Browsing by Author "Moore, Robert Bowen III"
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- Effects of Thermal Treatments on Perfluorosulfonate Ionomer MembranesYan, Bing (Virginia Tech, 2010-07-27)Perfluorosulfonate ionomer (PFSI) membranes were annealed at elevated temperature for various periods of time in order to investigate the morphological effects of thermal treatments. For Nafion® 117, the DSC thermograms of Na+-, Cs+- and tetramethylammonium(TMA+)-form membranes show an endothermic peak develops upon annealing at 200ºC, indicating the development of crystallinity in the membrane. For these three samples annealed under same conditions, the heat of fusion (ΠH) values of the endothermic event increases with increasing counterion size. Larger tetraalkylammonium ions, tetraethylammonium(TEA+) and tetrapropylammonium(TPA+), result in no significant peak upon annealing at 200ºC. DSC thermograms of annealed Na+-form 3M Ionomer show no peak upon annealing and DSC thermograms of annealed TMA+-form 3M Ionomer show a very small peak that develops with annealing time at high equivalent weights. Annealed TMA+-form Dow Ionomer, which has a side chain shorter than both Nafion® and 3M Ionomer and a smaller mole% of side chains at the same equivalent weight, shows a relatively high ΠH value, which might also be related to its blocky nature. These results show that the isothermal crystallization kinetics of PFSI is affected by the counterion attached to the sulfonate group, the length of side chain, the mole% of side chains and the nature of the membrane. Water uptake analysis has been performed on annealed membranes, and the result shows that water uptake decreases with increasing degree of crystallinity.
- Investigation of Phase Morphology and Blend Stability in Ionomeric Perfluorocyclobutane (PFCB)/Poly(vinylidene difluoride) (PVDF) Copolymer Blend MembranesOsborn, Angela Michelle (Virginia Tech, 2010-11-04)This research is focused on the investigation of phase morphology and blend stability within ionomeric perfluorocyclobutane (PFCB)/poly(vinylidene difluoride) (PVDF) copolymer blend membranes. The morphologies of these unique materials, designed as proton exchange membranes (PEMs) for proton exchange membrane fuel cells (PEMFCs), have been examined not only in the as-cast/as-received state, but also as a function of exposure to various ex-situ aging environments. The morphological investigations used to probe the response of these ionomer blends have been designed to mimic the environment within a PEMFC and will therefore enhance our understanding of the implications of morphological changes which may occur during fuel cell operation. Thermal annealing of the membranes has been conducted to determine the materials' morphological response to various temperatures in the absence of hydration. The results of these thermal annealing studies have facilitated the isolation of morphological contributions stemming from thermal exposure. Immersion of the blend membranes in liquid water has allowed for singular identification of the role of hydration in the blend membranes' morphological rearrangement and phase stability. However, as the typical fuel cell environment to which these membranes will be exposed is complicated by the presence of both temperature and humidity, our ex-situ investigations have also included the exposure of PFCB/PVDF copolymer blend membranes to simultaneous thermal annealing and hydration conditions – a treatment we refer to as "hygrothermal aging." This unique procedure serves as a simplified method whereby the complex fuel cell environment may be simulated, and the resultant morphological response researched. While the work presented herein has enhanced our understanding of the blend stability of the specific membranes investigated, we have also advanced the fundamental knowledge of the role of morphology with respect to the fuel cell performance of blend materials and the corresponding implications of morphological rearrangements. Such an understanding is essential in the development of morphology-property relationships and eventual optimization of membrane materials designed for use in fuel cells.
