This thesis research focused on the synthesis and characterization of disulfonated poly(arylene ether sulfone) hydrophilic-hydrophobic segmented and multiblock copolymers for application as proton exchange membranes (PEMs) in fuel cells or as reverse osmosis (RO) membranes for water desalination. The first objective was to demonstrate that synthesizing blocky copolymers using a one oligomer, two monomer segmented copolymerization afforded copolymers with similar properties to those which used a previous approach of coupling two preformed oligomers. A 4,4′-biphenol based hydrophilic block of disulfonated poly(arylene ether sulfone) oligomer of controlled number average molecular weight (Mn) with phenoxide reactive end groups was first synthesized and isolated. It was then reacted with a calculated amount of hydrophobic monomers, forming that block in-situ. Copolymer and membrane properties, such as intrinsic viscosity, tensile strength, water uptake, and proton conductivity, were consistent with those of multiblock copolymers synthesized via the oligomer-oligomer approach. The segmented polymerization technique was then used to synthesize a variety of other copolymers for PEM applications. The well known bisphenol phenolphthalein was explored as a comonomer for either the hydrophilic and hydrophobic blocks of the copolymer. Membrane properties were explored as a function of block length for both series of copolymers. Both series showed that as block length increases, proton conductivity increases across the entire range of relative humidity (30-100%), as does, water uptake. This was consistent with earlier research which showed that the water self-diffusion coefficient scaled with block length. Copolymers produced with phenolphthalein had higher tensile strength, but lower ultimate elongation than the 4,4′-biphenol based copolymers. Multiblock copolymers were also synthesized and characterized to assess their feasibility as RO membranes. A new series of multiblock copolymers was synthesized by coupling hydrophilic disulfonated poly(arylene ether sulfone) (BisAS100) oligomer with hydrophobic unsulfonated poly(arylene ether sulfone) (BisAS0) oligomer. Both oligomers were derived using 4,´-isopropylidenediphenol (Bis-A) as the bisphenol. Phenoxide-terminated BisAS100 was end-capped with decafluorobiphenyl and reacted at relatively low temperatures (~ 100 oC) with phenoxide-terminated BisAS0. Basic properties were characterized as a function of block length. The initial membrane characterization suggested these copolymers may be suitable candidates for reverse osmosis applications, and water and salt permeability testing should be conducted to determine desalination properties. The latter measurements are being conducted at the University of Texas, Austin and will be reported separately. / Ph. D.

The research herein focuses on the characterization of a PFCB/PVDF-HFP (70:30 wt:wt) blend fuel cell membrane including the constitutive and morphological properties, how these properties predict the stresses incurred under fuel cell operating conditions, and how these properties change over time under fuel cell operating conditions. Characterization was performed to mimic temperature and moisture conditions found in operating fuel cells to understand how these materials will behave in service.  This included thermal and hygral expansion, mass uptake, and the stress relaxation modulus.  These constitutive properties were chosen for characterization such that a model could be created to predict the stresses incurred during fuel cell operation, and examine how these stresses may change under different operating conditions and over time.  Based on the results of this model, lifetime predictions were made resulting in recommendations to further extend the operating time of this membrane beyond the DOE 5000 hr requirement. Stress predictions are useful, however if the material properties are changing over time under the fuel cell operating conditions, they may no longer be valid.  Therefore, PFCB/PVDF-HFP membranes were conditioned for different amounts of time under conditions similar to those commonly found in operating fuel cells.  These conditioned membranes were then characterized and compared with solvent exchanged membranes, the same materials used for previous material characterization.  The properties examined included stress relaxation modulus, bi-axial strength, mass uptake, water diffusion, and proton conductivity.  To further understand any changes noted in these properties after different environmental exposures, morphological analysis was performed.  This included small angle x-ray scattering, infrared spectroscopy, transmission electron microscopy, and differential scanning calorimetry. It was initially found that the proton conductivity decreased severely when the material was immersed at high temperatures over short time periods.  This was consistent with changes noted in other properties, and morphological analysis showed a decrease in the ionic network as well as an increase in the phase separation of the PFCB block copolymer as well as the PVDF-HFP crystallinity.  These large morphological changes could be very detrimental while in service, resulting in early termination of the fuel cell.  However, it was also noted that if these materials are annealed at high temperature (140"C), the negative property changes are abated.  This abatement is again tied to the morphology of the material, as annealing the material at high temperature creates stronger physical crosslinks, and induces a small amount of chemical crosslinking via condensation of the sulfonic acid groups, thus allowing the stress predictions performed earlier to have greater validity.   Therefore, it is important to not only understand the properties of a material during characterization, but also the underlying polymer structure, and how this structure can change over time, as all of these items control the long term material performance while in service. / Ph. D.

