Browsing by Author "Martin, Stephen M."

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    Assessing an Orientation Model and Stress Tensor for Semi-Flexible Glass Fibers in Polypropylene Using a Sliding Plate Rheometer: for the Use of Simulating Processes
    Ortman, Kevin Charles (Virginia Tech, 2011-08-05)
    Great interest exists in adding long fibers into polymeric fluids due to the increase in properties associated with the composite, as compared to the neat resin. These properties, however, are dependent on the fiber orientations generated during processing, such as injection molding. In an effort to optimize industrial processing, optimize mold design, and maximize desired properties of the final part, it is highly desirable to predict long fiber orientation as a function of processing conditions. The purpose of this research is to use rheology as a fundamental means of understanding the transient orientation behavior of concentrated long glass (> 1mm) fiber suspensions. Specifically, this research explores the method of using rheology as a means of obtaining stress tensor and orientation model parameters needed to accurately predict the transient fiber orientation of long glass fiber reinforced polypropylene, in a well-defined simple shear flow, with the hopes of extending the knowledge gained from these fundamental experiments for the use of simulating processing flows, such as injection molding. Two fiber orientation models were investigated to predict the transient orientation of the long glass fiber systems explored. One model, the Folgar-Tucker model, has been particularly useful for predicting fiber orientation in short glass fiber systems and was used in this paper to assess its performance with long glass fibers. A second orientation model, one that accounts for the semi-flexibility of fibers, was extended to describe non-dilute suspension and coupled with an augmented stress tensor that accounts for fiber bending. Stress tensor and orientation model parameters were determined (in all cases) by best fitting these coupled equations to measured stress data obtained using a sliding plate rheometer. Results showed the semi-flexible orientation model and stress tensor combination, overall, provided improved rheological results as compared to the Folgar-Tucker model when coupled with the stress tensor of Lipscomb (1988). Furthermore, it was found that both stress tensors required empirical modification to accurately fit the measured data. Both orientation models provided encouraging results when predicting the transient fiber orientation in a sliding plate rheometer, for all initial fiber orientations explored. Additionally, both orientation models provided encouraging results when the model parameters, determined from the rheological study, were used for the purpose of predicting fiber orientation in an injection molded center-gated disk.
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    Comparison of Multieffect Distillation and Extractive Distillation Systems for Corn-Based Ethanol Plants
    Dion Ngute, Miles Ndika (Virginia Tech, 2012-01-13)
    Recent publications on ethanol production and purification shows optimized energy and water consumptions as low as 22,000 Btu/gal ethanol and 1.54 gal water/gal ethanol respectively using multieffect distillation. Karuppiah, et al use column rating and mathematical optimization methods and shortcut design models to design evaluate and optimize the energy and water consumption. In this work, we compare shortcut design and rigorous simulation models for an ethanol purification distillation system, and we show that distillation systems based on shortcut design underestimate the true energy and water consumption of the distillation system. We then use ASPEN Plus, to design a multieffect distillation system and an extractive distillation system using rigorous simulation and compare the two for energy and water consumptions. We show that the extractive distillation system has lower steam and cooling water consumptions and consequently lower energy and water consumptions than multieffect distillation in corn-to-ethanol production and purification. We also show that the extractive distillation system is cheaper than the multieffect distillation system on a cost per gal ethanol basis. This work gives an energy consumption of 29987 Btu/gal ethanol and water consumptions 2.82 gal/gal ethanol for the multieffect distillation system at a manufacturing cost of $3.03/gal ethanol. For the extractive distillation system, we calculate an energy consumption of 28199 Btu/gal ethanol and a water consumption of 2.79 gal/gal ethanol at a manufacturing cost of $2.88/gal ethanol.