- Mechanics and Fracture Behavior of Thermomechanical Bonds in Nonwoven FabricRittenhouse, Joseph Anderson (Virginia Tech, 2016-09-22)The market for nonwoven fabrics has experienced extreme growth in recent years and is expected to double in size from 2010 to 2020. This remarkable growth can be attributed to its numerous applications, ease of manufacturing, and customizable properties such as fabric stiffness, extensibility, and composition. The lifetime of the fabric is extremely important to producers and depends strongly on its micro-mechanical properties. Previously published studies have investigated the bulk fabric properties and the constituent fiber properties. However, nothing has been done to determine the properties of individual thermo-mechanical bonds that connect the constituent fibers of the fabric together. These bonds provide the mechanical integrity of the nonwoven fabrics. This study is the first to examine individual bonds by measuring their mechanical properties via uniaxial tensile tests and by computing the basis weight and orientation of the fibers surrounding the bonds. The results demonstrate that there is a high correlation between the fiber structure around the bond and the bond mechanical properties. The amount and directions of fibers affect how the load is transmitted through the bond and distributed across the fabric. Namely, if there are a few fibers surrounding the bond, or the primary fiber direction is different from the loading direction, then the force sustained by the bond is significantly lower and the bond does not deform. Conversely, if there are many fibers in the loading direction then the bond can sustain a significantly large force and undergoes deformation. The fiber and bond deformation are also observed through microscopic images captured during the uniaxial tensile tests. Ultimately, this research details the results for an effective method to test and analyze the mechanical integrity of thermo-mechanically bond and the lifetime of the nonwoven fabrics.
- A Morphological Study of PFCB-Ionomer/ PVdF Copolymer Blend Membranes For Fuel Cell ApplicationMay, Nathanael Henderson (Virginia Tech, 2011-08-11)A new material for use as a proton exchange membrane in fuel cells has been developed: a blend of a perfluorocyclobutane-based block ionomer (S-PFCB) and Poly (vinylidene-co-hexafluoropropylene) (Kynar Flex, KF). This thesis details the work done thus far to characterize the morphology of this material, using small angle x-ray scattering, differential scanning calorimetry, atomic force micrscopy, and some other techniques to a lesser extent. Small angle x-ray scattering (SAXS) of pure S-PFCB showed a strong block copolymer- associated phase separation, on the order of 25 nm. Differential scanning Calorimetry (DSC) confirmed this finding. SAXS also revealed the presence of a peak representing individual ionic aggregates on the order of 3 nm. Finally, it was shown with DSC that no crystallinity develops in the S-PFCB block copolymer, while one of the blocks, known as 6F, crystallizes extensively. SAXS of incremental blend compositions of KF and S-PFCB revealed a steady increase in size of the block copolymer phase separation peak in SAXS, demonstrative of the miscibility of KF and the non-sulfonated 6F block of S-PFCB. Furthermore, this incremental study determined the scattering vector range relevant for comparing amounts of KF crystallinity. DSC of incremental blend compositions revealed two phases of KF crystallinity develops upon cooling a membrane, independent of cooling rate. Atomic force microscopy (AFM), small angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) corroborate to suggest a nonuniform morphology through the thickness of solution cast membranes. Also, the effect of different casting temperatures and after-casting anneals on morphology was assessed. Future work on this project involves morphological studies at various relative humidities and temperatures, as well as following up on discoveries already made. Finally, transmission electron micrscopy (TEM) should be performed to provide a visual analog, which will greatly help in developing an accurate morphological model.
- Photo-Curing Behavior and Thermal Properties of Silicone Semi Interpenetrating Polymer Network (Semi-IPN) OrganogelsKaymakci, Orkun (Virginia Tech, 2013-01-04)Silicone hydrogels are receiving considerable interest due to their important biomedical application areas such as contact lenses and wound dressings. The applications of such materials are usually in the hydrated state, as hydrogels. However, manufacturing and molding processes are mostly carried out in the organically solvated state, as organogels. This thesis investigates the effects of some of the manufacturing parameters such as curing time and thermal processing on thermal, mechanical, viscoelastic and adhesive/cohesive fracture properties of silicone semi-interpenetrating polymer network organogels. Curing time may affect the extent of reaction and the crosslink density of a gel network. In order to investigate the effect of this parameter, materials were photo-cured for different times within the range of 150s to 1800s. Gel content, uniaxial tensile, dynamic mechanical, adhesive fracture and cohesive fracture properties were obtained as a function of photo-curing time and results were correlated with each other in order to have a better understanding of the effects on the material properties. Additionally, thermal properties of the gels were studied in detail. Crystallization and melting behavior of one of the solvents in the organogel were investigated by differential scanning calorimetry and thermal optical microscopy. Correlation between the thermal properties of the solvent and the gel network structure was shown. Dynamic mechanical analysis experiments were performed to investigate the effect of solvent crystallization on the mechanical properties. Finally, the effect of thermal processing parameters such as the heating rate and the minimum cooling temperatures on the crystallization and the thermo-mechanical properties were studied.