The proton exchange membrane (PEM) is a key component in proton exchange membrane fuel cells (PEMFCs). During standard fuel cell operation, the PEM degrades due to cyclic hygrothermal loads, resulting in performance loss or total failure. Improvement of current PEM materials and development of cheaper, more durable materials is essential to the commercialization of PEMFC technology, which may provide an attractive alternative energy source for transportation. This dissertation investigates a new PEM material which is a blend of sulfonated perfluorocyclobutane (PFCB) and polyvinylidene fluoride (PVDF). Hereafter referred to as PFCB/PVDF, this polymer blend was developed by General Motors Company™ as a potential replacement for the current benchmark PEM, the DuPont™ product Nafion®. The PFCB/PVDF blend is less costly to manufacture than standard PEM materials and investigations into its long-term mechanical durability are ongoing. Specifically, this document discusses the experimental and analytical work performed in the material characterization, constitutive expression development, and implementation of that expression into uniaxial and biaxial finite element geometries. Extension of the model to time-varying temperature and moisture conditions is also explored. The uniaxial finite element model uses a non-linear viscoelastic viscoplastic (NLVE-VP) constitutive expression with parameters determined from uniaxial creep and recovery experiments at a single environmental condition. Validation tests show that this model accurately predicts results from uniaxial tension experiments, such as stress relaxation, force ramp, and multistep creep and recovery, to stresses of 8 MPa and strains approaching 15%, which is the maximum hygrothermal strain expected in an operating fuel cell. The biaxial finite element model combines the NLVE-VP constitutive expression with the geometry of a pressure-loaded blister experiment, which better approximates fuel cell membrane constraints. Results from the biaxial model are compared to experimental results. The model accurately predicts strain in the blister test but predicts stresses that differ from those estimated from blister curvature. Additionally, it is found that both the non-linear viscoelastic and viscoplastic parameters are functions of the operating environment. Future experimental work is needed to characterize that dependence before the constitutive model is used to simulate the response of the PFCB/PVDF blend to fuel cell operating conditions. / Ph. D.

Environmental fluctuations in operating fuel cells impose significant biaxial stresses in the constrained proton exchange membranes (PEM). The PEM's ability to withstand cyclic environment-induced stresses plays an important role in membrane integrity and consequently, fuel cell durability. In this thesis, pressure loaded blister tests are used to study the mechanical durability of Gore-Select® series 57 over a range of times, temperatures, and loading histories. Ramped pressure tests are used with a linear viscoelastic analog to Hencky's classical solution for a pressurized circular membrane to estimate biaxial burst strength values. Biaxial strength master curves are constructed using traditional time-temperature superposition principle techniques and the associated temperature shift factors show good agreement when compared with shifts obtained from other modes of testing on the material. Investigating a more rigorous blister stress analysis becomes nontrivial due to the substantial deflections and thinning of the membrane. To further improve the analysis, the digital image correlation (DIC) technique is used to measure full-field displacements under ramped and constant pressure loading. The measured displacements are then used to validate the constitutive model and methods of the finite element analysis (FEA). With confidence in the FEA, stress histories of constant pressure tests are used to develop linear damage accumulation and residual strength based lifetime prediction models. Robust models, validated by successfully predicting fatigue failures, suggest the ability to predict failures under any given stress history whether mechanically or environmentally induced - a critical step in the effort to predict fuel cell failures caused by membrane mechanical failure. / Master of Science

