Advanced Thin Film Composite and Nanocomposite Polyamide Membrane for Water Treatment

by Behnam Khorshidi Mianaee

A thesis submitted in partial fulfillment of the requirements for the degree of

Doctor of Philosophy

Department of Mechanical Engineering University of Alberta

©Behnam Khorshidi, 2017

Abstract

Membrane technology is currently widely used for separation of ions, , organic matter and macromolecules. Among various membrane processes, nanofiltration (NF) and (RO) with thin film nanocomposite (TFC) polyamide (PA) membrane at the heart of the is being increasingly employed for sea and brackish water treatment and wastewater reclamation. Over the past decade, the increasing need to implement highly cost and energy efficient membranes processes has accelerated the research effort to fabricate advanced composite membranes with enhanced permeation, thermomechanical, and antifouling properties. In the present research, systematic studies were conducted to fabricate high performance composite PA membrane with improved thermal stability and antifouling propensity. First, the effects of synthesis conditions and chemical additives were studied on the permeation properties of the TFC PA membranes. The composite membranes were prepared by interfacial polymerization (IP) reaction between meta-phenylene diamine (MPD)-aqueous and trimesoyl chloride (TMC)-organic solvents (such as heptane, hexane and cyclohexane) at the surface of polyethersulfone (PES) microporous support. Several influential factors including the concentration of the reacting monomers, reaction time and temperature, thermal curing temperature, and the concentration of chemical additive such as surfactant, pH regulator, co-solvents in the water-based monomer solution was investigated using design of experiment (DOE) methodology. The results revealed that the final permselectivity of a TFC PA membrane is remarkably dependent of its surface physicochemical properties, structural characteristics and the complex internal free volumes which can all be influenced by synthesis conditions. The findings of the first stage of this research provided valuable insight and useful guidelines for the development of TFC PA membranes with wide range of water permeation and salt rejection. These findings were used in the second stage of the research where robust and high performance nanocomposite membranes were prepared by incorporation of metal oxide nanoparticles (NPs) to the membrane structure. Initially, nanocomposite microporous membranes were prepared by integration of indium tin oxide (ITO) NPs to the PES matrix via phase inversion process. The resulting PES-ITO membranes demonstrated higher thermal stability and antifouling porosity comparted to pristine PES membranes when tested with industrially produced

ii water. Finally, titanium dioxide (TiO2) NPs were effectively incorporated to the PA active layer using a combination of biphasic solvothermal (BST) reaction and

IP reaction. The resulting thin film nanocomposite (TFN) PA-TiO2 membranes showed an enhanced thermal stability and anti-biofouling characteristics compared to base TFC PA membranes.

Keywords: Membrane , nanofiltration, reverse osmosis, thin film composite, thin film nanocomposite, polyamide, interfacial polymerization, metal oxide nanoparticle, thermal stable, antifouling.

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Preface

This thesis is the original work by Behnam Khorshidi. The majority of the context in chapter 3, 4, and 5 are published in the following journals:

1. B. Khorshidi, I. Biswas, T. Thundat, M. Sadrzadeh, A novel approach for the

fabrication of thin film polyamide-TiO2 nanocomposite membranes with enhanced thermal stability and anti-biofouling propensity, Scientific Reports (under review). 2. B. Khorshidi, T. Thundat, D. Pernitsky, M. Sadrzadeh, A parametric study on the synergistic impacts of chemical additives on permeation properties of thin film composite polyamide membrane, J. Memb. Sci. 535 (2017) 248–257. doi:10.1016/j.memsci.2017.04.052. 3. B. Khorshidi, B. Soltannia, T. Thundat, M. Sadrzadeh, Synthesis of thin film composite polyamide membranes: Effect of monohydric and polyhydric alcohol additives in aqueous solution, J. Memb. Sci. 523 (2017) 336–345. doi:10.1016/j.memsci.2016.09.062. 4. B. Khorshidi, T. Thundat, B.A. Fleck, M. Sadrzadeh, A novel approach toward fabrication of high performance thin film composite polyamide membranes, Sci. Rep. 6 (2016) 22069. doi:10.1038/srep22069. 5. B. Khorshidi, A. Bhinder, T. Thundat, D. Pernitsky, M. Sadrzadeh, Developing high throughput thin film composite polyamide membranes for forward osmosis treatment of SAGD produced water, J. Memb. Sci. 511 (2016) 29–39. doi:10.1016/j.memsci.2016.03.052. 6. B. Khorshidi, J. Hajinasiri, G. Ma, S. Bhattacharjee, M. Sadrzadeh, Thermally resistant and electrically conductive PES/ITO nanocomposite membrane, J. Memb. Sci. 500 (2016) 151–160. doi:10.1016/j.memsci.2015.11.015. 7. B. Khorshidi, T. Thundat, B.A. Fleck, M. Sadrzadeh, Thin film composite polyamide membranes: Parametric study on the influence of synthesis conditions, RSC Adv. 5 (2015) 54985–54997. doi:10.1039/C5RA08317F.

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Dedicated to my parents, Maryam and Mohammadtaghi And my wife, Fahimeh for their endless love and inspiring support. Love you

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Acknowledgement

It was a unique experience for me to finish my PhD studies in University of Alberta and it was not possible without the help and support of a number of incredible people whom I have to express my great appreciation to them. First of all, I would like to particularly thank my main supervisor, Dr. Mohtada Sadrzadeh. You have been more than a supervisor for me and I’d like to thank you so much for whatever I learned from you in my personal and professional life. I would also like to express my gratitude to my second supervisor, Dr. Thomas Thundat. I feel proud to have the opportunity of working with you. Your motivation, enthusiasm and your philosophies in academic life have always inspired me to go forward during my PhD. I am thankful to my committee member, Dr. Brian Fleck for his continuous support and guidance. I would like take the opportunity and give my special thanks to Dr. Subir Bhattacharjee, for being my supervisor in an academic year of 2013-2014. I am very grateful to you for teaching me to become an expert learner in my academic life. In addition, I am very grateful to Josie Nebo and Ni Yang for their continuous support and lab assistance. I am really fortunate that I have really good colleagues and friends in the Advanced Water Research Laboratory (AWRL) and University of Alberta. Special thanks to Hadi Nazaripoor for the numerous productive discussions that we had in his office. I really appreciate the help and support of my other friends: Behnam Sadri, Babak Vajdi, Ishita Biswas, Mohammad Nojumi, Amir hossein Mahdavi, Ali Mohammadtabar, Simin Shabani, Amin Karkooti, Babak Soltania, Farshad Mohammadtabar, Zayed Almansoori, Ayda Razi, Laleh Shmaei, Debanik Bhattacharjee, Asad Asad, Rouholluh Shokri, Mica Yousuf, Jannat Fatema, Ehsan Shahidi, Soundararajan Desikachari; thank you all. Above all, I’d like to give my deepest appreciation and gratitude to my family, Mohammadtaghi, Maryam, Farzaneh, Behrooz, Afsaneh, Hamidreza, Mahdi, Atrina and my wife, Fahimeh, for their endless love, patience and support. I can’t say enough to thank you for being my strength and inspiration of my life. Finally, I appreciate the financial support from the following agencies that helped me to finish my PhD research: Natural Sciences and Engineering Research Council of Canada (NSERC), Alberta innovates technology futures (AITF), Canada's Oil Sands Innovation Alliance (COSIA), Suncor Energy Company, ConocoPhillips Corporation, and Devon Energy Company.

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