Browsing by Author "Marand, Eva"

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    Adsorption of water and carbon monoxide on Cu₂O(111) single crystal surfaces
    Christiaen, Anne-Claire (Virginia Tech, 1994-08-04)
    Water and CO adsorptions were studied over the stoichiometric and the oxygen-deficient Cu₂O(111) surfaces, using thermal desorption spectroscopy (TDS), ultraviolet photoelectron spectroscopy (UPS), and X-ray photoelectron spectroscopy (XPS). Water is the only desorbing species detected in TDS and the extent of dissociation is unaffected by the surface condition: ≃ 0.25 monolayers of water dissociate on Cu₂O(111) regardless of surface condition. The local defect environment around oxygen vacancies does not play a significant role in the activity of the Cu₂O(111) surface for the dissociation of water. CO is found to bind molecularly to the surface through the carbon atom and with a heat of adsorption of 22 kcal/mol, higher value than that of CO on Cu₂O(100) (16.7 kcal/mol). This suggests that the local geometry of adsorption sites may play an important role in the way CO binds to Cu₂O surfaces. Electronic changes upon CO adsorption and the higher heat of adsorption indicate an increased σ-donor character for CO, with some π-backbonding interactions. The local defect environment around oxygen vacancies does not appear to affect CO adsorption on Cu₂O(111) surfaces.
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    Catalytic Transformation of Greenhouse Gases in a Membrane Reactor
    Prabhu, Anil K. (Virginia Tech, 2003-03-13)
    Supported Ni and Rh catalysts were developed for the reforming of two greenhouse gases, methane and carbon dioxide to syngas (a mixture of hydrogen and carbon monoxide). This is an endothermic, equilibrium limited reaction. To overcome the thermodynamic limitations, a commercially available porous membrane (Vycor glass) was used in a combined reactor-separator configuration. This was to selectively remove one or more of the products from the reaction chamber, and consequently shift the equilibrium to the right. However, the separation mechanism in this membrane involved Knudsen diffusion, which provided only partial separations. Consequently, there was some transport of reactants across the membrane and this led to only marginal improvements in performance. To overcome this limitation, a new membrane was developed by modifying the Vycor substrate by the chemical vapor deposition of a silica precursor. This new membrane, termed Nanosil, provided high selectivity to hydrogen at permeabilities comparable to the support material. Application of this membrane in the combined reactor-separator unit provided higher conversions than that obtained using the Vycor membrane.
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    Characterization of Structure-Property Relationships of Poly(urethane-urea)s for Fiber Applications
    O'Sickey, Matthew J. (Virginia Tech, 2002-01-18)
    Poly(urethane)s and poly(urethane-urea)s (PUU) are nearly ubiquitous, having been in existence since before the Second World War. Spandex, a poly(urethane-urea) elastomeric fiber, is found in nearly all articles of apparel as well as in an increasing array of other consumer items. The technology and chemistry of spandex is largely unchanged since its inception in the late 1950s, with the majority of spandex employing poly(tetramethylene ether glycol) as soft segments. Recent developments in catalyst technology have resulted in the production of ultra-low monol content poly(propylene glycol) (PPG), which is nearly difunctional (f=1.95+). This enhancement in difunctionality has potentially enabled the use of PPG as a spandex soft segment with potential spandex processing, performance, and economic benefits. PPG-based spandex elastomers were evaluated in both film and fiber form for the purpose of investigating morphological, orientational, mechanical, and thermal properties with the goal of understanding relationships between chemistry, morphology and properties. Key variables of interest were soft segment molecular weight (MW), molecular weight distribution (MWD), and composition, and hard segment content and composition. Of those, the influence of the molecular weight distribution of the polyol used for soft segments was of foremost interest and had previously been largely neglected during the course of poly(urethane) and poly(urethane-urea) research. It was found that over the range of PUU compositions suitable for production of spandex, that hard segment content and composition had little effect upon the morphology and thermal and mechanical properties. Appreciable trends as functions of soft segment molecular weight were observed. The soft segment MWD was adjusted through the addition of a low molecular weight homolog of PPG, tri(propylene glycol) (TPG), decreasing the number average soft segment MW. The results of these experiments were contrary to those for variation of soft segment molecular weight. It was determined that the low MW portion of the polyol MWD contributes to the building of hard segments in addition to or in lieu of soft segments. Incorporation of TPG in the PUUs resulted in larger, presumably less cohesive, hard domains and increased hard segment content. The TPG containing materials had enhanced tensile properties, less permanent set, and less residual orientation after deformation. These materials proved quite comparable to those using PTMEG soft segments. Comparison of film and fiber PUUs revealed only minor differences, implying that the trends and conclusions drawn from the study of films with spandex-like compositions would also hold for fibers. The key difference between films and fibers is that fibers maintain some residual ordering and orientation due to drawing of the fibers during processing. Of the processing variables investigated, none impacted the morphology as determined from small angle x-ray scattering. It was concluded, that of the various compositional variables germane to spandex, the polyol MW and MWD played key roles in development of morphology, and hence properties. The role of polyol MWD had been woefully neglected during the development of spandex previously, and was observed to be a critical variable.
