Ion exchange membranes (IEMs) have emerged as important components in a wide variety of electrochemical processes and applications, playing a vital role in facilitating the selective transport of ions while preventing species crossover between the anolyte and catholyte. These versatile polymer or polymer composite membranes find uses in diverse fields such as energy conversion and storage, water treatment, chemical synthesis, and biotechnology. At the core of their functionality, ion exchange membranes exhibit a unique property known as "selective permeability." This property allows them to permit the controlled movement of specific ions across their structure based on differences in charge and size, while restricting the transport of other species. Diffusion of other molecules, such as water, can also be controlled simultaneously by optimizing the ion content, water uptake, and polymer structure of these materials. The design and synthesis of ion exchange membranes involve the incorporation of charged functional groups capable of exchanging ions with the surrounding solution. This functional group can be embedded in the backbone of the polymer, in an ionene-type structure, or attached to the backbone by tethered side chains. IEMs are broadly classified by the charge of the functional group into cation exchange membranes (CEMs) and anion exchange membranes (AEMs). CEMs have anionic functional groups and permit the transport of cations, whereas AEMs have cationic functional groups and permit the transport of anions. Bipolar membranes (BPM) are a type of composite IEM consisting of an AEM and CEM laminated together and an interesting topic of future research. Most AEMs produced today contain chemically unstable arylene ether backbones, have poor mechanical properties, and require toxic reagents for functionalization. This dissertation seeks to synthesize new anion exchange membranes that are stable in alkaline conditions while maintaining the high conductivities required for the operation of electrochemical devices. To develop a chemically stable aliphatic polyolefin AEM, a library of polymers synthesized via Ziegler-Natta polymerization was examined. This library consisted of quaternized poly(11-bromo-1-undecene-co-4-phenyl-2-butene) with degrees of functionalization of 20 mol% to 50 mol% -- and was made utilizing a different catalyst system than previously explored. A TiCl3ˑAA catalyst was reacted with triisobutylaluminum (TiBA) co-catalyst to synthesize a more robust catalyst complex than the traditional AlEt2Cl catalyst. It was found that this new system could incorporate a higher amount of halogenated monomer (up to 50 mol %) on a multi-gram scale (50 g) at high yield without poisoning and deactivating the catalyst. The monomer incorporation was equal to the monomer feed and allowed for the targeting of specific ion exchange capacities. A large-scale synthesis (100 g) was conducted to assess the feasibility of pilot scale experiments. The dissolved polymers were solvent cast onto an ePTFE support and heterogeneously quaternized by immersing the alkylbromide-functionalized membrane in trimethyl amine solution. This procedure resulted in uneven wrinkled membranes, and a new method of casting supported membranes was subsequently developed, as described below. The hydroxide conductivity of the membranes was measured at room temperature, with conductivities up to 32 mS/cm reported. Given the issues with deformities in the supported membranes, further work focused on developing more efficient and consistent methods of membrane fabrication. It is speculated from initial experiments that high molecular weight polymer was being filtered from the sample during solution processing -- decreasing the mechanical strength of cast membranes. The quaternary ammonium-functionalized polyolefins were cryomilled to retain high molecular weight polymer without aggregation. Casting membranes from the cryomilled powder increased the mechanical properties of the membrane such that the mechanical membrane support was no longer needed. Moreover, cryomilling facilitated bulk heterogenous quaternization of the polymer prior to membrane fabrication, reducing the amount of trimethylamine solution needed. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) measurements confirmed that the Menshutkin reaction went to completion and all bromine moieties were quaternized for all degrees of functionalization. The quaternized polymer resins were cryomilled to yield a free-flowing powder that could be used for AEM fabrication. The polymers were examined with thermogravimetric analysis, and the degradation temperature of the ammonium was found to be 215 °C in the chloride form. Suggesting that thermal processing, such as heat pressing, is a viable option for membrane fabrication. Environmentally benign ethanol as a solvent was utilized to disperse the powder and cast membranes unsupported. The resulting AEMs were smooth, with even appearance across the sample, and thin, with thicknesses ranging between 15 [mu]m and 20 [mu]m. Preliminary synthesis on a monomer for ring opening metathesis polymerization (ROMP) was attempted in an effort to examine the effects of well-defined backbone architecture on conductivity and chemical durability. The monomer, 3-(N,N'-dimethylpropyl-1-amine)-cyclooctene, was synthesized in high purity and characterized by proton NMR. Unfortunately attempts to polymerize the monomer via ROMP were unsuccessful as of the writing of this dissertation.