Sulfonated polyaromatic hydrocarbon membranes have emerged as desirable candidates for proton exchange membranes (PEMs) due to their excellent mechanical properties, high thermal and chemical stability, and low cost. Specifically, sulfonated multiblock copolymers are attractive because their phase-separated morphologies aide in facile proton transport. In this work, the functionalization of semicrystalline gels of poly(ether ether ketone) (PEEK) is explored as a novel post-polymerization method to prepared blocky copolymers, and the effect of copolymer architecture on membrane physical properties, structure, and performance is extensively investigated. First, the blocky sulfonation of PEEK was explored to prepare blocky copolymers (SPEEK) with densely sulfonated domains and unfunctionalized, crystallizable domains. Compared to random SPEEK ionomers at similar ion content, blocky SPEEK exhibited enhanced crystallizability, decreased melting point depression, and faster crystallization kinetics. Phase separation between the hydrophilic sulfonated blocks and hydrophobic PEEK blocks, aided by polymer crystallization, resulted in enhanced water uptake, superior proton conductivity, and more closely associated ionic domains than random SPEEK. Furthermore, the random and blocky bromination of PEEK was investigated to prepare PEEK derivatives (BrPEEK) with reactive aryl-bromides. Spectroscopic evidence revealed long domains of unfunctionalized homopolymer for blocky BrPEEK, and this translated to an increased degree of crystallinity, higher melting temperature, and more rapid crystallization kinetics than random BrPEEK at similar degrees of bromination. The subsequent sulfonation of blocky BrPEEK resulted in a hydrophilic-hydrophobic blocky copolymer with clear multi-phase behavior. The phase-separated morphology contributed to decreased water uptake and areal swelling compared to random SPEEK and resulted in considerably higher proton conductivity at much lower hydration levels. Moreover, Ullmann coupling introduced superacidic perfluorosulfonic acid side chains to the BrPEEK backbone, which yielded membranes with less water content and less dimensional swelling than random SPEEK. Superior proton transport than random SPEEK was observed due to the superacid side chain and wider hydrophilic channels within the membranes, resulting in more continuous pathways for proton transport. Overall, this work provided a novel platform for the preparation of functionalized PEEK membranes using a simple post-polymerization functionalization procedure. The established methods produced blocky-type copolymers with properties reminiscent of multiblock copolymers prepared by direct polymerization from monomers/oligomers. / PHD / Block copolymers are an important class of polymers that are composed of two or more blocks of distinct polymeric segments covalently tethered to one another. Dissimilarity in the chemical nature of the blocks leads to self-organization into well-defined structures, and this unique structural order imparts material properties that are different from (and often superior to) the properties of the individual blocks alone. Thus, block copolymers are advantageous for a diverse array of applications including membranes, gas separation, water purification, medical devices, etc. Although considerable synthetic progress has been made towards discovering novel methods to prepare block copolymers, their widespread use is somewhat limited by the complex, energy-intensive procedures necessary to precisely control the block sequencing during polymerization. In this dissertation, a straightforward, inexpensive physical procedure is explored to synthesize blocky copolymers with controlled sequencing from commercially available polymers. This process relies on performing reactions in the gel state, whereby segments of the polymer chain are effectively shielded from the functionalizing chemistry. In particular, the gel state sulfonation and bromination of poly(ether ether ketone), a high performance polymer, is investigated to develop novel, blocky materials for membrane applications. This work not only expands the methodology towards the synthesis of block copolymers, but alaso provides critical insight into the effect of copolymer architecture on membrane physical properties, structure, and performance. Furthermore, this work provides an economically feasible method to prepare blocky copolymers from commercially derived materials, thereby providing a means to progress the widespread use of block copolymers in industry.

