The solution rheological and electrospinning behavior of a series of charge-containing polymers, surface-active agents, and carbon nanotube composites was studied to investigate the effect of intermolecular interactions, including electrostatic interactions, hydrogen bonding, surface activity, and surface functionalization of carbon nanotubes. The synthesis of novel polyelectrolytes with varied topologies, charge content, and counterions tailored the charged macromolecules to elucidate structure-rheology and structure-processing relationships. In addition, the use of additives for electrospinning, including surfactants and nanofillers, allows us to tailor the functionality of electrospun nanofibers for high-performance applications. Novel polyelectrolytes based on poly(2-(N,N-dimethyl)aminoethyl methacrylate) (DMAEMA) were synthesized with the counteranions Cl-, NO3-, (CN)2N-, BF4-, PF6-, triflate (TfO-), and bis(trifluoromethanesulfonyl)imide (Tf2N-). The counteranion selection controlled the thermal transitions and degradation; the larger and more charge-delocalized anions typically resulted in lower Tg and higher decomposition temperature. The polyelectrolyte behavior in solution was nearly independent of anion choice, though solution conductivity depended on the electrophoretic mobility of the counterion. Charge containing copolymers of DMAEMA and di(ethylene glycol) methyl ether methacrylate (MEO2MA) were synthesized and demonstrated that polyelectrolyte behavior in solution was also nearly independent of charge content. Low ionic contents resulted in extended solution conformations and high conductivities. Controlled atom-transfer radical polymerization allowed the synthesis of star-shaped polyelectrolytes with varying arm numbers and lengths. The solution behavior of the stars deviated slightly from the linear polyelectrolytes due to significant counterion condensation within the star core and constrained polymer conformations. The linear and star-shaped polyelectrolytes were electrospun to understand the interplay between polyelectrolyte structure and electrospinnability. Similar to other strong polyelectrolytes described in the literature, PDMAEMA-based polyelectrolytes with polar anions (e.g. Cl-) experienced significant instabilities during electrospinning, requiring high concentrations and viscosities to stabilize the electrospinning jet. The use of large, more hydrophobic anions (BF4-, TfO-) led to increased electrospinnability. Unlike neutral branched polymers, which electrospin nearly identically to linear polymers of similar molecular weight, the star-shaped PDMAEMA-based polyelectrolytes required even higher viscosities than linear polyelectrolytes for stable electrospinning. The correlations between electrospinnability and solution rheological analysis are detailed. The use of surfactants facilitates the electrospinning of neutral polymers at lower concentrations. However, we have demonstrated that specific cylindrical aggregates of surfactants (wormlike micelles) can be electrospun into microfibers under the proper conditions. Ammonium and phospholipids surfactants as well as organogelators were studied using solution rheology and DLS to determine the effects of micellar structure and solution viscosity on the electrospinnability of low molar mass surfactants. In addition, the effects of charged and uncharged surfactants on the electrospinning behavior of poly(methyl methacrylate) were determined. Added surfactant facilitated uniform fiber formation at lower PMMA concentrations. XPS analysis demonstrated the formation of core-shell fibrous structures resulting from the self-migration of surfactants to the fiber surface. Hydrogen bonding also influences fiber formation through electrospinning. Star-shaped poly(D,L-lactide)s (PDLLAs) were end-functionalized with adenine (A) or thymine (T) units. The complementary hydrogen bonding between the adenine and thymine lead to thermoresponsive rheological behavior for mixtures of PDLLA-A and PDLLA-T. The mixtures could be electrospun above the hydrogen bond dissociation temperature and resulted in thicker fibers compared to unfunctionalized PDLLA stars. The hydrogen bonding allows the preparation of polymers with a combination desirable solid-state properties and very low processing viscosities. The effects of carbon nanotube incorporation on electrospinning behavior and fiber morphology were also investigated. Nonfuntionalized and carboxylic-acid functionalized carbon nanotubes were electrospun into polyurethane nanofibers. The nonfunctionalized nanotubes required high-shear melt mixing to disperse within the polyurethane, but remained well dispersed through electrospinning. The surface functionalization with acid groups produced nanotubes which dispersed more readily into the polyurethane solutions. TEM analysis revealed that nanotube dispersion and alignment within the nanofibers was similar for both nonfunctionalized and acid-functionalized nanotubes. / Ph. D.

