THE CRYSTALLIZATION BEHAVIOUR OF ISOTACTIC …

1 I THE CRYSTALLIZATION BEHAVIOUR OF ISOTACTIC polybutene -1 A THESIS SUBMITTED TO THE DEPARTMENT OF CHEMISTRY AND THE INSTITUTE OF ENGINEERING AND SCIENCE OF BILKENT UNIVERSITY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE BY HACI BAYRAM ERDEM AUGUST 2002 ii I certify that I read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis for the degree of Master of Science. _____ Asst. Prof. Dr. G rhan Kalay (Supervisor) I certify that I read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis for the degree of Master of Science.

2 _____ Prof. Dr. efik S zer I certify that I read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis for the degree of Master of Science. _____ Assoc. Prof. Dr. C. Hakan G r Approved for Institute of Engineering and Science. _____ Prof. Dr. Mehmet Baray Director of Institute of Engineering and Science iiiABSTRACT THE CRYSTALLIZATION BEHAVIOUR OF ISOTACTIC polybutene -1 Haci Bayram Erdem in Chemistry Supervisor: Assist. Prof. Dr. G rhan Kalay August 2002 The CRYSTALLIZATION BEHAVIOUR of different commercial grades of ISOTACTIC polybutene -1 was investigated and an experimental set-up was designed for this research study.

3 The experimental set-up constructed provides both fast-cooling of the sample and the recording of the growth of spherulites as a real time movie. The radial growth rate of the spherulites were observed to be higher for the grades with higher molecular weights. The results were found to fit to the Lauritzenn-Hoffman CRYSTALLIZATION theory, and this theory is used to calculate the lateral surface free energy, , and fold surface free energy, e. The lateral surface free energy was found to be erg/cm2 for all the grades investigated. The fold surface free energy calculated to be between to erg/cm2. The fold surface free energies and the CRYSTALLIZATION rates do not exhibit any dependence on the molecular weight of the polymer. The polymer containing nucleating agents has the highest CRYSTALLIZATION rate.

4 It was observed that the likelihood of deviation from spherical shape is greater for the grades with lower molecular weights. Key-words : polybutene -1, Lauritzen-Hoffman theory, spherulite growth rate, nucleating agent, CRYSTALLIZATION rate, polymer CRYSTALLIZATION iv ZET ZOTAKT K POL B TEN-1 N KR STALLE ME DAVRANI I Hac Bayram Erdem Kimya Y ksek Lisans Tez Y neticisi: Assist. Prof. Dr. G rhan Kalay A ustos 2002 Polibuten-1 in d rt farkl ticari t r n n kristalle me davran incelendi ve bu inceleme i in bir deney d zene i haz rland . Haz rlanan deney d zene i, ayn zamanda numunelerin h zl -so utulmas n ve k resel kristal yap lar n b y mesini ger ek zamanl bir film olarak kaydedilmesini sa lad . Yar apsal b y me h zlar n n, b y k molek l a rl kl s n flar i in daha b y k oldu u g zlemlendi.

5 Bulunan sonu lar n Lauritzen-Hoffman kristalle me teorisine uygunlu u g sterildi ve bu teori yanal y zey serbest enerjisi, , ile katlanma y zeyi serbest enerjisi, e, de erlerini hesaplamada kullan ld . Yanal y zey serbest enerjisi n n b t n incelenen t rler i in de eri 10,4 erg/cm2 olarak bulundu. Katlanma y zeyi serbest enerjisi de erlerinin 15,5 erg/cm2 ile 17,4 erg/cm2 aras nda de i ti i hesapland . Katlanma y zeyi serbest enerjisi, e, ile kristalle me h z n n molek ler a rl a ba l olmad g r ld . ekirdekle me katk maddeleri i eren t r n kristalle me h z n n incelenen t rler i inde en y ksek oldu u bulundu. K resel yap dan sapma olas l n n, daha k k molek l a rl kl s n flar i in daha y ksek oldu u g zlendi. Anahtar Kelimeler : polib ten-1, Lauritzen-Hoffman teorisi, yar apsal b y me h z , ekirdekle me katk maddesi, kristalle me h z , polimer kristalle mesi v ACKNOWLEDGEMENT I warmly thank Asst.

6 Prof. Dr. Gurhan Kalay, for his great help and supervision throughout my studies. vi TABLE OF CONTENTS SIGNATURE TABLE OF LIST OF LIST OF LIST OF MOVIES INCLUDED IN THE CHAPTER-1. CHAPTER-2. LITERATURE Introduction ..3 Synthesis of ISOTACTIC Properties of Monomer ..3 Synthesis of Polymorphmism of ISOTACTIC Form-II to Form-1 Crystal The Rate of Transformation from Form-II to Polymer CRYSTALLIZATION During Strain Induced from Solutions under CRYSTALLIZATION from Melts under CRYSTALLIZATION under Quiescent from Quiescent from Quiescent vii Fringed Micelle Kinetics of Lateral Crystal Lauritzen-Hoffman secondary Nucleation Regimes of Spherulite Growth rate vs Bulk CRYSTALLIZATION Kinetics and Avrami Supermolecular Structure of iPB-1.