The purpose of this work was to investigate the effects of structure, humidity and aging on the mechanical behavior of Nafion® and Dais® ionomers. It was determined that the majority of the properties of these membranes were controlled by the formation and growth of the ionic clusters that were the direct result of the ionic nature of these materials. In the process of this study, the properties of Nafion® and sulfonated Dais® polymers were investigated by dynamic mechanical analysis and thermal gravimetric analysis and their water uptake and sorption and desorption isotherms were measured. A mastercurve and a shift factor plot were constructed for 60% sulfonated Dais® membrane. It was determined that an increase in the degree of sulfonation raised the glass transition temperature of these materials by facilitating the formation of the ionic clusters which acted as physical crosslinks, thereby reducing the mobility of polymeric chains. Water was found to effectively plasticize the membranes, especially in the case of Dais® materials, by reducing the storage modulus and decreasing the structural integrity of the ionomers. The effect of pre-treatment of Nafion® was investigated and the glass transition temperature was found to increase as a function of the severity of the treatment procedure. The maximum water uptakes were determined for virgin and aged Nafion® and Dais® membranes and their vapor phase water sorption diffusion coefficients were calculated. The sorption process was found to follow pseudo-Fickian behavior, while the movement of water out of the membranes during the desorption process was determined to be controlled by mechanisms other than diffusion. Lastly, the effect of exposure of Nafion® and 30% sulfonated Dais® membranes to the saturated environment at elevated temperatures was investigated and found to result in the increase in the glass transition temperature of the materials. Results of the exposure effects on the diffusion properties of Nafion® and Dais® were inconclusive. Preliminary findings attributed the changes in the properties of the materials to the counteractive actions of physical aging and the growth of the ionic clusters. / Master of Science

Proton exchange membrane fuels cells (PEMFCs) are one of the primary alternatives to internal combustion engines. The key component is the proton exchange membrane, or PEM, which should meet a number of requirements, including good proton conductivity under partially humidified conditions. A number of alternative PEMs have been synthesized by copolymerizing various aromatic comonomers, but the smaller ion channels prohibit rapid proton transport under partially hydrated conditions. One solution has been to synthesize multiblock copolymers from hydrophilic and hydrophobic oligomers to ensure sufficient ion channel size. Four multiblock systems were synthesized from hydrophobic and hydrophilic oligomers and were characterized in this thesis. The first multiblock system incorporated a partially fluorinated monomer into the hydrophobic block, to improve phase separation and performance under partially humidified conditions. The second study was focused on phase separation and structure-property relationships as a function of casting conditions of a biphenol-based multiblock series. The third study featured a novel hydroquinone-based hydrophilic oligomer in the multiblock copolymer, which showed the promise of a higher ionic density, degree of phase separation and proton conductivity values. The fourth study in this thesis entailed the comparison of a block copolymer produced with two distinct synthetic routes: the multiblock synthesis from separate oligomers as previously published in the literature, and a segmented route seeking to achieve comparable structure-property relationships with the same monomers, but using a simpler synthetic route. The two block copolymer series were found to be comparable in their structure-property relationships. / Master of Science

Thesis (M. Tech. - (Engineering: Electrical, Department: Electronic Engineering, Faculty of Engineering and Technology))--Vaal University of Technology. / Industrial countries, such as South Africa, rely heavily on energy sources to function profitably in today’s economy. Based on the 2008 fossil fuel CO2 emissions South Africa was rated the 13th largest emitting country and also the largest emitting country on the continent of Africa, and is still increasing. It was found that fuel cells can be used to generate electricity and that hydrogen is a promising fuel source. A fuel cell is an energy generation device that uses pure hydrogen (99.999%) and oxygen as a fuel to produce electric power. A regenerative fuel cell is a fuel cell that runs in reverse mode, which consumes electricity and water to produce hydrogen. This research was aimed at designing and constructing an optimised control system to control the hydrogen pressure in a proton exchange membrane regenerative fuel cell. The hydrogen generated by the fuel cell must be stored in order to be used at a later stage to produce electricity. A control system has been designed and constructed to optimise the hydrogen pressure control in a regenerative proton exchange membrane fuel cell. An experiment that was done to optimise the hydrogen system included the effects that the cathode chamber pressure has on the production of hydrogen and the most effective method of supplying hydrogen to a storage tank. The experiment also included the effects of a hydrogen buffer tank on the output hydrogen pressure and if the system can accommodate different output pressures. It was found that the cathode chamber pressure doesn’t need to be controlled because it has no effect on the rate of hydrogen produced. The results also showed that the flow of hydrogen need not to be controlled to be stored in a hydrogen storage tank, the best method is to let the produced hydrogen flow freely into the tank. The hydrogen produced was also confirmed to be 99.999% pure. The system was also tested at different output pressures; the control system successfully regulated these different output pressures.