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    The Design of Three-Dimensional Multicellular Liver Models Using Detachable, Nanoscale Polyelectrolyte Multilayers
    Larkin, Adam Lyston (Virginia Tech, 2012-08-29)
    We report the design and assembly of three-dimensional (3D) multi-cellular liver models comprised of primary rat hepatocytes, liver sinusoidal endothelial cells (LSECs), and Kupffer cells (KCs). LSECs and KCs in the liver model were separated from hepatocytes by a nanoscale, detachable, optically transparent chitosan and hyaluronic acid (HA) polyelectrolyte multilayer (PEM) film. The properties of the PEM were tuned to mimic the Space of Disse found in liver. The thickness of the detachable PEM was 650 to 1000 nm under hydrated conditions. The Young's modulus of the PEM was approximately 42 kPa, well within the range of modulus values reported for bulk liver. The 3D liver models comprised of all three cell types and a detachable PEM exhibited stable urea production and increased albumin secretion over a 12 day culture period. Additionally, the 3D liver model maintained the phenotype of both LSECs and KCs over the 12 day culture period, verified by CD32b and CD163 staining, respectively. Additionally, CYP1A1 enzyme activity increased significantly in the 3D liver models. The number of hepatocytes in the 3D liver model increased by approximately 60% on day 16 of culture compared to day 4 indicating. Furthermore, only the 3D hepatic model maintained cellular compositions virtually identical to those found in vivo. DNA microarray measurements were conducted on the hepatocyte fractions of the 3D liver mimic to obtain insights into hepatic processes. Gene sets up-regulated in the 3D liver model were related to proliferation, migration, and deposition of extracellular matrix, all functions observed in regenerating hepatocytes. Taken together, these results suggest that inter-cellular signaling between the different cell types in the 3D liver model led to increased hepatic functions. To the best of our knowledge, this is the first study where three of the major hepatic cell types have been incorporated into a model that closely mimics the structure of the sinusoid. These studies demonstrate that the multi-cellular liver models are physiologically relevant. Such models are very promising to conduct detailed investigations into hepatic inter-cellular signaling.
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    Developing Reference Materials for VOC, Formaldehyde and SVOC Emissions Testing
    Liu, Zhe (Virginia Tech, 2012-04-24)
    Volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) constitute important classes of indoor contaminants. Emissions of VOCs and SVOCs from myriad building materials and consumer products cause high indoor concentrations with health risks that may be orders-of-magnitude greater than outdoors. The need to control VOC and SVOC emissions from interior materials and thereby reduce indoor concentrations is made more urgent by the prevailing drive for air-tight, energy efficient buildings. To develop low-emission products, emission rates are usually measured in emission chambers. However, there are three significant problems associated with chamber tests: (1) VOC emissions testing procedures of individual laboratories are frequently subject to error and uncertainty; (2) SVOC emissions testing in chambers is extremely difficult and time-consuming, and also subject to error and uncertainty; and (3) chamber tests provide little insight into the mechanisms controlling emissions. This research aimed to solve these problems by developing reference materials for VOC and SVOC emissions testing. Formaldehyde was studied separately from other VOCs because of its unusual properties. Emission mechanisms, and the related modeling approaches for predicting emissions, were investigated by reviewing the literature and performing chamber studies. Based on the internally controlled VOC and formaldehyde emission mechanisms, diffusion-controlled reference materials, which mimic real sources, were created for VOCs and formaldehyde. Approaches for developing externally controlled reference materials for SVOC emissions testing were also explored. Appropriate mechanistic models can predict the true emission rates of the reference materials and therefore provide reference values to validate emissions testing results and certify procedures of individual laboratories. The potential of a solid phase microextraction (SPME) method was also evaluated and found to be a promising technique that can be used in chamber tests to simplify and improve sampling and analytical procedures. This research elucidates the mass-transfer mechanisms of VOC and SVOC emissions and provides practical approaches for developing reference materials for emissions testing. The fundamental understanding and methodological advances will enhance indoor air quality science, improve the emissions testing industry, and provide a sound basis on which to develop standards and regulations.
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    Dimensional Stability and Properties of Thermoplastics Reinforced with Particulate and Fiber Fillers
    DePolo, Wade Scott (Virginia Tech, 2005-09-12)
    This work has been concerned with the dimensional stability and the structure-property relationships of thermoplastics reinforced with particulate and fiber fillers. The first part of this study was concerned with ascertaining the main causes of warpage observed for injection-molded thermoplastics reinforced with high aspect ratio fibers. Typically, warpage in injection-molded fiber reinforced thermoplastics is primarily attributed to residual thermal stresses associated with shrinkage and thermal contraction of the parts. Therefore, it is assumed that flow-induced stresses generated during mold filling do not play a significant role in the warpage. The warpage of PP composites reinforced with TLCP fibers was found to increase with an increase in fiber loading. The shrinkage and the thermal expansion of the TLCP/PP composites and, hence, the thermally induced stresses decreased with an increase in fiber loading while the flow-induced stresses increased. The increase in the flow-induced stresses was attributed to an inhibition of stress relaxation and greater generation of orientation of the polymer chains with an increase in fiber loading. Therefore, it was found that in order to accurately predict the warpage of fiber reinforced thermoplastics, the flow-induced residual stresses must be accounted for. The second part of this work was concerned with minimizing the particle loading of reinforced PC/PBT composites while maintaining the stiffness, i.e. modulus, and the dimensional stability of injection molded flat panels. This was accomplished by using high aspect ratio (≈100-150) nano-clays as opposed to micron-size talc (≈5-10). It was found that by using nano-clays surface modified with a quaternary ammonium salt that contained two hydroxyl groups as opposed to fine talc particles, the level of particle reinforcement could be reduced from 6 to 1 wt% without sacrificing the modulus of the reinforced PC/PBT composites. Further benefits included a 26% increase in flexural strength, 77% increase in the tensile toughness and 3% reduction in the density of the reinforced PC/PBT composites. An increase in the modulus and tensile toughness was observed even though there was evidence of loss in molecular weight of the PC/PBT matrix, which was supported by the rheological behavior of the composites.