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    Effects of Electric Fields on Forces between Dielectric Particles in Air
    Chiu, Ching-Wen (Virginia Tech, 2013-05-01)
    We developed a quantitative measurement technique using atomic force microscopy (AFM) to study the effects of both DC and AC external electric fields on the forces between two dielectric microspheres. In this work we measured the DC and AC electric field-induced forces and adhesion force between two barium titanate (BaTiO?) glass microspheres in a low humidity environment by this technique. The objective here is to find out the correlation between these measured forces and applied field strength, frequency, and the separation distance between the two spheres was studied. Since the spheres would oscillate under an AC field, the AC field-induced force was divided into dynamic component (i.e., time-varying term) and static component (i.e., time-averaged term) to investigate. The oscillatory response occurs at a frequency that is twice the drive frequency since the field-induced force is theoretically proportional to the square of the applied field. This behavior can be observed in the fast Fourier transformation (FFT) spectra of the time series of the deflection signal. The magnitude of the vibration response increases when the frequency of the drive force is near resonant frequency of the particle-cantilever probe. The amplitude of this vibration increases with proximity of the two particles, and ultimately causes the particles to repeatedly hit each other as in tapping mode AFM. The effect of the Maxwell-Wagner interfacial relaxation on the DC electric field-induced force was discovered by monitoring the variation of the field-induced force with time. The static component of the AC electric field-induced force does not vary with the applied frequency in the range from 1 to 100 kHz, suggesting that the crossover frequency may equal to or less than 1 kHz and the permittivities of the BaTiO? glass microspheres and medium dominate the field-3 induced force. The AC field-induced force is proportional to the square of the applied electric field strength. This relationship persists even when the separation between the spheres is much smaller than the diameter of the microspheres. The large magnitude of the force at small separations suggests that the local field is distorted by the presence of a second particle, and the continued dependence on the square of the field but the measured force is much larger than the theoretical results, suggesting that the local electric field around the closely spaced spheres is distorted and enhanced but the effects of the local field distortion may have not much to with the applied electric field. Compared with the calculated results from different models, our results demonstrate that the field-induced force is much more long-range than expected in theory. In addition, the DC field-induced adhesion force is larger than the AC field-induced one due to the interfacial charge accumulation, agreeing with the discovery of the Maxwell-Wagner interfacial relaxation effect on the DC field-induced force. No obvious correlation between the field-induced adhesion and the applied frequency is found. However, both the DC and AC field-induced adhesion forces display the linearity with the square of the applied electric field strength as well.
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    Extension of the Method of Ellipses to Determining the Orientation of Long, Semi-flexible Fibers in Model 2- and 3-dimensional Geometries
    Hofmann, John (Virginia Tech, 2013-10-23)
    The use of fiber-reinforced polymer composites formed via injection molding is of increasing interest due to their superior mechanical properties as compared to those of the polymer matrix alone. These mechanical properties, however, are strongly dependent on the fiber length and orientation distributions within a molded part. As such, there is a need to understand and model the orientation evolution of chopped fibers in flow in order to accurately simulate the final fiber orientation distribution within injection molded parts. As a result of this, accurate and reliable experimental measurement of fiber orientation is needed. Within this research, the application and validity of the Method of Ellipses for determining the orientation of long, semi-flexible glass fibers within injection molded composites has been investigated. A fiber suspension with an average length of approximately 3.9 mm was the focus of this study and assumed to be representative of commercial distributions. A novel method to quantify fiber curvature was developed and utilized to show that flexibility in center-gated disc and the end-gated plaque samples was minimal on average for the selected fiber length distribution. Thus, it was determined that the Method of Ellipses was applicable when utilized to obtain reliable orientation data for the selected long glass fiber suspension and within the chosen geometries that exhibit 1-, 2-, and 3-dimensional velocity fields. However, a modified image analysis width was found to be necessary in regions of highly aligned fibers, due to the increase in ellipse size and the need to reduce the number of partial objects and thus minimize error. This allowed for a direct comparison of the experimental orientation behavior of short and long glass fibers within the center-gated disc and the end-gated plaque, as well as the effect of the orientation distributions on the global modulus of the part.
