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The Effect of Injection Molding Conditions on The THE EFFECT OF INJECTION MOLDING CONDITIONS ON THE NEAR- SURFACE RUBBER MORPHOLOGY, SURFACE CHEMISTRY, AND ADHESION PERFORMANCE OF SEMI-CRYSTALLINE AND AMORPHOUS POLYMERS by Shannon Christine Weakley-Bollin A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Materials Science and Engineering) in the University of Michigan 2010 Doctoral Committee: Professor J. Wayne Jones, Co-Chair Professor David C. Martin, Co-Chair Professor Ronald G. Larson Deborah F. Mielewski, Ford Motor Company “Anyone who stops learning is old, whether at twenty or eighty. Anyone who keeps learning stays young. The greatest thing in life is to keep your mind young." Henry Ford © Shannon Christine Weakley-Bollin 2010 Acknowledgments I'd like to thank all of the people in the Materials and Processes department at Ford Motor Company's Research and Innovation Lab for their help and support, especially: Debbie Mielewski for volunteering to be on my committee and guiding me the entire way of my thesis; Patti Tibbenham for teaching me from her vast knowledge of polymer processing and helping me with just about every part of this thesis including designing and running the DOE in Chapter 4; Matt Zaluzec and James Boileau, my manager and supervisor who supported my pursuit of this degree; Ann Straccia and Larry Haack for teaching me how to use the XPS and helping me interpret the data; Mark Nichols for some helpful (and not so helpful) discussions about polymers and graduate school in general; Kevin Ellwood for insight in to the foreign world of modeling for this experimentalist; Tony Godlewski for conducting the impact testing in Chapter 2. I'd also like to thank Professor Dave Martin for taking on a student who had a full- time job and being supportive and acknowledging of that fact. Thanks are also due to members of Dave's research group at UM, including Jihua Chen for his TEM imaging in Chapter 3 and Brenda Vyletel and Jinghang Wu for their work on the adhesion testing done for Chapters 3 and 4. Thank you to Ford Motor Company and the Detroit Chapter of the Society of Plastic Engineers, since without their financial support this degree would not be possible. ii Finally I'd like to thank my family, including: my husband, Rob, for all of his love and support along the way; my Dad for all of his help with my homework and my Mom for appreciating my thesis title – not to mention all of their help supporting me financially throughout my schooling; my sister-in-law Tracy for thesis commiseration and my brother Ryan for his motivation by never failing to ask "aren't you done with that yet?". And finally, Charlie - his "wiggle-butt" greetings never failed to brighten even the longest day of writing. iii Table of Contents Acknowledgments.............................................................................................. ii List of Figures................................................................................................... vii List of Tables ................................................................................................... xiii Chapter 1: Introduction...................................................................................... 1 1.1 Materials ..................................................................................................... 5 1.2 Processing .................................................................................................. 7 1.3 Injection Molding Equipment....................................................................... 8 1.3.A Injection Unit ........................................................................................ 8 1.3.B Mold ..................................................................................................... 9 1.3.C Clamping Unit .................................................................................... 10 1.4 Injection Molding Process ......................................................................... 10 1.5 Effect of processing on performance ........................................................ 11 1.6 Adhesion................................................................................................... 13 1.7 Problem Statement ................................................................................... 16 1.8 References................................................................................................ 20 Chapter 2: Anisotropic Structure and Molded-in Stress in Injection-Molded Neat Polypropylene .......................................................................................... 23 2.1 Introduction ............................................................................................... 23 2.2 Literature Review ...................................................................................... 26 2.2.A Micro (Spherulitic) Morphology .......................................................... 26 2.2.B Macro Morphology ............................................................................. 28 2.2.C Effect of Processing on Morphology .................................................. 29 2.2.D Effect of Morphology on Properties.................................................... 30 2.3 Experimental............................................................................................. 31 2.3.A Optical Microscopy............................................................................. 32 2.3.B Molded-in stress measurements ........................................................ 35 iv 2.3.C Coefficient of Linear Thermal Expansion (CLTE)............................... 35 2.3.D Low Temperature Impact Testing ...................................................... 36 2.3.E X-Ray Photoelectron Spectroscopy (XPS)......................................... 37 2.4 Results and Discussion............................................................................. 38 2.4.A Optical Microscopy............................................................................. 38 2.4.B Coefficient of Linear Thermal Expansion (CLTE)............................... 48 2.4.C Low Temperature Impact Testing ...................................................... 60 2.4.D X-Ray Photoelectron Spectroscopy (XPS)......................................... 62 2.5 Conclusions .............................................................................................. 64 2.6 References................................................................................................ 67 Chapter 3: Effect of Cooling Rate and Surface Treatment on Rubber Morphology and Paint Adhesion of Compounded and Reactor Grade TPO......................................................................................................... 72 3.1 Introduction ............................................................................................... 72 3.2 Literature Review ...................................................................................... 75 3.2.A Spherulitic Morphology....................................................................... 75 3.2.B Macro Morphology ............................................................................. 76 3.2.C Morphology Evaluation ...................................................................... 77 3.2.D Effect of Morphology on Properties.................................................... 80 3.3 Experimental............................................................................................. 84 3.3.A Optical Microscopy............................................................................. 85 3.3.B Surface Profilometry........................................................................... 86 3.3.C Coefficient of Linear Thermal Expansion (CLTE)............................... 86 3.3.D Atomic Force Microscopy................................................................... 87 3.3.E Transmission Electron Microscopy..................................................... 89 3.3.F X-Ray Photoelectron Spectroscopy (XPS)......................................... 89 3.3.G Adhesion Testing............................................................................... 90 3.4 Results and Discussion............................................................................. 90 3.4.A Optical microscopy............................................................................. 90 3.4.B Surface Profilometry........................................................................... 91 3.4.C Coefficient of Linear Thermal Expansion (CLTE)............................... 92 v 3.4.D Atomic Force Microscopy (AFM)........................................................ 95 3.4.E Transmission Electron Microscopy................................................... 104 3.4.F X-Ray Photoelectron Spectroscopy (XPS)....................................... 106 3.4.G Adhesion Testing............................................................................. 110 3.5 Conclusions ............................................................................................ 113 3.6 References.............................................................................................. 118 Chapter 4: Performance of Electroplated ABS and PC/ABS as a function of Injection Molding Processing Conditions .................................................... 125 4.1 Introduction ............................................................................................. 125 4.2 Literature Review ...................................................................................
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