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    Durability of Adhesive Joints Subjected to Environemntal Stress
    O'Brien, Emmett P. (Virginia Tech, 2003-08-28)
    Environmental stresses arising from temperature and moisture changes, and/or other aggressive fluid ingressions can degrade the mechanical properties of the adhesive, as well as the integrity of an adhesive interface with a substrate. Therefore such disruptions can significantly reduce the lifetime and durability of an adhesive joint.1-4 In this research, the durability of certain epoxy adhesive joints and coatings were characterized using a fracture mechanics approach and also by constant frequency impedance spectroscopy. The shaft-loaded blister test (SLBT) was utilized to measure the strain energy release rate (G) or adhesive fracture energy of a pressure sensitive adhesive tape. In this study, support for the value of the SLBT fracture mechanics approach was obtained. The SLBT was then used to investigate the effects of relative humidity on a model epoxy bonded to silicon oxide. Lastly, the effects of water and temperature on the adhesion of a commercial filled epoxy bonded to silicon oxide was characterized and interpreted. A novel impedance sensor for investigating adhesion was developed in a collaborative effort between Virginia Tech and Hewlett-Packard. Utilizing the technique of constant frequency impedance spectroscopy, the distribution and transport of fluids at the interface of adhesive joints was measured. A broad spectrum of adhesives was tested. In addition, the effects of hygroscopic cycling on the durability of adhesive coatings were measured for the commercial filled epoxy using the device. Lastly, recommended modifications of the experimental set-up with the new sensor are proposed to improve the technique.
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    Experimental and Modeling Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor
    Hacarlioglu, Pelin (Virginia Tech, 2007-11-12)
    This dissertation describes the preparation of a novel inorganic membrane for hydrogen permeation and its application in a membrane reactor for the study of the methane steam reforming reaction. The investigations include both experimental studies of the membrane permeation mechanism and theoretical modeling of mass transfer through the membrane and simulation of the membrane reactor with 1-D and 2-D models. A hydrothermally stable and hydrogen selective membrane composed of silica and alumina was successfully prepared on a macroporous alumina support by chemical vapor deposition in an inert atmosphere at high temperature. Before the deposition of the silica-alumina composite, multiple graded layers of alumina were coated on the alumina support with a mean pore size of 100 nm by the sequential application of three boehmite sols with gradually decreasing sol particle sizes of 630, 200 and 40 nm, respectively. The resulting supported composite alumina-silica membrane had high permeability for hydrogen in the order of 10-7 mol m-2 s-1 Pa-1 at 873 K with a H2 /CH4 selectivity of 940 and exhibited much higher stability to water vapor at the high temperature of 873 K. In addition, the same unusual permeance order of Heï¼ H2ï¼ Ne previously observed for the pure silica membrane was also observed for the alumina-silica membrane, indicating that the silica structure did not change much after introduction of the alumina. The permeation of hydrogen and helium through vitreous glass and silica membranes was modeled using ab initio density functional calculations. Comparison of the calculated activation energies to those reported for vitreous glass (20—40 kJ mol -1) indicated the presence of 5- and 6-membered siloxane rings, consistent with the accepted structure of glass as a disordered form of cristobalite. The experimental studies of the steam reforming of methane were examined at various temperatures (773-923 K) and pressures (1-20 atm) with a commercial Ni/MgAl2O4 catalyst in a hydrogen selective silica-alumina membrane reactor and compared with a packed bed reactor. One-dimensional and two-dimensional modeling of the membrane rector and the packed bed reactor were performed at the same conditions and their performances were compared with the values obtained in the experimental study. Improved methane conversions and hydrogen yields were obtained in the membrane reactor compared to the packed bed reactor at all temperatures and pressures. From the two modeling studies, it was also found out that the two-dimensional model performed better in the membrane reactor case especially at higher pressures.
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    Fabrication and characterization of poly(amide-imides)/TiO₂ nanocomposite gas separation membranes
    Hu, Qingchun (Virginia Tech, 1996-10-15)
    Nanosized Ti0₂ rich domains were generated in-situ within poly(amide-imide) (PAl) and 6F-poly(amide-imide) (6FPAl) by a sol-gel process. The composite films showed a high optical transparency. The morphology of the Ti0₂ rich domains was observed by transmission electron microscopy (TEM). The Ti0₂ rich domains were well dispersed within the poly(amide-imide) and 6F-poly(amide-imide) matrices and were 5 nm to 50 nm in size. Limited study was also carried out for the fabrication of the P AI/Si0₂ and PAI/fi0₂-Si0₂ composites. It was found that nanosized Si0₂ rich domains were difficult to form within the poly(amide-imide) matrix, although the Si0₂ could be bonded with the Ti0₂, forming nanosized domains within the poly(amide-imide) matrix. The PAI/Ti0₂ composites showed an increased glass transition temperature, and an increased rubbery plateau modulus, in comparison to the unfilled poly(amide-imide). Wide Angle X- ray Diffraction (W AXD) study and Differential Scanning Calorimetry (DSC) analysis suggest that the Ti0₂ filled poly( amide-imide) have a lower crystallinity as compared to the unfilled poly(amide-imide). The dynamic mechanical properties in rubbery regions suggest that Ti0₂ domains function as physical crosslinks, increasing the rubbery plateau modulus with increasing Ti0₂ content. This behavior can be explained by the theory of rubbery elasticity. The actual formation of the nanosized Ti0₂ and Ti0₂-Si0₂ rich domains was explained in terms of hydrogen bonding effects between the polymer, the solvent and the inorganic components.