The incorporation of substituted stilbenes in copolymers affects the resulting solution properties and their controlled radical polymerizations. Substituted stilbene monomers readily polymerize in an alternating fashion with acceptor comonomers such as maleic anhydride and maleimide. These sterically crowded polymer backbones are classified as semi-rigid. As this is an uncommon category of polymer backbone rigidity, examples of semi-rigid and rigid polyzwitterions in the literature were reviewed as well as stilbene-containing semi-rigid polymers. Using a deprotection strategy, anionic polyelectrolytes and polyampholytes of stilbene-maleic anhydride copolymers were synthesized and characterized by first synthesizing organic-soluble polymer precursors. Solution shear rheology and statistical segment length measurements reveal that carboxylated polyanions containing stilbene and maleic acid remain semi-rigid in aqueous solutions. It was found that these semi-rigid polyanions exhibited excellent anti-HIV activity possibly due to their more extended polymer chains. This was the first time that intrinsic polymer rigidity was introduced as a possible design parameter for microbicidal applications. Reversible addition fragmentation chain transfer (RAFT) polymerization techniques were used to copolymerize 4-diethylaminostilbene with maleic anhydride. These new semi-rigid copolymers were incorporated into double hydrophilic block copolymers (DHBCS) containing semi-rigid and flexible segments. The subsequent solutions properties of these DHBCs were evaluated with respect to pH and salt responsiveness. Notably, the DHBCs exhibited a "like-charge" attraction as ionic strength increased which was attributed to the semi-rigid character of the polyampholyte block copolymer. / Ph. D.

Polyelectrolyte complexes (PEC) are a novel class of copolymers formed from the reaction between polyanions and polycations (PE's) in polar solvents. / Master of Science

No description available.

Doctor of Philosophy / Department of Chemistry / Daniel A. Higgins / This doctoral thesis covers the synthesis, preparation, and characterization of a series of four perylene diimide derivatives, and the nanofibrous composite materials formed by these perylene diimides when complexed with oppositely charged polyelectrolytes. The perylene diimides include a symmetric dication (TAPDI2+), a symmetric dianion (PDISO32-), and two singly charged asymmetric varieties (C11OPDI+ and C7OPDI+) that contain a hydrophilic head group and hydrophobic ether tail. For all studies presented in the following chapters, poly(acrylate) (PA-) or poly(diallyldimethylammonium) chloride (PDDA+) are used as the polyelectrolytes (PEs). The patterned deposition of sheer aligned, nanofibrous material within a fluidic device is conclusively demonstrated. Thin films of the nanofibrous composite are prepared from aqueous solutions of the semiconducting perylene diimides and oppositely charged polyelectrolyte precursors. By sequentially exposing a clean glass substrate to the cationic and anionic precursor solutions, a thin film of composite material is deposited in a layer-by-layer fashion. By utilizing electrostatic self-assembly (ESA) and layer-by-layer (LbL) procedures, precise control of film thickness and optical density are obtained. The effect of perylene diimide structure and charge on resultant composite film morphology is explored. Through spectroscopic and microscopic studies of bulk perylene diimide solutions and composite thin films, it was determined that the formation of these fibrous materials is dependent on the aggregation of the PDI within the precursor solutions. The molecular orientation of the perylene diimide within the composite nanofiber was determined to be perpendicular to the fiber long axis. For the special case of C7OPDI+/PA- composite, flow induced fiber alignment was observed for both dip coated and flow coated samples. The influence of solution flow profile, PE molecular weight (MW), and PDI structure on deposition efficiency, macroscopic and microscopic morphology, and the potential for nanofiber alignment are investigated. Film formation mechanisms involving two unique routes are also presented.