- Poly(glycoamidoamine)s: Understanding their Structure and Structure-Bioactivity RelationshipsTaori, Vijay P. (Virginia Tech, 2010-07-07)In order to achieve efficient therapeutic effect, it is important to understand the structure of biomaterials that are used in the therapeutic delivery system. This dissertation is dedicated towards understanding the hydrolysis pattern of plasmid DNA (pDNA) delivery vehicles comprised of poly(glycoamidoamine)s (PGAAs) under physiological conditions and effects of subtle changes in the chemical structure of the PGAAs on its biological performance. The unusual hydrolysis of the tartarate and galactarate based PGAAs was investigated by studying the hydrolysis of small model molecules which mimic the repeat unit of the respective polymers. In the case of galactarate and tartarate based molecules with terminal amines showed faster hydrolysis of the amide bonds. In addition for the tartarate based compounds, it was also found that it is necessary to have terminal amine functionality for the intramolecular hydrolysis to occur. The model compounds consists of two amide bonds and were designed symmetric, however amide bond on only one side of the tartarate moiety show underwent hydrolysis. Further studies show that one side of the amine assists the hydrolysis of the amide bond on the other side of the tartarate moiety. The degradation of poly(L-tartaramidopentaethylenetetramine) (T4) was also used to study the sustained release of pDNA from the layer-by-layer constructs of T4/pDNA. The thickness of the constructs was characterized by ellipsometry while the UV-visible spectroscopy was used to characterize the loading capacity of the constructs for pDNA. The indirect sustained release of pDNA under the physiological conditions with respect to time was characterized by the cellular uptake studies in HeLa cells. The increase in the uptake of the Cy5 labeled pDNA was seen at extended period of eleven days. The integrity of the sustained released pDNA for the transgene expression was characterized with an assay to see the expression of the green fluorescent protein (GFP) from the T4/GFP-pDNA layer-by-layer constructs. PGAAs show a very efficient delivery of the pDNA in a non-toxic manner. The chemical structure of the polymer can dictate the binding with pDNA and also the release of the pDNA form the polymer-pDNA complexes. In order to better understand the fundamentals of the nucleic acid delivery and to better design the nucleic acid delivery vehicles, subtle changes in the chemical structure of the PGAAs were designed and studied for the biological activity. The effect of charge type was investigated by designing and synthesizing guanidine based polymer series analogues to galactarate and tartarate based PGAAs (G1 and T1) which incorporate secondary amines as the charge type on the polymer backbone. The guanidine based polymer series, poly(glycoamidoguanidine)s (PGAGs), show very non toxic behavior in HeLa cells at all the different polymer to pDNA ratio (N/P ratio) studied. Interestingly PGAGs are the only non-toxic guanidine containing polymers which are reported in the literature to the date. The cellular uptake of pDNA assisted from the PGAGs is a little higher than PGAAs compared although both the series of polymers show similar transgene expression. The transgene expression in case of PGAGs also imply the release of the polymer-pDNA complexes from the endosome. In another study of structure-bioactivity relationship based on the degree of polymerization (DP) of poly(galactaramidopentaethylenetetramine) (G4), it was found that the increase in the DP of G4 increases the toxicity of the polymers in the HeLa cells.
- Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular PolymersCheng, Shijing (Virginia Tech, 2011-08-26)Non-covalent interactions including nucleobase hydrogen bonding and phosphonium/ammonium ionic aggregation were studied in block and random polymers synthesized using controlled radical polymerization techniques such as nitroxide mediated polymerization (NMP) and reversible addition-fragmentation chain transfer polymerization (RAFT). Non-covalent interactions were expected to increase the effective molecular weight of the polymeric precursors through intermolecular associations and to induce microphase separation. The influence of non-covalent association on the structure/property relationships of these materials were studied in terms of physical properties (tensile, DMA, rheology) as well as morphological studies (AFM, SAXS). Ionic interactions, which possess stronger interaction energies than hydrogen bonds (~150 kJ/mol) were studied in the context of phosphonium-containing acrylate triblock (ABA) copolymers and random copolymers. Phosphonium-containing ionic liquid monomers with different alkyl substituent lengths and counterions enabled an investigation of the effects of ionic aggregation of phosphonium cations on the polymer physical properties. The polymerization of styrenic phosphonium-containing ionic liquid monomers using a difunctional alkoxyamine initiator, DEPN2, afforded an ABA triblock copolymer with an n-butyl acrylate soft center block and symmetric phosphonium-containing external reinforcing blocks. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) of triblock copolymers revealed pronounced microphase separation at the nanoscale. Phosphonium aggregation governed block copolymer flow activation energies. In random copolymers, the phosphonium cations only weakly aggregated, which strongly depended on the length of alkyl substituents and the type of counterions. Acrylate random copolymers consisting of quaternary ammonium functionalities were synthesized using reversible addition-fragmentation chain transfer polymerization (RAFT). The obtained copolymers possessed controlled compositions and narrow molecular weight distributions with molecular weights ranging from Mn =50,000 to 170,000 g/mol. DMA evidenced the weak aggregation of ammonium cations in the solid state. Additionally, this ionomer was salt-responsive in NaCl aqueous solutions. Hydrogen bonding, a dynamic interaction with intermediate enthalpies (10-40 kJ/mol) was introduced through complementary heterocyclic DNA nucleobases such as adenine, thymine and uracil. Our investigations in this field have focused on the use of DNA nucleobase pair interactions to control polymer self-assembly and rheological behavior. Novel acrylic adenine- and thymine-containing monomers were synthesized from aza-Michael addition reaction. The long alkyl spacers between nucleobase and polymer backbone afforded structural flexibility in self-assembly process. Adenine-containing polyacrylates exhibited unique morphologies due to adenine-adenine π-π interactions. The complementary hydrogen bonding of adenine and thymine resulted in disruption of adenine-adenine π-π interactions, leading to lower plateau modulus and lower softening temperatures. Moreover, hydrogen bonding interactions enabled the compatibilization of complementary hydrogen bonding guest molecules such as uracil phosphonium chloride.
- Synthesis and Properties of Ion-Containing Block and Segmented Copolymers and Their CompositesGao, Renlong (Virginia Tech, 2012-03-16)Ion-containing segmented polyurethanes exhibit unique morphology and physical properties due to synergistic interactions of electrostatic, hydrogen bonding, and hydrophobic interactions. A fundamental investigation on a series of well-defined ion-containing polyurethanes elucidated the influence of charge placement, charge density, and soft segment structure on physical properties, hydrogen bonding, and morphologies. An unprecedented comparison of poly(ethylene oxide)(PEO)-based sulfonated polyurethanes containing sulfonate anions either in the soft segments or hard segments revealed that sulfonate charge placement dramatically influenced microphase separation and physical properties of segmented polyurethanes, due to altered hydrogen bonding and thermodynamic immiscibility between soft and hard segments. Moreover, studies on sulfonated polyurethanes with identical sulfonated hard segments but different soft segment structures indicated that soft segment structure tailored sulfonated polyurethanes for a wide range of mechanical properties. Sulfonated polyurethanes incorporated with ammonium-functionalized multi-walled carbon nanotubes (MWCNTs) generated novel polyurethane nanocomposites with significantly enhanced mechanical performance. Modification