Characterizing the Cold Temperature
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Characterizing the Cold Temperature Performance of Guayule (Pathenium argetnatum) Natural Rubber and Improving Processing of Guayule and Agronomic Practices of Taraxacum kok-saghyz THESIS Presented in Partial Fulfillment of the Requirements for the Degree Master of Science in the Graduate School of The Ohio State University By Griffin Michael Bates Graduate Program in Food, Agricultural, and Biological Engineering The Ohio State University 2015 Master's Examination Committee: Katrina Cornish, Advisor Yebo Li Frederick Michel Copyright by Griffin Michael Bates 2015 Abstract Natural rubber (NR) is a vital commodity for modern economies with an expected global demand of 17 MT by 2025. This growth also will coincide with an expected supply shortfall of 1.5-3.0 MT by 2020. Guayule (Parthenium argenatum) is being investigated as a domestic source of NR due to its high molecular weight rubber content and its ability to grow in semiarid climates within the United States. Previous research has shown the ductility of guayule rubber particles fractured at -196°C compared to hevea particles which suffer shear fracture. In order to further promote guayule, the cold temperature flexibility of guayule was characterized using dynamic mechanical analysis in both green (uncompounded) and compounded latex and dry rubber samples. When compared to Hevea, Guayule NR has a lower glass transition temperature, storage modulus, and loss modulus, stiffness, and dynamic viscosity at -100°C which are evidence of greater flexibility under extreme cold conditions. There is also a correlation between the removal of protein content in both Hevea and Guayule to increased flexibility, as well as an increase of flexibility in Hevea through the removal of gel content. Membrane-removal from the rubber particles, in both species, increases flexibility. These characteristics prove the utility of Guayule and promote the continued research and cultivation of this vital commodity. Green guayule’s cold temperature flexibility was shown to be transferable to compounded latex samples, however the recipe was a major factor as to how much guayule’s cold temperature advantage can be translated to finish products. In dry rubber ii samples, there was little to no difference between hevea and guayule at -100°C, except that guayule may be able to use less filler to attain similar properties as hevea requires. In processing guayule latex, fine particles from leaf matter are a prohibitive factor for latex quality since guayule leaves do not abscise naturally. This requires mechanical or chemical defoliation that can be cost-prohibitive or decrease latex quality further. It was shown that exposure to N2(l) of less than one second and a swift impact is enough to quickly defoliate guayule shrub without significantly decreasing extractable latex quantities in fresh shrub. While small branches were more sensitive to this exposure, larger branches were able to withstand the exposure with little repercussions on the extractable latex quantities. Another alternative natural rubber source, Taraxacum kok-saghyz (referred to as TK; also known as Buckeye Gold, Kazak dandelion, and Russian dandelion) is being developed as a domestic source of rubber, but best agronomic practices must be established. By placing fresh August or November harvested roots in 4°C cold storage with humidity can increase the concentration of rubber in the roots over a period of 30 to 60 days. This ability did not occur in roots less than 7g fresh weight and June-harvested roots. This study shows that TK can be stored for extended periods the fact of which is vital for continuous production facilities necessary to advance TK as a viable source of domestic rubber. A planting density studied was carried out by planting densities of 1.24, 2.47, 4.94, and 9.88 million plants/ha in the Spring of 2013 and harvesting half in late October 2013 and the following May (2014). The October-harvested roots had greater plant iii retention the number of plants harvested divided by the number of transplanted plants, than the May-harvested roots. The October-harvested roots had higher root mass and higher overall extractable rubber per plot than the May-harvested plots. If post-harvest storage is considered as well, the 1.24 million plants/ha density could be the most advantageous planting density with a potential of 2,720kg dry rubber/ha/year. iv Dedication This document is dedicated to my family, friends, and all of the amazing teachers I have had in my life, especially my father, Philip M. Bates. v Acknowledgments I would like to sincerely thank my advisor Dr. Katrina Cornish for this amazing learning opportunity and her mentorship throughout my career at the Ohio Agricultural Research and Development Center and The Ohio State University. Her guidance has been immeasurably valuable to any success I have had in my academic endeavors as a graduate student and even back to my undergraduate days. Without her ingenuity, vision, and drive, I do not believe I would be the same scientist I am today. I would also like to thank my academic committee members, Dr. Yebo Li and Dr. Frederick Michel, for their patience, guidance, and mentorship. Special thanks to J. Lauren Slutzky for rubber knowledge, sample prep, and DMA expertise. Another special thanks to Eun Hyang Han (Grace), Shirin Mohammad Ali Monadjemi, and Dr. Joshua Blakeslee for preparation of natural rubber samples necessary to complete this work. I would like to thank all of my lab members for the chance to be part of such a wonderful team: Steven Kopicky, Sarah McNulty, Nikita Amstutz, Clare Knebusch, Scott Wolfe, Brian Iaffaldano, Shirin Mohammad Ali Monadjemi, Richard Kamenik, Zhenyu Li, Mohammad Akbar Abdul Gaffar, Yingxiao Zhang, Lu Zhao, Lily Luo, and Wenshuang Xie. I would like to thank the Jared Baisden for his initial work as an ORIP intern as well as Dr. Charles Goebel for his expertise with statistical analysis. All of your contributions both personally and professionally have made my time memorable and have opened my eyes to thinking and experiences I had not envisioned I ever would have seen. vi This work has been supported by an OARDC SEED grant, the Institute of Materials Research at The Ohio State University, and The Ohio Third Frontier. This work was also supported by the USDA National Institute of Food, Agriculture, Hatch project 230837. Most importantly, I would like to thank my mother Melanie, and my family Emma, Jon, and Paul for their love, continual support, and guidance throughout my life. Finally, I would like to thank my father, Philip, for a passion and curiosity for science that I will never leave me. vii Vita May 2006………………………………..…...Walnut Hills High School, Cincinnati, Ohio 2011……………………………………B.S. Food Agricultural, & Biological Engineering The Ohio State University, Columbus, Ohio 2014 to present …………………………….Graduate Research Associate, Department of Food, Agricultural, & Biological Engineering The Ohio State University, Columbus, Ohio Fields of Study Major Field: Food, Agricultural, and Biological Engineering viii Table of Contents Abstract ............................................................................................................................... ii Dedication ........................................................................................................................... v Acknowledgments.............................................................................................................. vi Vita ................................................................................................................................... viii Table of Contents ............................................................................................................... ix List of Tables ................................................................................................................... xvi List of Figures ................................................................................................................. xxv Chapter 1: Introduction ....................................................................................................... 1 References ....................................................................................................................... 5 Chapter 2: Review of Literature ......................................................................................... 7 2.1 Natural rubber ........................................................................................................... 7 2.2 Sources of rubber ...................................................................................................... 8 2.2.1 Rubber producing plants ........................................................................................ 8 2.2.1.1 Hevea brasiliensis ............................................................................................... 9 2.2.1.2 Parthenium argentatum .................................................................................... 10 2.2.1.3 Taraxacum kok-saghyz ...................................................................................... 12 2.2.2 Synthetic sources of rubber .............................................................................. 13 2.3 Properties of rubber ................................................................................................. 15 ix 2.3.1 Testing methods ................................................................................................ 16 2.3.1.1 Tensile