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Surface Freezing in N-Alkanes: Experimental and Molecular Dynamics Studies

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Surface Freezing in N-Alkanes: Experimental and Molecular Dynamics Studies Surface Freezing in n-Alkanes: Experimental and Molecular Dynamics Studies DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Viraj Prakash Modak Graduate Program in Chemical Engineering The Ohio State University 2015 Dissertation Committee Barbara E. Wyslouzil, Advisor Sherwin J. Singer Isamu Kusaka David L. Tomasko Copyright by Viraj Prakash Modak 2015 Abstract Crystallization from the melt is a common process encountered in both industrial and natural settings. Nucleation is the first step in the process and hence, understanding where nucleation occurs is critical to controlling the process. For systems with free surfaces, like droplets, nucleation can occur on the surface or throughout the bulk. This aspect of crystallization has been extensively debated for water droplets because of its implications in the atmospheric sciences. For intermediate chain length n-alkanes (14 < n < 50), experiments show that surfaces can freeze above the melting point. Since an organized surface can then template freezing of the bulk, these alkanes are hard to supercool. There are competing theories regarding the physics that dive the phenomenon, but both state that shorter alkanes will not surface freeze. The goal of this work is to investigate surface freezing in n-alkanes, from both experimental and theoretical perspectives. Experiments will identify if surface freezing occurs for short chain n-alkanes containing 8 to 10 carbon atoms. Molecular dynamics will help identify the driving force. In experiments, an alkane carrier gas-vapor alkane mixture flows through a supersonic nozzle and cools at a rate of ~106 K/s. Eventually the vapor alkane condenses initially forming liquid nanodroplet aerosols, that can then freeze if the temperatures are cold ii enough. Static pressure measurements characterize the flow; whereas x-ray scattering and Fourier transform infrared spectroscopy, characterize the aerosol. Experiments yielded evidence for surface freezing in C8H18 to C10H22 droplets as well as estimates for the surface and volume based nucleation rates. In n-decane, decreasing the inlet conditions eventually led to the formation of nanoparticles that had a fractal-like structure and were not fully crystalline. Molecular Dynamics (MD) simulations at the united atom level provided both visualization of surface freezing as well as estimates of the thermodynamic quantities and understand the driving force behind the phenomenon. Droplet simulations, for example clearly showed an organized monolayer developed within ~4 ns on a supercooled droplet of n-octane followed by freezing of the adjacent liquid in a layer-by-layer manner, confirming our experimental hypothesis. To understand the driving force quantitatively, MD simulations were done crystals and slabs, to determine surface free energies of the liquid-vapor (LV) and the solid-vapor (SV) interfaces. The usual pressure tensor approach sufficed for LV interfaces, but a new, less computationally intensive method was developed for the SV surface free energies. The new method works well for the LJ solid and n-octane, but overestimates SV surface free energy for n-nonadecane. Simulations also provide estimates for the entropic changes associated with surface freezing. Overall these results suggest that the entropic contribution to the driving force is significant for n-octane but not for n-nonadecane. iii To Aai-Baba, who believe in me more than I do myself iv Acknowledgements I would like to thank my advisor, Prof. Barbara Wyslouzil – she is the best advisor, and the aerosol research lab is the best group that I could have asked for. She has been a constant inspiration to me throughout my time in graduate school. She has been instrumental in not just helping me reach my scientific goals, but also in improving my approach and thought process towards solving scientific problems. She has been a great source of knowledge and working with her has been a tremendous learning experience for me. I also greatly appreciate the independence as well as encouragement that she gave me to formulate and express my ideas and opinions freely. It has helped me indentify my own strengths as well as improve on my weaknesses. I would also like to thank my co-advisor, Prof. Sherwin Singer. I had the opportunity to work with him on Molecular Dynamics simulations – something about which I had very little knowledge, when I started. Dr. Singer was more than welcoming to take a novice like me under his wings. He was extremely patient and I am sure had to endure all sorts of inane questions while I was on the learning curve. I still recall the initial few meetings