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    Formation of Cyclodextrin-Drug Inclusion Compounds and Polymeric Drug Delivery Systems using Supercritical Carbon Dioxide
    Grandelli, Heather Eilenfield (Virginia Tech, 2013-10-10)
    New methods for the preparation of porous biomedical scaffolds have been explored for applications in tissue engineering and drug delivery. Scaffolds with controlled pore morphologies have been generated which incorporate cyclodextrin-drug inclusion complexes as the drug delivery component. Supercritical CO2 was explored as the main processing fluid in the complex formation and in the foaming of the polymer scaffold. The co-solvents, ethanol, ethyl acetate and acetone, were explored in each stage, as needed, to improve the solvent power of CO2. The first goal was to promote cyclodextrin-drug complex formation. Complex formation by traditional methods was compared with complex formation driven by processing in supercritical CO2. Complex formation was promoted by melting the drug in supercritical CO2 or in CO2 + co-solvent mixtures while in the presence of cyclodextrin. Some drugs, such as piroxicam, are prone to degradation near the drug's ambient melting temperature. However, this approach using CO2 was found to circumvent drug thermal degradation, since drug melting temperatures were depressed in the presence of CO2. The second goal was to produce porous polymeric matrices to serve as tissue engineering scaffolds. Poly(lactide-co-glycolide) and poly(ε-caprolactone) were investigated for foaming, since these biomedical polymers are already commonly used and FDA approved. Polymer foaming with CO2 is an alternative approach to conventional solvent-intensive methods for porosity generation. However, two major limitations of polymer foaming using CO2 as the only processing fluid have been reported, including the formation of a non-porous outer skin upon depressurization and limited pore interconnectivity. Approaches to circumvent these limitations include the use of a co-solvent and controlling depressurization rates. The effect of processing parameters, including foaming temperatures and depressurization rate, as well as co-solvent addition, were examined in polymer foaming using CO2. Drug release dynamics were compared for foams incorporated with either pure drug, cyclodextrin-drug physical mixture or cyclodextrin-drug complex. Pore morphology, polymer choice and drug release compound choice were found to alter drug release profiles.
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    Functionalized Cellulose Nanocrystal Nanocomposite Membranes with Controlled Interfacial Transport for Improved Reverse Osmosis Performance
    Smith, Ethan D.; Hendren, Keith D.; Haag, James; Foster, Earl Johan; Martin, Stephen M. (MDPI, 2019-01-20)
    Thin-film nanocomposite membranes (TFNs) are a recent class of materials that use nanoparticles to provide improvements over traditional thin-film composite (TFC) reverse osmosis membranes by addressing various design challenges, e.g., low flux for brackish water sources, biofouling, etc. In this study, TFNs were produced using as-received cellulose nanocrystals (CNCs) and 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanocrystals (TOCNs) as nanoparticle additives. Cellulose nanocrystals are broadly interesting due to their high aspect ratios, low cost, sustainability, and potential for surface modification. Two methods of membrane fabrication were used in order to study the effects of nanoparticle dispersion on membrane flux and salt rejection: a vacuum filtration method and a monomer dispersion method. In both cases, various quantities of CNCs and TOCNs were incorporated into a polyamide TFC membrane via in-situ interfacial polymerization. The flux and rejection performance of the resulting membranes was evaluated, and the membranes were characterized via attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The vacuum filtration method resulted in inconsistent TFN formation with poor nanocrystal dispersion in the polymer. In contrast, the dispersion method resulted in more consistent TFN formation with improvements in both water flux and salt rejection observed. The best improvement was obtained via the monomer dispersion method at 0.5 wt% TOCN loading resulting in a 260% increase in water flux and an increase in salt rejection to 98.98 ± 0.41% compared to 97.53 ± 0.31% for the plain polyamide membrane. The increased flux is attributed to the formation of nanochannels at the interface between the high aspect ratio nanocrystals and the polyamide matrix. These nanochannels serve as rapid transport pathways through the membrane, and can be used to tune selectivity via control of particle/polymer interactions.
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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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    Mitigation of bidirectional solute flux in forward osmosis via membrane surface coating of zwitterion functionalized carbon nanotubes
    Zou, Shiqiang; Smith, Ethan D.; Lin, Shihong; Martin, Stephen M.; He, Zhen (Elsevier, 2019-07-08)
    Forward osmosis (FO) has emerged as a promising membrane technology to yield high-quality reusable water from various water sources. A key challenge to be solved is the bidirectional solute flux (BSF), including reverse solute flux (RSF) and forward solute flux (FSF). Herein, zwitterion functionalized carbon nanotubes (Z-CNTs) have been coated onto a commercial thin film composite (TFC) membrane, resulting in BSF mitigation via both electrostatic repulsion forces induced by zwitterionic functional groups and steric interactions with CNTs. At a coating density of 0.97 gm⁻², a significantly reduced specific RSF was observed for multiple draw solutes, including NaCl (55.5% reduction), NH₄H₂PO₄(83.8%), (NH₄)₂HPO₄ (74.5%), NH₄Cl (70.8%), and NH₄HCO₃ (61.9%). When a synthetic wastewater was applied as the feed to investigate membrane rejection, FSF was notably reduced by using the coated membrane with fewer pollutants leaked to the draw solution, including NH₄⁺-N (46.3% reduction), NO₂⁻₋N (37.0%), NO₂⁻₋N (30.3%), K⁺ (56.1%), PO₄³⁻₋P (100%), and Mg²⁺ (100%). When fed with real wastewater, a consistent water flux was achieved during semi-continuous operation with enhanced fouling resistance. This study is among the earliest efforts to address BSF control via membrane modification, and the results will encourage further exploration of effective strategies to reduce BSF.
