Engineering Commons^™

Effect Of Chemical Identity And Morphology On Amphiphilic-Zwitterionic Block Copolymer Membranes, Ria Ghosh

Doctoral Dissertations

Amphiphilic block copolymers have gained a broad research interest attributed to their self-assembly properties over a range of pH, temperature, and ionic strength. Polyzwitterions have attracted special attention due to their hydrophilicity, charge sensitivity and coulombic attraction of the opposite charges over a range of environments making them a popular material of study in the field of stimuli responsive systems, for example in self-healing hydrogels, and water transport membranes. Combining the stimuli responsiveness and higher hydrophilicity of zwitterionic polymers with self-assembly behavior of amphiphilic block copolymers created an interest to study the effect of composition and identity of the zwitterionic …

Physical And Biological Factors Affecting Oxygen Transfer In The Activated Sludge Wastewater Treatment Process, Kenneth A. Campbell

Doctoral Dissertations

“The activated sludge (AS) process is widely utilized for wastewater treatment due to its versatility and general resiliency, but is energy intensive, requiring aeration and mixing energy inputs to maintain the biochemical reaction and optimize treatment performance. This study is focused on determining different factors that influence oxygen transfer and consequently its energy demand.

AS morphology, as described by the d₁₀, d₂₀, d₃₂, specific filament length (SFL), 30 min settleability (SV₃₀), etc., does influence the OTE. Filamentous organisms increase the hydrodynamic radius of suspended particles, which dilates mixed liquor apparent viscosity (µ …

Polyurea Aerogels: From Nanoscopic To Macroscopic Properties, Tahereh Taghvaee

Doctoral Dissertations

"The morphology of a material is intrinsically a qualitative property and in order to relate nanomorphology to synthetic conditions, it is necessary to express nano/micro-structure quantitatively. In this context, polyurea aerogels were chosen as a model system with demonstrated potential for rich nanomorphology and being guided by a statistical Design-of-Experiments model, a large array of materials (208) with identical chemical composition, but quite different nanostructures were prepared. By reflecting upon the SEM images, it was realized that our first pre-verbal impression about a nanostructure is related to its openness and texture; the former is quantified by porosity (Π), and the …

Synthesis, Characterization And Application Of Block Copolymer And Nanoparticle Composites, Yue Gai

Doctoral Dissertations

The “bottom-up” fabrication of functional hybrid material can be achieved by using directed self-assembly of functional nanoparticles (NP) and block copolymers (BCP) as templates. The versatile nanostructures of BCP provide possibilities to precisely control NPs spatial distribution and the resulting hybrid materials exhibit enhanced electrical, mechanical and optical functionalities. Three main topics related to BCP/NP composites are discussed in this dissertation: I) the spatial distribution of large NP in linear BCP; II) the morphology control of BCP templates with new architectures; and III) the magneto-optical properties of hybrid material using magnetic NPs. For well-ordered BCP/NP composite, the ratio of NP …

Polymer And Small Molecule Designs For Anion Conducting Membranes: Connected Ion-Channel Morphologies And Highly Alkaline Stable Ammonium Cations, Sedef P. Ertem

Doctoral Dissertations

Fuel cells are one of the oldest sustainable energy generation devices, converting chemical energy into electrical energy via reverse-electrolysis reactions. With the rapid development of polymer science, solid polymer electrolyte (SPE) membranes replaced the conventional liquid ion transport media, rendering low-temperature fuel cells more accessible for applications in portable electronics and transportation. However, SPE fuel cells are still far from commercialization due to high operation cost, and insufficient lifetime and performance limitations. Anion exchange membrane fuel cells (AEMFCs) are inexpensive alternatives to current proton exchange membrane fuel cell (PEMFC) technology, which relies on utilizing expensive noble-metal catalysts and perfluorinated SPE …

Synthesis And Characterization Of Polymeric Anion Exchange Membranes, Wenxu Zhang

Doctoral Dissertations

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 …

Morphology Evolution Mechanisms Of Low Band Gap Polymer-Based Photovoltaics, Sunzida Ferdous