of MWCNTs followed a dendritic strategy, which doubled the functionality by incorporating two ammonium cations per acid site. Complementary characterization demonstrated successful covalent functionalization and formation of surface-bound ammonium salts. Upon comparison with pristine MWCNTs, ammonium-functionalized MWCNTs exhibited significantly enhanced dispersibility in both DMF and sulfonated polyurethane matrices due to good solvation of ammonium cations and intermolecular ionic interactions between anionic polyurethanes and cationic MWCNTs. Segmented polyurethanes containing sulfonated PEO-based soft segments and nonionic hard segments were incorporated with various contents of room temperature ionic liquid, 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES), to investigate the influence of ionic liquid on physical properties, morphologies, and ionic conductivity. Results indicated that EMIm ES preferentially located in the sulfonated PEO soft phase, leading to significantly enhanced ionic conductivity and well-maintained mechanical properties. These properties are highly desirable for electromechanical transducer applications. Electromechanical actuators fabricated with sulfonated polyurethane/IL composite membranes exhibited effective response under a low applied voltage (4 V). However, in the case of an imidazolium-containing segmented polyurethane with imidazolium ionic hard segments and hydrophobic poly(tetramethylene oxide) (PTMO) soft segments, EMIm ES selectively located into the imidazolium ionic hard domains, as evidenced with a constant PTMO soft segment glass transition temperature (Tg) and systematically reduced imidazolium hard segment Tg. Dielectric relaxation spectroscopy demonstrated that ionic conductivity of imidazolium-containing segmented polyurethanes increased by five orders of magnitude upon incorporation of 30 wt% EMIm ES. Imidazolium-containing sulfonated pentablock copolymers were also investigated to elucidate the influence of imidazolium counter cation structures on solution rheology, morphology, and thermal and mechanical properties. Combination of living anionic polymerization and post functionalization strategies provided well-defined sulfonated pentablock copolymers containing structured imidazolium cations in sulfonated polystyrene middle block. Varying alkyl substitute length on imidazolium cations tailored physical properties and morphologies of sulfonated pentablock copolymers. Results indicated that long alkyl substitutes (octyl and dodecyl) on imidazolium cations significantly influenced solution rheological behavior, morphology, and water uptake properties of sulfonated pentablock copolymers due to the altered characteristic of imidazolium cations. Imidazolium-containing sulfonated pentablock copolymers exhibited systematically tailored mechanical properties due to the plasticizing effect of alkyl substitutes. In addition, incorporation of ionic liquids into sulfonated pentablock copolymers further tailored their mechanical properties and ionic conductivity, which made these materials suitable for electromechanical transducer applications. All sulfonated pentablock copolymers were successfully fabricated into actuator devices, which exhibited effective actuation under a low applied voltage (4 V).
- Thermal and Morphological Study of Segmented Multiblock Copolyesters Containing 2,2,4,4-Tetramethyl-1,3-cyclobutanediolDixit, Ninad (Virginia Tech, 2012-04-16)Thermal and morphological studies of the segmented multiblock copolyesters containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol and dimethyl-1,4-cyclohexane dicarboxylate were carried out using differential scanning calorimetry, small angle X-ray scattering, wide angle X-ray diffraction and dynamic mechanical analysis. Molecular origins of the thermal transitions appearing in copolyesters were assigned by the copolyester analysis at different temperatures. The hard segments in copolyesters underwent short-range and long-range ordering (crystallization) during cooling or annealing above glass transition temperature, as concluded from thermal and wide angle X-ray diffraction analysis. Annealing process affected the ordering in hard segments and annealing temperatures of 160 °C and above led to increased microphase mixing. The small angle X-ray scattering studies confirmed the microphase separated morphology of copolyesters and supported the argument of increased microphase mixing in copolyesters annealed at higher temperatures. The amount of sulfonate containing co-monomer and its presence in either hard or soft microphase affected the morphology of the copolyesters. Introduction of the sulfonate groups led to increased microphase mixing in copolyesters as well as destruction of long-range order in the hard segments.