Anion exchange membrane fuel cells (AEMFCs) are an alternative renewable energy source with potential benefits including use of non-precious metal catalysts, facile electro-kinetics, and high power density. Despite these advantages, development of chemically robust and highly conductive anion exchange membranes (AEMs) is the great challenge. The properties of polymeric AEMs depend on many parameters, for example, backbone structures, morphology of membranes, and chemical stability of the ion transporting group. Therefore, all of these interconnected parameters have to be addressed and studied for AEM development. The objectives of this dissertation are 1) to develop durable membranes with high anion conductivity by cost effective materials and methods, and 2) to understand the structure-property relationship by designing polymer structures and membrane morphology. To achieve these goals, the presented research focuses on development of polystyrene (PS) based AEMs by the post-crosslinking method using the click reaction. The first work of this dissertation (chapter 2) was to establish a facile and effective AEM fabrication method. AEMs with optimized ion exchange capacity (IEC) and degree of crosslinking showed the improvement of electrochemical properties and fuel cell performance. Different PS architectures including block and random copolymers with the benchmark cation for AEM, benzyltrimethylammonium (BTMA), were designed and synthesized in our next step (chapter 3). The focus in this particular series was to study the effect of membrane morphology on ion conductive properties. Significant differences were observed between random and block copolymer based AEMs. The nano-scale ordered morphology of the block membranes led to satisfactory ion transport properties as well as improved durability of the membranes. Furthermore, the fuel cell test revealed that the block membranes maintained superior performance after multiple polarization curves in comparison with one of the best commercial AEMs (A201). The stability of cations is another crucial subject for AEM progress. Therefore, a novel AEM with phenyltrimethylammonium (PTMA) was fabricated from the PS based block copolymer, which was designed to avoid cation degradation through the elimination and nucleophilic substitution reactions (chapter 4). The preliminary data indicated that this novel AEM had higher thermal and chemical stability than the BTMA based AEM with similar structure.

As alkaline anion exchange membrane fuel cells (AAEMFC) are regarded as promising and important energy devices, the development of high performance anion exchange membranes are in urgent need, as well as fundamental investigation on the structure-property relationship, which are the motivation of this dissertation. Three different polymer systems are presented and focused on polymer synthesis, material morphology, and ion transport phenomena. Crosslinked membranes are promising as practical materials, however, the understanding and further improvement of its performance is hindered by the lack of an ordered morphology or well-defined chemical structure. In Chapter 2, a series of crosslinked membranes were design to bear cationic groups organized via covalent linkages, which were synthesized by sequential reversible addition-fragmentation chain transfer radical polymerization (RAFT), "click" chemistry, cast/crosslinking process, and solid state quaternization. Significant enhancement in conductivities was observed and presumably attributed to the formation of ion transport channels directed by polycation chains. Excellent membrane performance were observed, including conductivities, water diffusivities, and fuel cell power densities. In Chapter 3, phosphonium containing block copolymers were synthesized and subjected to morphology characterization. Using Small Angle X-ray Scattering (SAXS) and Transmission Electron Microscopy (TEM), it was observed that these materials form well-ordered morphologies upon solvent casting, and the ionic block preferred to form a continuous phase. By comparing the anion conductivities, the matrix in a hexagonal phase was proved to be more efficient in ion transport than lamellae. Polycyclooctene (PCOE) based triblock copolymers were synthesized in Chapter 4, by using a special chain transfer agent (CTA) to mediate Ring-Opening Metathesis Polymerization (ROMP) and reversible addition-fragmentation chain transfer radical polymerization (RAFT). The well-defined melting transition (~50 oC) of PCOE enabled the investigation of the thermal transition in hydrophobic block affecting ionic domain behavior. Then metal ion doped star block copolymers were investigated in bulk and thin film forms to demonstrate that the star block copolymer architecture can facilitate microphase separation and thus the preparation of smaller features. Using an ortho-nitrobenzyl ester junction, triblock copolymers based on PEO and PSt were synthesized and applied to hierarchical pattern fabrication in self-assembled thin films. During these studies, the single monomer insertion methodology was developed for high efficiency synthesis of (multi)functional RAFT CTAs. The molecular characterization and controlled polymerization results were documented in Chapter 7. The last chapter contains outlooks based on the research in this dissertation. Methods to improve the previously presented materials were listed. Also, fundamental questions were raised on ion transport membranes, and possible ways to answer them were provided. In addition, potential research directions are proposed.

Ion Exchange Membranes A comprehensive introduction to the electro-membrane technologies of the future An ion exchange membrane is a polymer-based membrane which can be permeable by some ions in a solution while blocking others, making them ideal for processes such as water desalination, salt concentration control, clean production and—given their electrical conductivity—power generation and energy storage etc. Recent advances have given rise to new electro-membrane processes that promise drastically to expand the applications of this technology. Scientists in both research and industry will increasingly need to draw on these membranes in vital ways with strongly positive potential environmental impact. Ion Exchange Membranes summarizes recent research into these membranes and electro-membrane processes before moving to an overview of the historical background. It then attends in detail to cutting-edge fabrication technologies and the most recent areas of use. The result is a comprehensive introduction to the design, fabrication, and applications of these increasingly essential membranes. Ion Exchange Membranes readers will also find: In-depth treatment of industrial-scale applications Detailed discussion of topics including side-chain engineering, polyacylation, superacid-catalyst polymerization, and more Analysis of electro-membrane processes such as alkaline membrane water electrolysis, solar-driven water splitting, and many more Ion Exchange Membranes is ideal for membrane scientists, materials scientists, inorganic chemists, polymer chemists, and researchers and engineers in a variety of fields working with ion exchange membranes and electro-membrane processes.