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    Fabrication and Characterization of Polyimide-based Mixed Matrix Membranes for Gas Separations
    Pechar, Todd W. (Virginia Tech, 2004-07-14)
    A series of mixed matrix membranes based on zeolites incorporated into fluorinated polyimides were fabricated and characterized in this study. The first system consisted of a polyimide (6FDA-6FpDA-DABA) with carboxylic acid groups incorporated into its backbone and amine-functionalized zeolite particles (ZSM-2). FTIR indicated that these functional groups interacted with each other through hydrogen bonding. Both SEM and TEM images revealed good contact between the polyimide and the zeolite. Permeability studies showed a drop in He permeability suggesting there were no voids between the two components. While simple gases such as O2 and N2 followed effective permeabilities predicted by mixing theories, polar gases such as CO₂ did not. The second system fabricated used the same polyimide with amine-functionalized zeolite L. This zeolite differs from ZSM-2 in that zeolite L's pores are not clogged with an organic template, and it possesses 1-D pores as opposed to ZSM-2's 3-D pore structure. XPS and zeta potential experiments were performed to verify the presence of amine groups on the zeolite surfaces. FTIR data showed that after a heat treatment, amide linkages were created between the amine group on the zeolite and the carboxylic acid group of the polyimide. SEM images showed a good distribution of zeolite L throughout the polymer matrix, and no indication of voids between the two components. Permeability experiments were performed to determine if the addition of zeolite L to the polyimide improved its separation performance. The permeability was unchanged between the pure polyimide membrane and the mixed matrix membrane, suggesting there were no voids present within the matrix. Permeability results of larger gases followed a Maxwell Model. A third system was prepared using a poly(imide siloxane) (6FDA-6FpDA-PDMS) and untreated zeolite L. The primary focus of this investigation was to determine if the addition of the flexible segment would promote direct contact with the zeolite surface and remove the need to amine-functionalize the zeolite. Poly(imide siloxane)s were synthesized at 0, 22, and 41 wt % PDMS as verified using 1H-NMR. FTIR was employed to qualitatively verify the successful imidization of the polymers. SAXS patterns and TEM images did not reveal distinct phases indicative of phase separation, however, AFM images did show the presence of phase separation of the surfaces of the poly(imide siloxane)s. Permeability results showed a decrease in selectivity and an increase in permeability as the wt % of PDMS was increased. Permeabilities and selectivities dropped as the zeolite loading was increased from 0 to 20 wt %. Upon increasing the zeolite loading from 20 to 30 wt %, increases in permeability were observed, but both the permeability and selectivity were still below that of the pure polymer. The final system studied employed the 41 wt % PDMS poly(imide siloxane) as the polymer matrix and either closed-ended or open-ended carbon nanotubes as the filler. SEM images showed regions of agglomeration for both types of nanotubes. Helium permeability dropped in both types MMMs, but more so in closed-ended carbon nanotubes MMM. Nitrogen permeability was unchanged for the closed-ended carbon nanotubes MMM, and dropped slightly in the open-ended carbon-nanotube MMM.
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    Fabrication and Gas Permeation Studies on Polyimide/Layered-Aluminum Phosphate Nanocomposite Membranes
    Krych, Wojtek S. (Virginia Tech, 2003-07-01)
    Polymer – clay nanocomposites have improved thermal, mechanical, and barrier properties when compared with the pure polymer. The objective of this study was to examine if gas separation performance could be improved by introducing a layered nanopourous aluminum phosphate with a large aspect ratio into a polymeric matrix. The aluminum phosphate has eight membered rings, which could potentially serve as a size selective medium. A hexafluorinated polyimide, 6FDA-6FpDA-8%-DABA, was used as the polymeric matrix. The polyimide and the aluminum phosphate were synthesized separately according to well documented procedures. The two materials were blended and fabricated into nanocomposite membranes. The effect of mixing temperature and percentage of layered aluminum phosphate added to the polymer on the permeation properties were examined. These factors had a direct effect on the degree of intercalation and exfoliation of the nanocomposite structure. Transmission FTIR, TEM, DMTA, and X-ray diffraction were used to characterize the morphology, structure, and composition of these nanocomposite films. The permeation properties of the nanocomposite membranes were evaluated using pure gases (He, O₂, N₂, CH₄, CO₂) at 35°C and a feed pressure of 4 atm. In general, the permeability decreased and the selectivity coefficients increased when adding 10 wt% aluminum phosphate to the polyimide. Furthermore, the membranes showed size selectivity, consistent with the pore size in the layered aluminum phosphate.