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    Modeling of Microstructures and Stiffness of Injection Molded Long Glass Fiber Reinforced Thermoplastics
    Chen, Hongyu (Virginia Tech, 2018-11-19)
    An enhanced demand for lightweight materials in automotive applications has resulted in the growth of the use of injection molded discontinuous fiber-reinforced thermoplastics. During the intensive injection molding process, severe fiber breakage arises in the plasticating stage leading to a broad fiber length distribution. Fiber orientation distribution (FOD) is another highly anisotropic feature of the final injection molded parts induced by the mold filling process. The mechanical and other properties can be highly dependent on the fiber length distribution and fiber orientation distribution. The residual fiber length in the final part is of great significance determining the mechanical performances of injection molded discontinuous fiber reinforced thermoplastic composites. One goal of this research is to develop a fiber length characterization method with reproducible sampling procedure in a timely manner is described. In this work is also proposed an automatic fiber length measurement algorithm supported by Matlab®. The accuracy of this automatic algorithm is evaluated by comparing the measured results using this in-house developed tool with the manual measurement and good agreement between the two methods is observed. Accurate predictions of fiber orientation are also important for the improvement of mold design and processing parameters to optimize mechanical performances of fiber-reinforced thermoplastics. In various fiber orientation models, a strain reduction factor is usually applied to match the slower fiber orientation evolution observed experimentally. In this research, a variable strain reduction factor is determined locally by the corresponding local flow-type and used in fiber orientation simulation. The application of the variable strain reduction factor in fiber orientation simulations for both non-lubricated squeeze flow and injection molded center-gated disk, allows the simulated fiber re-orient rate to be dependent on the local flow-type. This empirical variable strain reduction factor might help to improve the fiber orientation predictions especially in complex flow, because it can reflect the different rates at which fibers orient during different flow conditions. Finally, the stiffness of injection-molded long-fiber thermoplastics is investigated by micro-mechanical methods: the Halpin-Tsai (HT) model and the Mori-Tanaka model based on Eshelby's equivalent inclusion (EMT). We proposed an empirical model to evaluate the effective fibers aspect ratio in the computation for the fiber bundles under high fiber content in the as-formed fiber composites. After the correction, the analytical predictions had good agreement with the experimental stiffness values from tensile tests on the composites. Our analysis shows that it is essential to incorporate the effect of the presence of fiber bundles to accurately predict the composite properties.
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    Phase behavior and ordering kinetics of block copolymers in solution during solvent removal
    Heinzer, Michael J. (Virginia Tech, 2011-08-25)
    This dissertation is part of an effort to understand and to facilitate the modeling of the ordering kinetics of block copolymers in solution during the extraction of solvent from a solution-cast film. Central to this work was determining a suitable method for measuring the ordering kinetics during solvent removal and being able to interpret the measurements in terms of structure development. It was also necessary to assess a model for quantifying the ordering kinetics to use in conjunction with a mass transfer model to predict structure formation during solvent extraction. Changes in the dynamic mechanical response (DMR) over time of block copolymer solutions at fixed concentrations following solvent removal were explored as a means to track the growth of ordered domains. It was found that DMR measurements performed following solvent extraction were sensitive to the nucleation and growth process of the phase separation process over a wide range of concentrations, beginning near the order-disorder transition concentration. Based on complimentary small angle X-ray measurements, it was determined that the changes in the DMR are caused by the development of individual microstructures, The SAXS experiments also indicated that the DMR is insensitive to late stages of the growth process. Ultimately, DMR measurements under-predicted the ordering times at several concentrations and did not detect ordering at concentrations above which SAXS data indicated ordering was still occurring. The ability to use the parallel and series rules of mixtures for determining ï ¦(t) in conjunction with the Avrami equation to quantitatively model the ordering kinetics was also determined. These models allowed the ordering kinetics during solvent removal to be qualitatively analyzed. However, using the two different rules of mixtures resulted in a wide range of possible ordering times for a given copolymer concentration, making these approximations unsuitable for modeling a real solvent extraction process. Further, the parameters of the model were insensitive to the type of microstructures developing. As a continuation of this work, a new apparatus to track block copolymer ordering in situ during solvent extraction was designed. Experiments using the apparatus allowed the ordering kinetics and domain dimensions as a function of concentration to be monitored in real-time under several solvent removal conditions. These experiments study the ordering kinetics is a manner more akin to real processing conditions and will allow future assessment of the ability of iso-concentration ordering kinetics to predict phase separation during film processing.