7 32 Applications of ISOTACTIC CHAPTER-3. EXPERIMENTAL PROCEDURE AND THE DESCRIPTION OF THE CRYSTALLIZATION DSC FT-IR Spherulite Growth Rate CRYSTALLIZATION Spherulite Growth Rate (SGR) The Measurement of Spherulite Growth Preperation of the L-H Plots and Calculation of the Regime Calculation of the Overall CRYSTALLIZATION and Avrami CHAPTER-4. RESULTS AND Form-II to Form-I Transformation by DSC Spherulite Growth Rate Grade PB Grade PB 0300 ..49 Grade PB Grade PB The Effect of Molecular Weight on the Spherulitic Growth Effect of Molecular Weight on the Fold Surface Free Energy Avrami Analysis ..67 Effect of Molecular Weight on the Overall CRYSTALLIZATION CHAPTER-5.

8 CONCLUSIONS and FUTURE Future CHAPTER-6. APPENDIX-1. CD INCLUDING THE SPHERULITE GROWTH MOVIES ix LIST OF FIGURES Figure Molecular Structure of ISOTACTIC Figure Helical Conformations of (a)Form-1,3/1 helix,(b) Form-II, 11/3 Figure DSC Thermograms of Various Polymorphous of Figure X-Ray Diffraction Patterns of Various Polymorphous of Figure Interconversion Between Polymorphs of Figure (a) Shirankage of Square Form-II Crystal upon Conversion to Form-I .9 (b) Development of Cracks and Elongated Figure Percentage Conversion to stable Form-I as a Function of Annealing Time for Different Take up Speeds ..11 Figure IR Spectra of iPB-1 aged for various ..12 Figure General BEHAVIOUR of Thermodynamic Variables at the Equilibrium Melting Figure AFM Image of The Shear region of iPB-1 Processes by Figure Electron Micrograph of Linear Polyethylene Grown from a Solution of Figure Schematic Two Dimensional Representations of Models of the Fold Figure Fringed Micelle Model of the Crystalline-Amorphous Structure of Figure Schematic Diagram of Ordering of the Indicatrices in a Figure Schematic Diagram of Fully Developed Spherulite Grown from the Figure Electron Micrograph of Central Sheaf-Like Part Observed at an Early Stage of Development of a Spherulite of Figure Free Energy of Crystal Nuclei Formation as a Function of Figure Primary and Secondary Nucleus Formation Rates as a Function of CRYSTALLIZATION Figure Scheme Illutrating the Rates of Stem Deposition

9 During the Three Different Regimes of CRYSTALLIZATION Figure Radial Growth Rate of Spherulites of iPS vs CRYSTALLIZATION Temperature ..28 x Figure Schematic Diagram of Conversion of Growth Rate Data to L-H Figure Creep BEHAVIOUR of Polyolefin Resins Compared to Figure Dimensions of Polymer Mould Prepared for Figure Schematic Diagram of SGR Figure Close-up Picture of the SGR Figure Picture of the SGR Set-up during the Figure Micrograph of the Figure Micrographs of iPB-1 Thin Films Crystallized at 70 Figure IR Spectra of iPB-1 Grade PB0100 ageing times at room Figure Micrographs of Grade Figure Growth of Spherulites of Figure Radial Growth Rate and L-H Plot for Figure Micrographs of Grade Figure Growth of Spherulites of Figure Radial Growth Rate and L-H Plot for Figure Micrographs of Grade Figure Epitaxial CRYSTALLIZATION and Non-spherical Figure Growth of Spherulites of Figure

10 Radial Growth Rate and L-H Plot Figure Micrographs of Grade Figure Ringed Spherulites for Figure Growth of Spherulites of Figure Radial Growth Rate and L-H Plot for Figure Fit of Equation to the Spherulitic Growth Rate for Figure Avrami Analysis and Fit of the Avrami Equation to Overalll CRYSTALLIZATION Change vs. Figure (a),(b),(c),(d) Micrographs of PB0110, PB0300, PB0400, PB0800 crystallized at 70 oC for 90 seconds, respectively. (e)Q plots for PB0110, PB0300, PB0400 and PB0800 at 70 oC(f)Spherulite Size vs. time plots for PB0110, PB0300, PB0400 and PB0800 at 70 xi LIST OF TABLES Table Millions of Pounds Per Year of Butene-1 for Chemical Table Avrami Exponents for Various Geometries, Nucleation Types and Rate Determining Step for Crystal Growth Table The Densities and Melt Flow Indices of the Investigated PB Table Number Average Molecular Mass, Weight Average Molecular Mass, Polydispersities of the Grades Table The Values of Variables for iPB-1 Used in the Table Melting Peak Temperature, Enthalpy of Fussion and Percent Crystallinity of Table Spherulite Growth Rates for the Grades.