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Mechanical Properties of Thin-Film Composite Membranes and Their Role in Osmotic Processes

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Mechanical Properties of Thin-Film Composite Membranes and Their Role in Osmotic Processes Clemson University TigerPrints All Dissertations Dissertations May 2020 Mechanical Properties of Thin-Film Composite Membranes and Their Role in Osmotic Processes Jaime Andres Idarraga-Mora Clemson University, [email protected] Follow this and additional works at: https://tigerprints.clemson.edu/all_dissertations Recommended Citation Idarraga-Mora, Jaime Andres, "Mechanical Properties of Thin-Film Composite Membranes and Their Role in Osmotic Processes" (2020). All Dissertations. 2588. https://tigerprints.clemson.edu/all_dissertations/2588 This Dissertation is brought to you for free and open access by the Dissertations at TigerPrints. It has been accepted for inclusion in All Dissertations by an authorized administrator of TigerPrints. For more information, please contact [email protected]. MECHANICAL PROPERTIES OF THIN-FILM COMPOSITE MEMBRANES AND THEIR ROLE IN OSMOTIC PROCESSES A Dissertation Presented to the Graduate School of Clemson University In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Chemical Engineering by Jaime Andres Idarraga-Mora May 2020 Accepted by: Dr. Scott M. Husson, Committee Chair Dr. Amod A. Ogale Dr. Eric M. Davis Dr. David A. Ladner ABSTRACT My research goal was to understand the role of membrane mechanical properties (e.g. strength and stiffness) in the transport of water and salt through polymer-based thin- film composite (TFC) membranes used for osmotic processes (OP). OP are membrane processes in which the main driving force is a concentration difference of solute(s) in the solutions in contact with the two sides of a semipermeable membrane. OP applications may include removing water from products/contaminants, harvesting energy from salinity gradients, and lowering costs of seawater desalination. The study system for my research was a set of TFC reverse osmosis (RO) membranes designed for rejecting salts in desalination. These TFC RO membranes have thick supporting layers (~150 μm), which increases the diffusion pathway for salts within the membranes. This decreases the effective salinity gradient between the two surfaces of the membrane active layer, which ultimately decreases the process productivity (i.e., water flux). I aimed to provide guidelines for the improved design of TFC membranes for OP, considering the trade-off between membrane mechanical integrity and productivity. My research approach comprised measurements and analysis of the individual mechanical properties of the three polymeric layers (active, porous support, and backing) that comprise TFC RO membranes, and correlation of these mechanical properties with TFC membrane transport properties and performance in OP. Initially, I studied helically coiled and multiwall carbon nanotubes as additives to create nanocomposite porous supports with improved mechanical properties. The results support the idea that increasing the mechanical stiffness of TFC membrane nanocomposite supports is an effective strategy for enhancing water production in desalination operations. Secondly, I ii evaluated woven polyester mesh as a backing layer and analyzed the role of mesh opening size on burst strength and mass-transfer resistance of TFC membranes used for OP. The findings show that mass-transfer resistances in OP are an additive effect of the multiple layers that compose a membrane and can be reduced by using more open (yet functional) backing layers such as polyester woven mesh in place of standard nonwoven mesh. Thirdly, I aimed to correlate the reduction in stiffness of the active layer with the change in water permeance of five commercial TFC membranes after contact with five different C1-C4 monohydric alcohols. The motivation was to explain the improvements in water flux after alcohol contact, which is used to pre wet membranes before OP operation. Correlation of results suggests that the mixing of water with the alcohols facilitates penetration of the alcohols into the active layer, likely by disrupting inter-chain hydrogen bonds, thus increasing the active layer free volume for water permeation. Finally, I studied water and sodium chloride transport through TFC membranes that were subjected to known degrees of mechanical strain. I demonstrated the importance of knowing the stress-strain curve of the membrane and highlighted that stiffer membrane structures are desirable to avoid reaching a strain above the reported onset fracture strain of the selective layer. With this information, I introduced a deformability coefficient and a solution-diffusion model with defects to guide the design of membranes and modules for pressurized osmotic processes. In closing the dissertation, I provided