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    Functionalized Single Walled Carbon Nanotube/Polymer Nanocomposite Membranes for Gas Separation and Desalination
    Surapathi, Anil Kumar (Virginia Tech, 2012-10-26)
    Polymeric membranes for gas separation are limited in their performance by a trade-off between permeability and selectivity. New methods of design are necessary in making membranes, which can show both high permeability and selectivity. A mixed matrix membrane is one such particular design, which brings in the superior gas separation performance of inorganic membranes together with the easy processability and price of the polymers. In a mixed matrix membrane, the inorganic phase is dispersed in the polymeric continuous phase. Nanocomposite membranes have a more sophisticated design with a thin separation layer on top of a porous support. The objective of this research was to fabricate thin SWNT nanocomposite membranes for gas separation, which have both high permeability and selectivity. SWNT/polyacrylic nanocomposite membranes were fabricated by orienting the SWNTs by high vacuum filtration. The orientation of SWNTs on top of the porous support was sealed by UV polymerization. For making these membranes, the CNTs were purified and cut into small open tubes simultaneously functionalizing them with COOH groups. Gas sorption of CO2 in COOH functionalized SWNTs was lower than in purified SWNTs. Permeabilities in etched membrane were higher than Knudsen permeabilities by a factor of 8, and selectivities were similar to Knudsen selectivities. In order to increase the selectivities, SWNTs were functionalized with zwitterionic functional groups. Gas sorption in zwitterion functionalized SWNTs was very low compared to in COOH functionalized SWNTs. This result showed that the zwitterionic functional groups are kinetically blocking the gas molecules from entering the pore of the CNT. SWNT/polyamide nanocomposite membranes were fabricated using the zwitterion functionalized SWNTs by interfacial polymerization. The thickness of the separation layer was around 500nm. Gas permeabilities in the CNT membranes increased with increasing weight percentage of the SWNTs. Gas permeabilities were higher in COOH SWNT membrane than in zwitterion SWNT membrane. Gas selectivities were similar to the Knudsen selectivities, and also to the intrinsic selectivities in the pure polyamide membrane. The water flux in SWNT-polyamide membranes increased with increasing weight percentage of zwitterion functionalized SWNTs, along with a slight increase in the salt rejection. Membranes exhibited less than 1% variability in its performance over three days.
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    Gas Transport in Proton Exchange Membranes for use in Fuel Cell Applications
    James, Charles William Jr. (Virginia Tech, 2007-11-19)
    The objectives of this research were to study the gas transport properties of proton exchange membranes (PEM), namely disulfonated poly(arylene ether sulfone) (BPSH-35), post sulfonated diels-alder poly(phenylene) (SDAPP), and poly(perfluoro sulfonic acid) (Nafion). The O2 gas permeabilities were found to be lower in BPSH and SDAPP as compared to poly(perfluoro sulfonic acid) because of difference in Tg (TgBSPH= 250 oC, TgSDAPP= 330 oC versus TgNafion=150 oC). Higher Tg polymers have a more rigid, inflexible polymer segments causing a reduction in gas permeability. In comparison to SDAPP, BPSH has a lower O2 gas permeability because of the bulky side groups in the SDAPP backbone. O2 sorption measurements were carried out both under non-humidified and humidified conditions as a function of relative humidity and temperature at a normal PEM operating pressure of 1 atm. Under non-humidified conditions, BPSH, SDAPP, and Nafion 112 exhibited Henry's Law sorption, consistent with dilute dissolution of O2 into the polymer matrix. The enthalpies of sorption were calculated to determine the interaction of O2 with each membrane. The sorption enthalpies in BPSH and SDAPP increased with increasing pressure indicating the formation of more O2-O2 interactions. The enthalpies in Nafion 112 were relatively constant with increasing pressure. In the presence of moisture, the sorption behavior changed from Henry's Law to Type IV sorption behavior, which is common in hydrophilic polymers. The SDAPP membrane was found to have the highest percent wet O2 mass uptake because of a higher number of sulfonic acid groups interacting with the water/O2 system. Finally the O2 sorption for various porous catalyst powders, consisting of platinum supported on carbon was measured in the non-humidified and humidified state. The catalysts were found to have Knudsen diffusion in the non-humidified state with 20 wt% Pt-C having the largest O2 sorption. In the humidified state, the highest O2 mass uptake was achieved with 40 wt% Pt-C. These results are explained in terms of the trade-off between catalyst dispersion and catalyst size. Furthermore, O2 sorption measurements were utilized for membrane electrode assemblies containing 40 wt% Pt-C and hot pressed at 210 oC for BPSH-35 (25 and 80K) and Nafion 112 membranes. The same sorption behavior occurred in the MEAs as in the neat membrane, but at a lower capacity. This is because the electrode introduces a more tortuous path to the gas molecules permeating across the membrane.
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    Gas transport properties in polycarbonate - Influence of the cooling rate, physical aging, and orientation
    Laot, Christelle Marie (Virginia Tech, 2001-10-17)
    The objective of this research work was to understand the molecular mechanism of gas transport through amorphous glassy polymers. Especially, emphasis was placed on determining whether or not gas transport in amorphous glassy polymers is directly correlated with the free volume content. Free volume arguments are indeed commonly used to explain the gas transport process. The gas transport properties of bisphenol-A polycarbonate films were examined as a function of the cooling rate, physical aging, and orientation. Such conditions affect the free volume content and its size and shape distribution. Results obtained from permeation experiments were accompanied with dynamic mechanical and density measurements. The experimental results suggest that the diffusion coefficient of small gas molecules in glassy polycarbonate is influenced by the local dynamics or mobility of the polymer chains rather than by the overall free volume content. Indeed, the diffusion coefficient of nitrogen for instance was reduced in fast-cooled samples, despite of the fact that those samples possessed a greater overall free volume content. Fast cooling rates may generate highly restricted conformations which hinder local motions, and therefore tend to increase the activation energy of diffusion. As expected, the greater the free volume content, the greater was the solubility coefficient. The increase in the polymer relaxation times with aging time is believed to restrict the local chain motions, leading to enhanced activation energies of diffusion, and therefore to reduced diffusion coefficients. The change in the solubility coefficients with physical aging revealed that the aging process might not affect all the cavity sizes in polycarbonate equally. According to free volume arguments, one would anticipate that the physical aging of fast-cooled samples (which possess more free volume) should be enhanced compared to that of slowly-cooled samples. Quite interestingly, the decrease in the diffusion coefficient with aging was found to occur much slower in fast-cooled samples, despite of the higher initial free volume content. In contrast, properties directly related to the free volume content, such as density or isothermal DMTA measurements actually showed a greater aging rate in the sample containing the greatest amount of free volume. Slow-cooled samples that are in a low energy conformational state may loose their internal degrees of freedom more rapidly, due to the closer interchain packing and the possibly restricted segmental motions. Studies dealing with orientation and gas transport were complicated by several factors. For instance the fact that the permeation experiments were performed perpendicularly to the orientation of the chains and not along the orientation axis limited the sensitivity of the gas transport properties to orientation. This work points out that dynamic rather than static models should be developed to predict the gas transport phenomenon.