Submitted in the fulfillment of the requirements for the Master of Engineering, Durban University of Technology, Durban, South Africa. 2016. / The effectiveness of using a low cost non - platinum (Pt) material for the catalyst layer of a polymer electrolyte fuel cell (PEMFC) was investigated. A test cell and station was developed. Two commercial Pt loaded membrane electrode assemblies (MEA) and one custom MEA were purchased from the Fuelcelletc store. Hydrogen and oxygen were applied to either side of the custom MEA which resulted in an additional sample tested. An aluminium flow field plate with a hole type design was manufactured for the reactants to reach the reaction sites. End plates made from perspex where used to enclose the MEA, flow field plates, and also to provide reactant inlet and outlet connection points. The developed test station consisted of hydrogen and oxygen sources, pressure regulators, mass flow controllers, heating plate, and humidification units. A number of experimental tests were carried out to determine the performance of the test cells. These tests monitored the performance of the test cell under no-load and loaded conditions. The tests were done at 25 °C and 35 °C at a pressure of 0.5 bar and varying hydrogen and oxygen volume flow rates. The no-load test showed that the MEA’s performed best at high reactant flow rates of 95 ml/min for hydrogen and 38 ml/min for oxygen. MEA 1, 2, 3, and 4 achieved an open circuit voltage (OVC) of 0.936, 0.855, 0.486 and 0.34 V respectively. The maximum current density achieved for the MEAs were 0.3816, 0.284, 15x10-6, and 50x10-6 A/cm2. Under loaded conditions the maximum power densities achieved at 25 °C for MEA’s 1, 2, 3, and 4 were 0.05, 0.038, 2.3x10-6, 1.99x10-6 W/cm2 respectively. Increasing the temperature by 10°C for MEA 1, 2, 3, 4 resulted in a 16.6, 22.1, 1.79, 10.47 % increase in the maximum power density. It was found that increasing platinum loading, flow rates, and temperature improved the fuel cell performance. It was also found that the catalytic, stability and adsorption characteristics of silver did not improve when combining it with iridium (Ir) and ruthenium oxide (RuOx) which resulted in low current generation. The low maximum power density thus achieved at a reduced cost is not feasible. Thus further investigation into improving the catalytic requirements of non Pt based catalyst material combinations is required to achieve results comparable to that of a Pt based PEMFC. / M

Peng Shufu. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Because of its high specific strength, durability, and biocompatibility, titanium is a widely used material for orthopedic implants. However, its insufficient binding with the surrounding bone tissue regularly leads to stress shielding, bone resorption and implant loosening. A promising solution to improve adhesion is to modify the implant surface chemistry and topography by coating it with a protein-eluting polyelectrolyte complex. Bone morphogenetic protein 2 (BMP-2), a potent osteoconductive growth factor, was adsorbed onto the surface of anodized titanium, and polyelectrolyte multilayer (PEM) coatings prepared from solutions of poly-L-histidine (PLH) and poly(methacrylic acid) (PMAA) were built on top of the BMP-2. The effect of solution pH during the deposition process was investigated. High levels of BMP-2 released over several months were achieved. Approximately 2 μg/cm² of BMP-2 were initially adsorbed on the anodized titanium and a pH-dependent release behavior was observed, with more stable coatings assembled at pH = 6-7. Three different diffusion regimes could be determined from the release profiles: an initial burst release, a sustained release regime and a depletion regime. Mass adsorption monitoring using quartz crystal microbalance with dissipation monitoring (QCM-D) showed that PLH was adsorbed in greater quantities than PMAA, and that more mass was adsorbed per bilayer as the number of bilayers grew. Moreover, the pH of the water used during the rinsing step significantly impacted the composition of the multilayer. Atomic force microscopy (AFM) and contact angle analysis (CAA) were used to determine the topography and surface energy of the PEMs. No visible change was observed in surface morphology as the assembly pH was varied, whereas the surface energy decreased for samples prepared at more basic pH. These variations indicate that the influence of the initial BMP-2 layer can be felt throughout the PEM and impact its surface structure.