that went on for hours in Dr. Singer’s office. Had it not been for his calm and encouraging demeanor, it would have been an overwhelming experience for me. It is v solely due to Dr. Singer that I can at least speak the MD language, if not declare myself as someone who is well versed. I consider myself lucky to have known and worked with two amazing scientists and advisors in Dr. Wyslouzil and Dr. Singer and I owe all my accomplishments completely to them. I would like to thank Dr. Harshad Pathak, who was my mentor during the first few months when I joined the research group. He was my go-to person for anything that went wrong and for anything that I could not understand. I continued to seek his advice even after I gained a foothold in my projects, until he graduated in December 2013. I would also like to thank Andrew Amaya – he is an amazing person to work with. I still remember the crazy few months that we had around our trip to Stanford Linear Accelerator Center (SLAC). Having colleagues like Harshad and Andrew turned it into a great, fulfilling experience. I greatly appreciate the support and encouragement that I received from Dr. Ashutosh Bhabhe and Dr. Kelley Mullick, when I joined the lab. I am also thankful my current and former colleagues, Dr. Shinobu Tanimura, Yensil Park, Kehinde Ogunronbi, Matt Gallovic, Matt Souva, Gauri Nabar and Alyssa Robson for keeping the atmosphere in my workplace lively. I would like to thank the National Science Foundation and the Ohio Supercomputer Center for providing the funding and the computational resources respectively, for my research. I would like to thank the scientists at SLAC and Argonne National Lab (ANL) and in particular, our collaborators Dr. Hartawan Laksmono and Dr. Judith Wolk, for vi their help in running the X-ray scattering experiments. I would like to thank Dr. Soenke Seifert, for the stimulating discussions and the unending supply of coffee during our trip to the Advanced Photon Source at ANL. I have been lucky to have several friends who have made my life in Columbus enjoyable. Special thanks to Dr. Nihar Phalak, Dr. Kalpesh Mahajan, Dr. Hrishikesh Munj, Mandar Kathe, Dr. Niranjani Deshpande Dr. Anshuman Fuller, Prateik Singh, Dr. Somsumndaram Chettiar, Dr. Shweta Singh, Dr. Shreyas Rao, Dr. Kartik Ramasubramanian, and Dr. Preshit Gawade. I would also like to thank Sumant, Varun, Ankita, Sreshtha, Dhruvit, Insiya, Varsha, Nitish, Aamena, Janani, Abhilasha, Deeksha, Sourabh, Amoolya, Yaswanth, and Atefeh. Last but not the least; I would like to thank my parents, my brother and my close family for their constant love and support. They are the ones that I turned to during times of stress and frustration. They never once doubted my capability to overcome any obstacle and have always encouraged me to pursue my dreams and for that, I am forever grateful. vii Vita July 2006 – June 2010………………………. Bachelor of Chemical Engineering, Institute of Chemical Technology, University of Mumbai, Mumbai, India September 2010 – August 2011…..………… Graduate School Fellow The Ohio State University September 2010 – May 2013…..…………… MS in Chemical Engineering The Ohio State University August 2014 – December 2015…..…………. Graduate Teaching Associate Engineering Education Innovation Center, The Ohio State University September 2010 – Present………..…………. Graduate Research Associate The Ohio State University viii Publications V. P. Modak, H. Pathak, M. Thayer, S. J. Singer, B. E. Wyslouzil, Experimental evidence for surface freezing in supercooled n-alkane nanodroplets, Physical Chemistry Chemical Physics, 15, 6783-6795, (2013) Fields of Study Major Field: Chemical Engineering ix Table of Contents Abstract……………………………………………………………………………… ii Dedication…………………………………………………………………………… iv Acknowledgements………………………………………………………………….. v Vita…………………………………………………………………………………... viii List of Tables………………………………………………………………………… xiii List of Figures……………………………………………………………………….. xvi Chapter 1: Introduction……………………………………………………………… 1 1.1 Liquid-solid phase transitions……………………………………………….... 1 1.2 Background for current work………………………………………………… 2 1.3 Objective……………………………………………………………………… 6 1.4 Thesis outline…………………………………………………………………. 7 Chapter 2: Aerosol generation flow system and experimental techniques………….. 13 2.1 Experimental setup…………………………………………………………… 13 2.2 Pressure Trace Measurements (PTM) ……………………………………….. 16 2.3 Small Angle X-ray Scattering (SAXS) ………………………………………. 17 2.4 Fourier Transform Infrared Spectroscopy……………………………………. 19 2.5 Integrated data analysis………………………………………………………. 24 2.6 Wide Angle X-ray Scattering (WAXS) ……………………………………… 25 2.7 Materials……………………………………………………………………… 25 Chapter 3: Surface freezing in supercooled n-octane and n-nonane nanodroplets….. 30 3.1 Introduction…………………………………….…………………………….. 30 3.2 Experiments…………………………………….…………………………….
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