Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1995 The ffecE ts of Shear Stress on the Crystallization Kinetics of Syndiotactic Polystyrene. Douglas Henry Krzystowczyk Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Krzystowczyk, Douglas Henry, "The Effects of Shear Stress on the Crystallization Kinetics of Syndiotactic Polystyrene." (1995). LSU Historical Dissertations and Theses. 5965. https://digitalcommons.lsu.edu/gradschool_disstheses/5965 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. Hie quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely, event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note wifi indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6” x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. A Bell & Howell Information Company 300 North Zeeb Road. Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 THE EFFECTS OF SHEAR STRESS ON THE CRYSTALLIZATION KINETICS OF SYNDIOTACTTC POLYSTYRENE A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy m The Department of Chemical Engineering by Douglas Henry Krzystowczyk B.S. University of Kentucky, Lexington, Ky, 1986 MS. Vanderbilt University, Nashville, Tn, 1988 May, 1995 UMI Number: 9538745 UMI HicroCorm 9538745 Copyright 1995, by UMI Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 To Niomi, the love of my life, and to our son, James Douglas ACKNOWLEDGEMENTS The author would like to thank the following individuals and corporations for their contributions to this work: Dr. Niomi Krzystowczyk Dr. John Collier Dr. Rosemarie Wesson Dr. loan Negulescu Dr. William Daly Dr. Charles Harlow Dr. Armando Conipio Mr. Paul Rodriguez Mr. Xuxian Niu Mr. Ajit Pendse Mr. Erick Comeaux Mr. Frank Krzystowczyk Holley Replacement Parts Mr. Felice Lomangino Computer Partners Albemarle Corporation Dow Chemical Corporation Shell Oil Corporation The National Science Foundation Oak Ridge Associated Universities State of Louisiana Board of Regents TABLE OF CONTENTS DEDICATION .......................................................................................................u ACKNOWLEDGEMENTS ................................................................................ iii LIST OF TABLES ............................................................................................. vi LIST OF FIGURES ............................................................................................. vii ABSTRACT ...........................................................................................................x CHAPTER 1. INTRODUCTION ....................................................................................... 1 1.1 Shear Effects .......................................................................................1 1.2 Syndiotactic Polystyrene .....................................................................2 1.3 Experimental Design .......................................................................... 3 1.4 Objectives .......................................................................................... 3 2. LITERATURE REVIEW .............................................................................5 2.1 Shear Induced Crystallization ............................................................. 5 2.1.1 Shear Stress Response ............................................................ 5 2.1.2 Thermodynamics of Alignment ................................................ 8 2.1.3 Nucleation ............................................................................10 2.1.4 Crystallization ...................................................................... 12 2.1.5 Temperature Effects.............................................................. 13 2.1.6 Crystallographic Effects .........................................................14 2.2 Crystallization Kinetics .....................................................................18 2.2.1 Quiescent Crystallization Models ........................................... 19 2.2.2 Shear Induced Crystallization M odels .....................................22 2.3 Syndiotactic Polystyrene .................................................................. 26 2.3.1 Introduction ......................................................................... 26 2.3.2 Synthesis ............................................................................. 28 2.3.3 Physical Properties................................................................ 30 2.3.4 Production ........................................................................... 31 2.3.5 sPS Structure ........................................................................32 2.3.6 Infrared Properties ................................................................37 2.3.7 Crystallization Kinetics .......................................................... 39 2.4 Experimental Design ........................................................................ 41 3. EQUIPMENT ............ 45 3.1 Calibration Equipment ...................................................................... 45 3.2 Rheometer Equipment ......................................................................47 4. PROCEDURES........................................................................................... 57 4.1 Calibration Procedures ........................................................................57 4.2 Stress Measurement Experiments ........................................................ 60 4.3 IR Measurement Experiments ..............................................................62 5. RESULTS AND DISCUSSION ..................................................................74 5.1 Calibration Experiments ..................................................................... 74 5.2 Stress Measurement Experiments ........................................................ 78 5.2.1 Induction Time Measurement ................................................ 80 5.2.2 Viscosity Measurements ........................................................ 83 5.2.3 Final Sample Ciystallinity ...................................................... 85 5.2.4 Crystallographic Effects ........................................................ 91 5.3 IR Measurement Experiments ..............................................................93 5.3.1 Non-Isothermal Heating S cans...............................................95 5.3.2' Isothermal Crystallization .....................................................101 5.3.3 Non-Isothermal Crystallization from the Melt ......................I l l 6. SUMMARY AND CONCLUSIONS ........................................................ 117 7. RECOMMENDATIONS ......................................................................... 120 REFERENCES ................................................................................................... 124 APPENDICES ................................................................................................... 129 A. Rheometer Control ......................................................................... 129 B. Manipulation of the Isothermal Rheometer Scans .............................. 147 C. Experimental D a ta ........................................................................... 150 VITA ...................................................................................................................159 v LIST OF TABLES Table 2.2.1.I: Values of n for various types of nucleation and growth acts. 20 Table 2.2.2.1: Material parameters of the Eder, Janeschitz-Kriegl SIC model. 25 Table 2.3.3.1: Physical properties of neat sPS resin ..................................31 Table 2.3.4.1: Properties of sPS produced by the Idemitsu Kosan process ... 32 Table 2.3.6.1: Assignments of several sPS IR bands