Membrane technologies are currently the most effective and sustainable methods utilized in diversified water filtration, wastewater treatment, as well as industrial and sustainable energy applications. This book covers essential subsections of membrane separation and bioseparation processes from the perspectives of technical innovation, novelty, and sustainability. The book offers a comprehensive overview of the latest improvements and concerns with respect to membrane fouling remediation techniques, issues of bioincompatibility for biomedical applications, and various subareas of membrane separation processes, which will be an efficient resource for engineers.

This book presents a detailed discussion of the fundamentals and practical applications of membrane technology enhancement in a range of industrial processes, energy recovery, and resource recycling. To date, most books on the applications of membrane technology have mainly focused on gas pollution removal or industrial wastewater treatment. In contrast, the enhancement of various membrane processes in the areas of energy and the environment has remained largely overlooked. This book highlights recent works and industrial products using membrane technology, while also discussing experiments and modeling studies on the membrane enhancement process.

Advanced Nanomaterials for Membrane Synthesis and Its Applications provides the academic and industrial communities the most up-to-date information on the latest trends in membrane nanomaterials and membrane nanotechnology used in wastewater treatment, environmental technology and energy. The rapid advances in nanomaterials and nanotechnology development over the past decade have resulted in significant growth of the membrane business for various industrial processes, particularly in nanotechnology-based membrane processes. While membrane technology is increasingly being used for liquid and gas separations, it has great potential in a variety of additional applications. As the worldwide academic community has a strong interest in advanced membrane processes, particularly membrane nanotechnology for specific separations, this book provides a timely update on the topic. - Presents a unique focus on the use of advanced nanomaterials in membrane fabrication/modification, and in the description of membrane nanotechnologies, such as nanofiltration, thin film nanocomposites and nanofibers for various applications - Describes next generation membranes, providing first resource details on the development and commercialization stages of these new membranes - Represents the state-of-the-art on the use of nanomaterials in membrane science

Ion Exchange Membranes A comprehensive introduction to the electro-membrane technologies of the future An ion exchange membrane is a polymer-based membrane which can be permeable by some ions in a solution while blocking others, making them ideal for processes such as water desalination, salt concentration control, clean production and—given their electrical conductivity—power generation and energy storage etc. Recent advances have given rise to new electro-membrane processes that promise drastically to expand the applications of this technology. Scientists in both research and industry will increasingly need to draw on these membranes in vital ways with strongly positive potential environmental impact. Ion Exchange Membranes summarizes recent research into these membranes and electro-membrane processes before moving to an overview of the historical background. It then attends in detail to cutting-edge fabrication technologies and the most recent areas of use. The result is a comprehensive introduction to the design, fabrication, and applications of these increasingly essential membranes. Ion Exchange Membranes readers will also find: In-depth treatment of industrial-scale applications Detailed discussion of topics including side-chain engineering, polyacylation, superacid-catalyst polymerization, and more Analysis of electro-membrane processes such as alkaline membrane water electrolysis, solar-driven water splitting, and many more Ion Exchange Membranes is ideal for membrane scientists, materials scientists, inorganic chemists, polymer chemists, and researchers and engineers in a variety of fields working with ion exchange membranes and electro-membrane processes.

Nanostructured materials are revolutionizing various industries with their unique properties. Yet, researchers and practitioners need help accessing comprehensive and up-to-date literature on their synthesis, characterization, and applications. Existing books often focus narrowly on synthesis methods, overlooking critical aspects such as design, spectroscopic characterization techniques, and diverse applications in electronics, optoelectronics, biomedical devices, and more. This gap in the literature leaves academics, researchers, and industrial scientists needing a comprehensive resource to address their pressing questions and needs in the field. Design, Fabrication, and Significance of Advanced Nanostructured Materials bridges this gap by offering a holistic approach to understanding these materials. It provides in-depth coverage of the latest synthetic approaches, spectroscopic characterization techniques, and advanced applications in various fields. With ten chapters covering a wide range of topics, from the basics of nanostructured materials to advanced fabrication techniques, this book serves as a one-stop resource for anyone looking to delve into this exciting field. This book aims to empower researchers and industrialists with the knowledge to innovate and advance in their fields by providing clear explanations and solutions to critical questions surrounding nanostructured materials.