Structure and Properties of Nanoclay Reinforced Polymer Films, Fibers and Nonwovens
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University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 8-2009 Structure and Properties of Nanoclay Reinforced Polymer Films, Fibers and Nonwovens Raghavendra Ratnakar Hegde University of Tennessee - Knoxville, [email protected] Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Polymer and Organic Materials Commons Recommended Citation Hegde, Raghavendra Ratnakar, "Structure and Properties of Nanoclay Reinforced Polymer Films, Fibers and Nonwovens. " PhD diss., University of Tennessee, 2009. https://trace.tennessee.edu/utk_graddiss/39 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Raghavendra Ratnakar Hegde entitled "Structure and Properties of Nanoclay Reinforced Polymer Films, Fibers and Nonwovens." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Polymer Engineering. Gajanan Bhat,, Major Professor We have read this dissertation and recommend its acceptance: Roberto Benson, Joseph Spruiell, David Joy Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) To the Graduate Council: I am submitting herewith a dissertation written by Raghavendra Ratnakar Hegde entitled ―Structure and Properties of Nanoclay Reinforced Polymer Films, Fibers and Nonwovens.‖ I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a major in Polymer Engineering. Gajanan Bhat, Major Professor We have read this dissertation and recommend its acceptance: Roberto Benson Joseph Spruiell David Joy Accepted for the Council: Carolyn R. Hodges, Vice Provost and Dean of the Graduate School (Original signatures are on file with official student records.) STRUCTURE AND PROPERTIES OF NANOCLAY REINFORCED POLYMER FILMS, FIBERS AND NONWOVENS A Dissertation Presented for the Doctor of Philosophy Degree The University of Tennessee, Knoxville Raghavendra Ratnakar Hegde August 2009 With Eternal Love and Respect to My Mother – Geeta Ganapati Bhat ii Copyright © 2008 by Raghavendra Hegde All rights reserved. iii ACKNOWLEDGEMENTS I would like to express sincere thanks to following people who made this work possible: First my academic adviser, Dr. Gajanan Bhat, for his advice, guidance and encouragement throughout the PhD studying. I am also grateful to all of my committee members-Dr. Joseph Spruiell, Dr David Joy and Dr. Roberto S. Benson for all the invaluable source of advice and support to my research. Dr Svetlana Zivanovic for allowing to access characterization facilities in Food science and Technology laboratory. I would like to thank the staff and professors of TANDEC for their help through this research. Special thanks to Van Brantley for training me to become acquainted with all nonwoven testing instruments. Thanks to Dr. Bhushan Deshpande who is one of the industrial advisors for my PhD degree, for his active participation, providing raw materials and important input for this research. Also don‘t want to miss an opportunity to express thanks to Dr. Joseph Spruiell for training me to use x-ray characterization facilities. I am truly thankful to Dr.Dayakar Penumadu for providing the financial support for the last semester of my PhD degree. The financial support for this research from Techmer PM through the Center for Materials Processing (CMP) is truly appreciated. Also special thanks to Techmer PM for providing the polymer concentrates and the nanoclay reinforced samples. Finally and most importantly, I express my special gratitude to my mother Geeta G Bhat, wife Dhanu Hegde, sister Ramya Hegde for their constant support, love and encouragement. Thanks to Vanitakka, Bava, Sneha and Sunay in Knoxville for all their love and encouragement during my stay in Knoxville and making me feel at home every time I visited them. Thanks to all my colleagues and friends in Knoxville who helped me in various ways and made my stay enjoyable at The University of Tennessee. iv ABSTRACT In this research, influence of different levels of Closite Na+ additives on the microstructure, morphology and mechanical properties of polymer products was studied. Importance was given to understand the additive level, extent of dispersion in matrix, change in microstructure and respective property observed in the end product. Polypropylene spunbond and meltblown web samples with various levels of Closite Na+ additives were produced and characterized. Injection molded polypropylene nanocomposite with 1 to 15 wt% nanoclay additives were also prepared and characterized for microstructure and mechanical properties. Crystallization kinetics studies showed significant increase in crystallization rates on nylon 6 even at 0.25 wt % additives. Near surface and bulk stiffness of the film significantly increased in the presence of nanoclay additives. Intercalated and flocculated morphology was observed for all the polypropylene concentrate and the same morphology was retained in spunbond fibers also. About 25 to 30 % increase in cross direction tear strengths were observed for 1 to 2 wt % clay loading. Fibers with even as low as 1 % clay retains their morphology and integrity in bond point after thermal bonding. At higher weight percentage, stiffness of webs significantly increased and tear strength of webs decreased due to exclusion of excess clay platelets in the interspherulite regions. Property benefits were not observed in the case of melt blown samples with nanoclay additives, but the additives were well dispersed in the fiber web. Compared to control meltblown webs, stiff and open web structure with high irregularity was obtained for samples with clay additive. In case of injection-molded polypropylene composite, significant increase in breaking energy was observed for sample with just with 1 wt % clay additive. At higher weight percentage, segregation was observed in the inter-spherulitic region and failure mode shifted from ductile to brittle. v TABLE OF CONTENTS Chapter Page No 1. Introduction ................................................................................................................................. 1 CHAPTER II ................................................................................................................................... 3 Literature Review............................................................................................................................ 3 2.1. Nanoclay .................................................................................................................. 3 2.1.1 Crystal structure of sodium montmorillonite ......................................................... 5 2.1.2 Different morphologies of melt blended nanocomposite ...................................... 7 2.1.3 Influence of processing condition on nanoclay dispersion .................................... 9 2.1.4 Thermodynamics of mixing ................................................................................... 9 2.2 Nylon 6 nanoclay composites ................................................................................. 11 2.2.1 Crystallization kinetics and melting behaviors of nylon 6 nanocomposites ........ 15 2.3 Polypropylene-nanoclay composites ...................................................................... 17 2.3.1 Influence of clay additives on crystal structure of polypropylene ....................... 19 2.3.2 Challenges involved in dispersion on nanoclay in polypropylene ...................... 20 2.4 Melt spun fiber with nanoclay ................................................................................ 25 2.5 Injection molded polypropylene-nanoclay composite ............................................ 26 2.6 Scientific concepts of crystallization ...................................................................... 27 2.6.1 Primary and Secondary crystallization ................................................................ 28 2.6.2 Secondary nucleation theory ................................................................................ 29 2.6.3 Avrami equation .................................................................................................. 34 2.6.4 Crystallization half time t1/2 ................................................................................. 35 2.6.5 Maximum rate of crystallization .......................................................................... 36 2.6.6 Isothermal crystallization activation energy ........................................................ 36 2.6.7 Non-isothermal crystallization kinetics ............................................................... 38 2.6.8 Scientific concepts of spherulite .......................................................................... 39 2.7 Modeling mechanical properties of nanoclay based composites ............................ 43 2.7.1 Different models