Indiana University-Purdue University Indianapolis (IUPUI) / The innovation and investigation of catalysts in proton exchange membrane fuel cells are included in this thesis. In the first part of this work, stability of the catalyst support of PEMFC catalyst is investigated. Nanoscale platinum particles were loaded on two different kinds of carbon supports, nano graphene sheets and functionalized carbon black/graphene hybrid were developed by the liquid phase reaction. The crystal structure of two kinds of catalysts was characterized by X-ray diffractometer (XRD). The morphology and particle size were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). Pt loading was measured by thermal gravimetric analysis (TGA). The Brunauer, Emmett and Teller (BET) method was applied to test the surface area of the catalysts. The electrochemical surface area (ECSA) and mass activity during oxygen reduction reaction (ORR) process for two kinds of catalyst were tested by cyclic voltammetry method under different conditions. The stability of the catalysts were tested by accelerated durability test (ADT). The results show that although the mass activity of Pt/graphene is much lower, the stability of it is much better than that of the commercial catalyst. After adding functionalized carbon black (FCB) as spacer, the stability of the catalyst is preserved and at the meantime, the mass activity becomes higher than 20% Pt/XC72 catalyst. The lower mass activity of both catalysts are due to the limitation of the electrolyte diffusion into the carbon support because of the aggregation nature of graphene nano-sheets. After introducing functional carbon black as spacer, the mass activity and ECSA increased dramatically which proved that FCB can be applied to prevent the restacking of graphene and hence solved the diffusion problem. In the meantime, the durability was still keeping the same as Pt/graphene catalyst. In the second part of the work, the restacking problem was solved by introducing FCB as spacers between functionalized graphene nanosheets. The same measurement was applied to test the electrochemical performance of Pt/FCB/FG catalyst. The new catalyst showed a higher mass activity compared to Pt/graphene catalyst which meant the restacking problem was partially solved. The durability of the Pt/FCB/FG catalyst was still excellent.

Solar Energy and Hydrogen (energy carrier) are possible replacement options for fossil fuel and its associated problems of availability and high prices which are devastating small, developing, oil-importing economies. But a major drawback to the full implementation of solar energy, in particular photovoltaic (PV), is the lowering of conversion efficiency of PV cells due to elevated cell temperatures while in operation. Also, hydrogen as an energy carrier must be produced in gaseous or liquid form before it can be used as fuel; but its‟ present major conversion process produces an abundance of carbon dioxide which is harming the environment through global warming. In search of resolutions to these issues, this research investigated the application of Thermal Management to Photovoltaic (PV) modules in an attempt to reverse the effects of elevated cell temperature. The investigation also examined the effects of coupling the thermally managed PV modules to a proton exchange membrane (PEM) Hydrogen Generator for the production of hydrogen gas in an environmentally friendly and renewable way. The research took place in Kingston, Jamaica. The thermal management involved the application of two cooling systems which are Gravity-Fed Cooling (GFC) and Solar-Powered Adsorption Cooling (SPAC) systems. In both systems Mathematical Models were developed as predictive tools for critical aspects of the systems. The models were validated by the results of experiments. The results of the investigation showed that both cooling systems stopped the cells temperatures from rising, reversed the negative effects on conversion efficiency, and increased the power output of the module by as much as 39%. The results also showed that the thermally managed PV module when coupled to the hydrogen generator impacted positively with an appreciably increase of up to 32% in hydrogen gas production. The results of this work can be applied to the equatorial belt but also to other regions with suitable solar irradiation. The research has contributed to the wider community by the development of practical, environmentally friendly, cost effective Thermal Management Systems that guarantee improvement in photovoltaic power output, by introducing a novel way to use renewable energy that has potential to be used by individual household and/or as cottage industry, and by the development of Mathematical Tools to aid in photovoltaic power systems designs.