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    Halocarbon Reactions on the Chromium (III) Oxide (101̲2) Surface
    York, Steven C. (Virginia Tech, 1999-08-13)
    A nearly stoichiometric, (1×1) Cr₂O₃ (101̲2) surface was prepared from a single crystal of α-Cr₂O₃. The five-coordinate cations exposed at the stoichiometric surface dissociatively adsorb molecular oxygen to form a (1×1), terminating chromyl (Cr=O) layer that is stable to >1100 K. TDS and AES were used to investigate the reactivity of the halo-alkanes CFCl₂CH₂Cl, CF₂ClCH₂Cl, CF₃CH₂Cl, and CF₂CH₂F, in addition to the halo-alkenes CFCl=CH₂ and CF₂=CH₂. The halo-alkanes CFCl₂CH₂Cl, CF₂ClCH₂Cl, and CF₃CH₂Cl undergo 1,2-dihalo elimination similar to the Zn-catalyzed dehalogenation of vicinal dihalides to form alkenes. Some acetylene is also formed. The halo-alkenes CFCl=CH₂ and CF₂=CH₂ decompose to yield acetylene. Halogen removed from the molecules remains bound to the surface following TDS experiments and eventually terminates the surface chemistry due to site blocking of the cations. Reactivity is directly related to the chlorine content of the molecules investigated. Only CFCl₂CH₂Cl was reactive on a chromyl-terminated surface.
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    High Permeability/High Diffusivity Mixed Matrix Membranes For Gas Separations
    Kim, Sangil (Virginia Tech, 2007-03-22)
    The vast majority of commercial gas separation membrane systems are polymeric because of processing feasibility and cost. However, polymeric membranes designed for gas separations have been known to have a trade-off between permeability and selectivity as shown in Robeson's upper bound curves. The search for membrane materials that transcend Robeson's upper bound has been the critical issue in research focused on membranes for gas separation in the past decade. To that end, many researchers have explored the idea of mixed matrix membranes (MMMs). These membranes combine a polymer matrix with inorganic molecular sieves such as zeolites. The ideal filler material in MMMs should have excellent properties as a gas adsorbent or a molecular sieve, good dispersion properties in the polymer matrix of submicron thickness, and should form high quality interfaces with the polymer matrix. In order to increase gas permeance and selectivity of polymeric membranes by fabricating MMMs, we have fabricated mixed matrix membranes using carbon nanotubes (CNTs) and nano-sized mesoporous silica. Mixed matrix membranes containing randomly oriented CNTs showed that addition of nanotubes to a polymer matrix could improve its selectivity properties as well as permeability by increasing diffusivity. Overall increases in permeance and diffusivity for all tested gases suggested that carbon nanotubes can provide high diffusivity tunnels in the CNT within the polymer matrix. This result agreed well with molecular simulation estimations. In order to prepare ordered CNTs membranes, we have developed a simple, fast, commercially attractive, and scalable orientation method. The oriented CNT membrane sample showed higher permeability by one order of magnitude than the value predicted by a Knudsen model. This CNT membrane showed higher selectivities for CO₂ over other gas molecules because of preferential interaction of CO₂ with the amine functionalized nanotubes, demonstrating practical applications in gas separations. Recently, mesoporous molecular sieves have been used in MMMs to enhance permeability or selectivity. However, due to their micrometer scale in particle size, the composite membrane was extremely brittle and tended to crack at higher silica loading. In this study, we have developed fabrication techniques to prepare MMMs containing mesoporous MCM-41 nanoparticles on the order of ~50 nm in size. This smaller nanoparticle lead to higher polymer/particle interfacial area and provides opportunity to synthesize higher loading of molecular sieves in polymer matrix up to ~80 vol%. At 80 vol% of nano-sized MCM-41 silica loading, the permeability of the membrane increased dramatically by 300 %. Despite these increases in permeability, the separation factor of the MMMs changed only slightly. Therefore, these nanoscale molecular sieves are more suitable for commercialization of MMMs with very thin selective layers than are micro-sized zeolites or molecular sieves.
