 10 i=1,elemnum READ(5,*)theta(i), sl(i), Tr(i), dp(i), ff(i) write(10,*)theta(i), sl(i), Tr(i), dp(i), ff(i) 165

10 continue ****************************************************** * syntax of f ile r unning * c:> fibers < data.txt ****************************************************** ****************************************************** c D=30. C RPM = 1.67. c H = 6.5 c C= 3800. c n=.5 c E=72000000000. c nb=1. c fd=0.014 c LO = 4. ****************************************************** c Do 1 1 i =1,elemnum c theta(i) = 45.+i c theta(i) = theta(i)*3.14159/180 c sl(i) = 30. c Tr(i) = 10. c dp(i) = 100. c ff(i) = (-1.)**i c write(*,*)theta(i), sl(i), Tr(i), dp(i), ff(i) c11 continue ******************************************************* eta1 = in starved region eta2 = in fully filled region ******************************************************* write(10,*) write(10,*) write(10,*) ' ssrate ', 'eta1 ', 'sfrate ', 'eta2' 166

Do 20 i=1, elemnum ssrate(i)=(3.14159*D*RPM*theta(i)/H) eta1(i)=C*(ssrate(i)**(n-1.)) sfrate(i)=ssrate(i)+(DP(i)*H/2/eta1(i)) eta2(i)=C*(sfrate(i)**(n-1.)) write(10,*) ssrate(i), eta1(i), sfrate(i), eta2(i) 20 continue ******************************************************* * Calculating shear stress * ******************************************************* write(10,*) write(10,*) write(10,*) 'sstress ', 'fstress ', 'stress ' Do 30 i=1, elemnum sstress(i) = ssrate(i) * eta1(i) fstress(i) = sfrate(i) * eta2(i) if (ff(i).GT.0) then stress(i)=fstress(i) else stress(i)=sstress(i) end if write(10,*) sstress(i), fstress(i), stress(i) continue

30

******************************************************* * Find maximum stress &LACL * ******************************************************* maxstress = maxval(stress) LACL=(9.86*E*((nb*fd)**3.)/256.*maxstress)**(1./3.) write(10,*) write(10,*) 'maxstress ', 'LACL' write(10,*) maxstress, LACL write(10,*) 167

write(10,*) 'k' Do 40 i=1, elemnum if (ff(i).GT.0) then k(i)=0.01*((256.*((L0)**3.)*eta2(i)*sfrate(i))/(9.86*E*(nb*fd)**3.)) else k(i)=0.01*((256.*((L0)**3.)*eta1(i)*ssrate(i))/(9.86*E*(nb*fd)**3.)) end if write(10,*) k(i) 40 continue write(10,*) write(10,*) ******************************************************* * Fiber Length c alculation * ******************************************************* sl1(1)=0 write(10,*) 'Length ', L '' write(10,*) 0., LO Do 50 i=1,elemnum if (i.gt.1) then if (i.LT.3) then L(i) = (L(i-1)-LACL)*exp(-k(i)*3.*tr(i)) L(i) = L(i) + LACL else L(i) = (L(i-1)-LACL)*exp(-k(i)*tr(i)) L(i) = L(i) + LACL end if else L(i) = (LO-LACL)*exp(-k(i)*3.*tr(i)) L(i) = L(i) + LACL 168

50

end if if (i.GT.1) then sl1(i)=sl(i)+sl1(i-1) else sl1(i)=sl(i) end if write(10,*) sl1(i), L(i) continue close(10) stop END

169

RESIDENCE TIME AND FILL FACTOR FROM AKRO-CO-TWIN SCREW EXTRUDER VERSION 4.0 Fill Factor Fill Factor 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 L(mm) PA12 100 rpm 0.09 0.09 0.1 0.1 0.1 0.12 0.12 0.12 0.12 0.12 0.12 0.15 0.15 1 1 1 PA12 200 rpm 0.04 0.04 0.05 0.05 0.05 0.06 0.06 0.06 0.06 0.06 0.06 0.07 0.07 0.07 1 1 PP1 50 rpm 0.2 0.2 0.23 0.23 0.23 0.27 0.27 0.27 0.27 0.27 1 1 1 1 1 1 PP1 100 rpm 0.1 0.1 0.11 0.11 0.11 0.13 0.13 0.13 0.13 0.13 0.13 0.17 0.17 1 1 1 PP1 200 rpm 0.05 0.05 0.06 0.06 0.06 0.07 0.07 0.07 0.07 0.07 0.07 0.08 0.08 0.08 1 1 PP2 200 rpm 0.05 0.05 0.06 0.06 0.06 0.07 0.07 0.07 0.07 0.07 0.07 0.09 0.09 0.09 1 1

45.0 45.0 37.5 37.5 37.5 30.0 30.0 30.0 30.0 30.0 30.0 22.5 22.5 22.5 22.5 22.5

170

Residence time in (sec) Time L(mm) PA12 100 rpm 1.80 1.80 1.76 1.77 1.78 1.47 1.51 1.54 1.62 1.63 1.65 1.27 1.77 2.28 2.74 3.16 29.55 PA12 200 rpm 1.20 0.90 0.88 0.95 0.89 0.77 0.75 0.80 0.84 0.82 0.85 0.63 0.66 0.66 1.20 1.69 14.50 PP1 50 rpm 4.80 4.50 3.88 3.95 3.89 3.25 3.29 3.38 3.40 3.88 4.71 3.93 4.29 4.62 4.91 5.18 65.89 PP1 100 rpm 1.80 2.10 1.76 1.91 1.89 1.55 1.58 1.66 1.67 1.69 1.69 1.30 1.67 2.13 2.54 2.92 29.87 PP1 200 rpm 1.20 1.20 0.88 0.95 1.00 0.77 0.82 0.86 0.84 0.87 0.85 0.67 0.69 0.87 1.34 1.77 15.59 PP2 200 rpm 1.20 0.90 0.88 0.95 0.89 0.77 0.75 0.80 0.78 0.82 0.85 0.63 0.63 1.05 1.46 1.83 15.20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Sum

45.0 45.0 37.5 37.5 37.5 30.0 30.0 30.0 30.0 30.0 30.0 22.5 22.5 22.5 22.5 22.5

171

172

173

174

175

176

177

178

179

180

181

182

183

184

185

186

187

188

189

190

191

192