Cheng Kwok Kei = 高分子電解質-膠體複合體系的相互作用和極化率 / 鄭國基. / Thesis submitted in: November 2004. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 68-73). / Text in English; abstracts in English and Chinese. / Cheng Kwok Kei = Gao fen zi dian jie zhi-jiao ti fu he ti xi de xiang hu zuo yong he ji hua lü / Zheng Guoji. / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Polyelectrolyte Colloid Complex --- p.1 / Chapter 1.2 --- Image charges --- p.3 / Chapter 1.3 --- Objective of the thesis --- p.3 / Chapter 2 --- Equations for induced image charges (Review) --- p.5 / Chapter 2.1 --- Introduction --- p.5 / Chapter 2.2 --- Image effect --- p.6 / Chapter 2.2.1 --- The potential --- p.6 / Chapter 2.2.2 --- Surface charge density --- p.8 / Chapter 2.2.3 --- Potential energy --- p.9 / Chapter 3 --- Polarizability of a polyelectrolyte colloid complex --- p.11 / Chapter 3.1 --- Introduction --- p.11 / Chapter 3.2 --- The Simulation Model --- p.12 / Chapter 3.2.1 --- Energy of the Complex --- p.13 / Chapter 3.2.2 --- Dipole of the Complex --- p.15 / Chapter 3.2.3 --- Thermal Energy --- p.18 / Chapter 3.3 --- Calculating Method --- p.18 / Chapter 3.3.1 --- Monte Carlo Simulation --- p.19 / Chapter 3.3.2 --- Partition Function Calculation --- p.20 / Chapter 3.4 --- Polarizability --- p.22 / Chapter 3.4.1 --- Compare polarizability of the complex with a permanent dipole --- p.22 / Chapter 3.4.2 --- Results and Discussion --- p.23 / Chapter 3.5 --- Effect of image charges for the complex --- p.33 / Chapter 3.6 --- Conclusion --- p.37 / Chapter 4 --- Correlation and Interaction of complexes - without induced charges --- p.38 / Chapter 4.1 --- Introduction --- p.38 / Chapter 4.2 --- The Simulation Model --- p.39 / Chapter 4.2.1 --- Energy of the system --- p.40 / Chapter 4.2.2 --- Dipole Moment --- p.42 / Chapter 4.3 --- Results and Discussion --- p.43 / Chapter 4.3.1 --- Polarizability of complex --- p.43 / Chapter 4.3.2 --- Correlations between two complexes --- p.46 / Chapter 4.3.3 --- Potential of mean force --- p.50 / Chapter 4.4 --- Conclusion --- p.52 / Chapter 5 --- Correlation between Two Complexes - with induced charges --- p.53 / Chapter 5.1 --- Introduction --- p.53 / Chapter 5.2 --- Induced Surface Charges --- p.54 / Chapter 5.2.1 --- Surface charges --- p.54 / Chapter 5.2.2 --- Energy of system --- p.55 / Chapter 5.2.3 --- Dipole Moment --- p.57 / Chapter 5.3 --- Results and Discussion --- p.58 / Chapter 5.3.1 --- Polarizability of complexes --- p.59 / Chapter 5.3.2 --- Correlation between two complexes --- p.61 / Chapter 5.3.3 --- Potential of mean force --- p.63 / Chapter 5.4 --- Conclusion --- p.64 / Chapter 6 --- Summary --- p.66 / Bibliography --- p.68 / Chapter A --- Mathematical calculation of the dipole moment of a complex --- p.74 / Chapter A.1 --- Equation of mean squared dipole --- p.74 / Chapter A.2 --- z-component of dipole and squared dipole --- p.76

Graduation date: 1996