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    High-pressure viscosity and density of polymer solutions at the critical polymer concentration in near-critical and supercritical fluids
    Dindar, Cigdem (Virginia Tech, 2001-09-26)
    The motivation for the determination of the viscosity of polymer solutions in dense fluids at the critical polymer concentration stems from the need to understand the factors that influence the time scale of phase separation in systems that undergo spinodal decomposition upon a pressure quench. In a recent investigation of PDMS + CO₂ and PE + n-pentane where molecular weights of the polymers and the critical polymer concentrations were comparable, significant differences were observed in the time evolution of new phase growth. Among the reasons that contribute to the difference in phase separation kinetics is the viscosity of the solutions. This thesis has been carried out to experimentally demonstrate the differences in viscosities of solutions at their critical polymer concentration. Specifically, the thesis focused on the high-pressure density and viscosity of solutions of poly(dimethylsiloxane) (Mw = 93,700, Mw/Mn = 2.99) in supercritical carbon dioxide and of polyethylene (Mw = 121,000, Mw/Mn = 4.3) in near-critical n-pentane. The measurements have been carried out at the critical polymer concentrations, which is 5.5 wt % for solution of PDMS in CO2 and 5.75 wt % for solution of PE in n-pentane. For PDMS + CO₂ system, the measurements were conducted at 55, 70, 85 and 100 oC and pressures up to 50 MPa. For PE + n-pentane system, the measurements were conducted at 140 and 150 °C and again up to 50 MPa. All measurements were conducted in the one-phase homogenous regions. At these temperatures and pressures, the viscosities were observed to be in the range from 0.14 mPa.s to 0.22 mPa.s for PDMS + CO₂, and from 2.3 mPa.s to 4.6 mPa.s for PE + n-pentane systems. In both systems the viscosities increase with pressure and decrease with temperature. The temperature and pressure dependence could be described by Arrhenius type relationships in terms of flow activation energy (E#) and flow activation volume (V#) parameters. The flow activation energies in PDMS + CO₂ system were about 7 kJ/mol compared to about 18 kJ/mol for the PE + n-pentane system. The activation volumes were in the range 40-64 cm3/mol for PDMS + CO₂ system and 65-75 cm3/mol for the PE + n-pentane solution. The higher values of E# and V# represent the higher sensitivity of viscosity to temperature and pressure changes in the PE + n-pentane system. The viscosity data could also be correlated in terms of density using free-volume based Doolittle type equations. Density is shown to be an effective scaling parameter to describe T/P dependency of viscosity. The closed packed volumes suggested from density correlations were found to be around 0.33 cm³/g for the PDMS and 0.48 cm3/g for the PE systems. Comparison of the viscosity data in these systems with the data on the kinetics of pressure-induced phase separation confirms that the slower kinetics in the PE + n-pentane stems from the higher viscosity in this solution compared to the PDMS + CO₂ system, despite the similarity in the molecular weight of the polymer and the critical polymer concentrations. These viscosity and density measurements were conducted in a special falling-body type viscometer. In the course of this thesis a more reliable procedure for determining the terminal velocity of the falling sinker was implemented. This is based on the precise and more complete description of the position of the sinker with time with the aid of a set of linear variable differential transformers (LVDTs). The design of the new arrangement and procedure for terminal velocity determination and calibration procedures for the viscometer are also presented. The densities and viscosities are determined with an accuracy of ± 1 % and ± 5 % or better, respectively.
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    Hybrid Inorganic-Organic Materials: Novel Poly(Propylene Oxide) Based Ceramers, Abrasion Resistant Sol-Gel Coatings for Metals, and Epoxy-Clay Nanocomposites. With an Additional Chapter On: Metallocene Catalyzed Linear Polyethylene
    Jordens, Kurt (Virginia Tech, 1999-08-03)
    The sol-gel process has been employed to generate hybrid inorganic-organic network materials. Unique ceramers were prepared based on an alkoxysilane functionalized soft organic oligomer, poly(propylene oxide) (PPO), and tetramethoxysilane (TMOS). Despite the formation of covalent bonds between the inorganic and organic constituents, the resulting network materials were phase separated, composed of a silicate rich phase embedded in a matrix of the organic oligomer chains. The behavior of such materials was similar to elastomers containing a reinforcing filler. The study focused on the influence of initial oligomer molecular weight, functionality, and tetramethoxysilane, water, and acid catalyst content on the final structure, mechanical and thermal properties. The sol-gel approach has also been exploited to generate thin, transparent, abrasion resistant coatings for metal substrates. These systems were based on alkoxysilane functionazized diethylenetriamine (DETA) with TMOS, which generated hybrid networks with very high crosslink densities. These materials were applied with great success as abrasion resistant coatings to aluminum, copper, brass, and stainless steel. In another study, intercalated polymer-clay nanocomposites were prepared based on various epoxy networks montmorillonite clay. This work explored the influence of incorporated clay on the adhesive properties of the epoxies. The lap shear strength decreased with increasing clay content. This was due to a reduction in the toughness of the epoxy. Also, the delaminated (or exfoliated) nanocomposite structure could not be generated. Instead, all nanocomposite systems possessed an intercalated structure. The final project involved the characterization of a series of metallocene catalyzed linear polyethylenes, produced at Phillips Petroleum. Polyolefins synthesized with such new catalyst systems are becoming widely available. The influence of molecular weight and thermal treatment on the mechanical, rheological, and thermal behavior was probed. Although the behavior of this series of metallocene polyethylenes was not unlike that of traditionally catalyzed materials, this work is one of the first comprehensive studies of these new linear polyethylenes. The main distinction between the metallocene and traditional Ziegler-Natta catalyzed polyethylenes is the narrow molecular weight distributions produced by the former (for this series of materials, 2.3< Mw  Mn <3.6).