recommendations and research opportunities that I envision would improve TFC membrane productivity in OP. iii DEDICATION This work is dedicated to my mother Adriana who always showed me the value of pursuing higher education. Also, I dedicate this work to the mentors, role models and friends that I have been privileged to be surrounded by throughout my life. Thank you. iv ACKNOWLEDGMENTS I thank God for creating a fascinating universe to do research on. I would like to thank my mother Adriana who always showed me the importance of getting high quality education and working hard towards your goals. I would like to thank my mentor Dr. Scott M. Husson. His dedication to my improvement as a researcher is very humbling. His dexterity in the topics of membrane separations, surface science and chemistry are impressive. His work ethic is inspiring. His approachability always made me feel comfortable to share my thoughts with him. I am privileged and lucky to have had him as my adviser during these years. He is a role model. I want to thank Jinxiang, Juan, Nikki, Christine, Joe, Anna, Mark, James, Abenazer, Valery and Josh. They helped me to perform safe and efficient experiments, introduced me to technical skills, and listened and shared ideas about both research and life. I want to thank the undergraduate students Parker, Michael, Alton, Mary Beth, Morgan and Emily who were instrumental in the development of the projects presented here. I would like to thank the Clemson University members that enabled my research. They and their teams provided access and assistance to advanced scientific techniques that I used to investigate TFC membranes. They are Kimberly Ivey, James Lowe, Donald Mulwee, George Wetzel, Dr. Taghi Darroudi, Dr. Apparao Rao, Dr. David Ladner, Dr. Anthony Childress, Dr. Eric Davis, Dr. Amod Ogale, Dr. Christopher Kitchens, Dr. Mark Roberts, and Dr. David Bruce. v I would like to thank researchers in the membrane science community who provided insightful conversation that allowed me to refine my methods, to understand better my results, and to generate ideas. Some of them are Dr. Jeffrey McCutcheon, Dr. Caleb Funk, Dr. Heather Chenette, Dr. Daniel Wandera, Dr. Pinar Cay Durgun, and multiple graduate students from other institutions. I would like to thank my committee members Dr. Amod A. Ogale, Dr. Eric M. Davis, and Dr. David A. Ladner for reviewing and providing constructive feedback to the improvement of the work presented here. Finally, I would like to thank the funding from the U.S. National Science Foundation (NSF) under Award CBET-1510790 and Award CBET-1534304, and Clemson University Creative Inquiry Project ID 986. Opinions, findings, conclusions or recommendations expressed in my dissertation are personal and they do not necessarily reflect the views of the NSF. vi TABLE OF CONTENTS Page ABSTRACT ..................................................................................................................... ii DEDICATION ................................................................................................................ iv ACKNOWLEDGMENTS ................................................................................................v TABLE OF CONTENTS ............................................................................................... vii LIST OF TABLES ............................................................................................................x LIST OF FIGURES ...................................................................................................... xiii CHAPTER ONE: INTRODUCTION ..............................................................................1 1.1 Water-Energy nexus and osmotic processes ...............................................................1 1.2 Membrane state-of-the-art: Thin-film composite membrane .....................................9 1.3 Concentration polarization ........................................................................................10 1.4 Strategies to improve transport properties of TFC membranes for OP ....................13 1.5 Studies on the effects of mechanical properties on membrane performance............24 1.6 Evaluation of membrane performance in osmotic processes ....................................29 1.7 Dissertation structure ................................................................................................36 CHAPTER TWO: THIN-FILM COMPOSITE MEMBRANES ON POLYESTER WOVEN MESH WITH VARIABLE OPENING SIZE FOR PRESSURE-RETARDED OSMOSIS ............................................................................37 2.1 Introduction ...............................................................................................................37 2.2 Experimental .............................................................................................................39 2.3 Results
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