Doctoral Dissertations

An optimal nanoscale phase separation between the donor (generally, a conjugated polymer) and the acceptor (generally, a fullerene derivative) materials is one of the major requirements for obtaining high efficiency organic photovoltaic (OPV) device. Recent methods of controlling such nanostructure morphology in a bulkheterojunction (BHJ) OPV device involve addition of a small amount of solvent additive to the donor and acceptor solutions. The idea is to retain the acceptor materials into the solution for a longer period of time during the film solidification process, thus allowing the donor material to crystallize earlier. The ultimate morphology resulting from the solvent casting …

Functional Nanocomposites From Self-Assembly Of Block Copolymers With Nanoparticles, Xinyu Wang

Doctoral Dissertations

This dissertation studied the proper distribution and location control of nanoparticles (NPs) within block copolymer (BCP) templates. A facile ligand exchange reaction was introduced for the hydrophilic magnetic NPs (MNPs) that are readily dispersed in polar solvents with outstanding stability. Small molecule ligands were selected to associate strongly with particle surfaces, provide hydrophilic termini for polarity matching with polar solvents, and offer the potential for hydrogen-bonding interactions to facilitate NP incorporation into polymers. Areal ligand densities of NPs indicated a significant increase in the ligand coverage after the exchange reaction. Hydrophilic MNPs were shown to drive the self-assembly of BCPs …

Creasing Instability Of Hydrogels And Elastomers, Dayong Chen

Doctoral Dissertations

CREASING INSTABILITY OF HYDROGELS AND ELASTOMERS MAY 2014 DAYONG CHEN, B.S., TIANJIN UNIVERISTY M.S., TIANJIN UNIVERSITY M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Ryan C. Hayward Soft polymers placed under compressive stress can undergo an elastic creasing instability in which sharp folds spontaneously form on the free surfaces. This process may play an important role in contexts as diverse as brain morphogenesis, failure of tires, and electrical breakdown of soft polymer actuators. While the creasing instability has been used for collotype printing since as early as the 1850s, the scientific appreciation of this instability …

Structure And Morphology Of Sulfonated Polysulfone And Perfluorosulfonic Acid Ionomers, Chen Wang

Doctoral Dissertations

The limitations of conventional perfluorosulfonic acid (PFSA) based membrane materials have provoked the search for alternative materials which can function as the electrolyte in PEM fuel cells operated at higher temperatures (> 100 °C) and without humidification. A novel class of sulfonated poly(phenylene) sulfone (sPSO2) ionomers have shown much higher proton conductivity than typical PFSA membranes at elevated temperatures. In this dissertation, both computational and experimental methods were used to investigate proton transfer, morphological and structural properties of sPSO2 and PFSA ionomers. We have undertaken ab initio electronic structure calculations to understand the primary hydration and the transfer of protons …

The Effect Of Processing Parameters On Barrier Properties Of Polymers, Russell Louis Hallman Jr.

Doctoral Dissertations

The intent of this work was to learn if polyethylene could be made with predictable water transfer rates by control of the microstructure. A series of films were formed from three different polyethylenes with a range crystallinities using melt pressing, a controlled cooling rate, and subsequent heat treatments. The samples were tested on a novel device called the polymer characterization device that measures the water transfer flux as a function of temperature. The samples’ morphology was examined using differential gradient column, differential scanning calorimetry, Fourier transform infrared microscopy, wide-angle X-ray diffractions, small-angle X-ray scattering, and small angle light scattering, and …

Investigation Of The Processing, Structure And Properties Of Poly(Phenylene Sulfide) (Pps) Melt Spun Fibers, Prabhakar Gulgunje

Doctoral Dissertations

Numerous publications are available on the structure and properties correlation of fibers spun from polymers with flexible chains such as polyethylene terephthalate (PET), nylon, polypropylene. Also considerable amount of work is reported in fibers spun from rigid rod polymers like poly(p-phenylene terephthalamide) due to their value in high performance fibers category. However, very limited literature is available on the structure-properties relationship in fibers manufactured from poly(phenylene sulfide) (PPS), a high performance polymer which possesses chain flexibility between above two classes of polymers. A few researchers have studied crystallization kinetics and the fibers by extruding the polymer using capillary rheometers. However, …