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    An Investigation of the Structure-Property Relationships for High Performance Thermoplastic Matrix, Carbon Fiber Composites with a Tailored Polyimide Interphase
    Gardner, Slade Havelock II (Virginia Tech, 1998-08-17)
    The aqueous suspension prepregging technique was used to fabricate PEEK and PPS matrix composites with polyimide interphases of tailored properties. The structure-property relationships of Ultem-type polyimide and BisP-BTDA polyimide which were made from various water soluble polyamic acid salts were studied. The molecular weight of the polyimides was shown to be dependant upon the selection of the base used for making the polyamic acid salt. The development of an Ultem-type polyimide with controlled molecular weight and properties similar to commercial Ultem 1000 was accomplished with the Ultem-type TPA+ polyamic acid salt. Both the Ultem-type polyimides and the BisP-BTDA polyimides derived from the NH4+ salt and the TMA+ salt were shown to crosslink at elevated temperatures. Blends of Ultem-type polyimide with PEEK and BisP-BTDA polyimide with PEEK were prepared to study the structure-property relationships of model composite matrices. Since both polyimides are miscible with PEEK, interdiffusion of the polyimides with PEEK is expected, however, the interdiffusion behavior is complicated by the crosslinking mechanism of the polyimides. Ultem-type polyimide interphase, PEEK matrix composites and BisP-BTDA polyimide interphase, PEEK matrix composites were fabricated using the aqueous suspension prepregging technique and evaluated to determine the effects of the interphase properties on the bulk composite performance and durability. Three different Ultem-type polyimides from the NH4+, TMA+ and TPA+ polyamic acid salts were used and two different BisP-BTDA polyimides from the NH4+ and TMA+ polyamic acid salts were used. The transverse flexure strength was used to qualitatively rank the composites by level of interfacial shear strength. The longitudinal tensile strength of the composites was shown to vary with relative interfacial shear strength. The trend of these data qualitatively support the existence of a maximum longitudinal tensile strength at an optimum interfacial shear strength. Notched fatigue testing of the Ultem-type polyimide interphase, PEEK matrix composites showed that the initial split growth rate increased with decreasing relative interfacial shear strength. Ultem-type polyimide interphase, PPS matrix composites were fabricated using the aqueous suspension prepregging technique and evaluated to determine the effects of the interphase properties on the bulk composite performance. Three different Ultem-type polyimides from the NH4+, TMA+ and TPA+ polyamic acid salts were used. The transverse flexure strength was used to qualitatively rank the composites by level of interfacial shear strength. The longitudinal tensile strength of the composites was shown to vary with relative interfacial shear strength. The trend of these data qualitatively support the existence of a maximum longitudinal tensile strength at an optimum interfacial shear strength.
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    Investigation of the Wood/Phenol-Formaldehyde Adhesive Interphase Morphology
    Laborie, Marie-Pierre Genevieve (Virginia Tech, 2002-02-01)
    This work addresses the morphology of the wood/ Phenol-Formaldehyde (PF) adhesive interphase using yellow-poplar. In this case, morphology refers to the scale or dimension of adhesive penetration into wood. The objective is to develop methods for revealing ever smaller levels of wood/resin morphology. Dynamic techniques that are commonly utilized in polymer blend studies are investigated as potential methods for probing the wood/ adhesive interphase morphology. These are Dynamic Mechanical Analysis (DMA) and solid state NMR using CP/MAS. PF resin molecular weight is manipulated to promote or inhibit resin penetration in wood, using a very low or a very high molecular weight PF resin. With DMA, the influence of PF resin on wood softening is investigated. It is first demonstrated that the cooperativity analysis according to the Ngai coupling model of relaxation successfully applies to the in-situ lignin glass transition of yellow-poplar and spruce woods. No significant difference in intermolecular coupling is detected between the two woods. It is then demonstrated that combining simple DMA measurements with the cooperativity analysis yields ample sensitivity to the interphase morphology. From simple DMA temperature scans, a low molecular weight PF (PF-Low) does not influence lignin glass transition temperature. However, the Ngai coupling model of relaxation indicates that intermolecular coupling is enhanced with the low molecular weight PF. This behavior is ascribed to the low molecular weight PF penetrating lignin on a nanometer scale and polymerizing in-situ. On the other hand, a high molecular weight resin with a broad distribution of olecular weights (PF-High) lowers lignin glass transition temperature dramatically. This plasticizing effect is ascribed to a small fraction of the PF resin being low enough in molecular weight to penetrate lignin on a nanoscale, but being too dispersed for forming a crosslinked network. With CP/MAS NMR, intermolecular cross-polarization experiments are found unsuitable to probe the angstrom scale morphology of the wood adhesive interphase. However, observing the influence of the PF resins on the spin lattice relaxation time in the rotating frame, HT1r, and the cross-polarization time (TCH) is useful for probing the interphase morphology. None of the resins significantly affects the cross-polarization time, suggesting that angstrom scale penetration does not occur with a low nor a high molecular weight PF resin. However, the low molecular weight PF substantially modifies wood polymer HT1r, indicating that the nanometer scale environment of wood polymers is altered. On the other hand, the high molecular weight PF resin has no effect on wood HT1r. On average, the high molecular weight PF does not penetrate wood on a nanometer scale. Interestingly, the low molecular weight PF resin disrupts the spin coupling that is typical among wood components. Spin coupling between wood components is insensitive to the high molecular weight PF. Finally, it is noteworthy that the two PF resins have significantly different T1r 's in-situ. The low molecular weight resin T1r lies within the range of wood relaxations, suggesting some degree of spin coupling. On the other hand, the T1r of the high molecular weight PF appears outside the range of wood relaxations. Spin coupling between the high molecular weight resin and wood components is therefore inefficient. The CP/MAS NMR and DMA studies converge to identify nanometer scale penetration of the low molecular weight PF in wood. On the other hand, the high molecular weight PF resin forms separate domains from wood, although a very small fraction of the PF-High is able to penetrate wood polymers on a nanoscale.