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    Polymer/Clay Nanocomposites as Barrier Materials Used for VOC Removal
    Herrera-Alonso, Jose M. (Virginia Tech, 2009-08-31)
    The objective of this study was to determine if the method of incorporation of a silicate layered nanoclay into a polymer matrix can affect the barrier properties of the pristine polymer in order to decrease the transport of volatile organic compounds (VOC) in indoor air. Building materials are a primary source for VOCs. These emissions are a probable cause of acute health effects and discomfort among occupants and are known to diminish productivity. The predicted concentrations of several of the VOCs emitted by structural insulated panels (SIP) are of concern with respect to health and comfort of occupants. The main issue related to the barrier membranes is the dispersion properties of the nanoclays in the polymer matrix, and the generation of a tortuous pathway that will decrease gas permeation. The tortuous pathway is created by a nanoclay filler, whose ideal exfoliated structure has high surface area, and high aspect ratio. By choosing the appropriate surfactants, the nanoclays can be modified to allow improved molecular interactions between the nanoclay and the polymer matrix. Several studies were performed in order to evaluate the dispersion properties of the nanoclay in the polymer matrix. Polymer/clay nanocomposites barrier membranes were generated via different synthesis methods. In the first study, barrier membranes were composed of a polyurethane, Estane ® 58315, and different nanoclays, Cloisite ® 10A, Cloisite ® 20A, Cloisite ® 30B. The interaction of the polyurethane and the different surfactants used to organically modify the nanoclay was evaluated. The dispersion of the clay platelets was analyzed by varying the pre-processing method; sonication vs stirring. The decrease in gas permeability results was enhanced by the effect of pre-processing via sonciation in comparison to plain stirring. These results also suggest that nanoclay platelets modified with alkylammonium groups with one tallow tail Cloisite ® 10A and Cloisite ® 30B, allow better dispersion and penetration of the polymer within the basal spacing of the nanoclays. Once the decrease in gas permeability was confirmed, the next challenge was to study and evaluate the performance of the polyurethane/clay nanocomposites barrier membranes in the determination of diffusivity coefficients for volatile organic compounds (VOCs). This was achieved via gravimetric sorption characterization. This method allowed for characterization of the sorption and desorption phenomena of VOC in barrier membranes. Barrier membranes pretreated with sonication demonstrated lower diffusivity coefficients than those only treated with stirring. At high clay loadings, 50 wt% of nanoclay in the polymer, the decrease in diffusivity coefficients for VOCs such as butanol and toluene, was found to be one order of magnitude. Other VOCs such as decane and tetradecane also showed a significant decrease in diffusivity coefficient. The results for VOC sorption studies suggest that there is some variability. In order to enhance the exfoliation of the clay, we decided to examine in situ polymerization of poly (n-butyl methacrylate) in the presence of nanoclay. In this study the clay wt% was kept at a low concentration of 1-5 wt%. The surface modification of natural montmorillonite, Cloisite ® Na+, was achieved via ion exchange, and the effect of pre-processing was also explored. The modification rendered a tethered group on the surface of the clay that was able to react with the monomer/oligomer chains and thus expand and exfoliate the clay platelets. Gas permeation data suggest that sonication also produced better barrier properties than its counterpart stirring. XRD diffractograms also confirmed exfoliation of the clay platelets in the poly (n-butyl methacrylate) polymer matrix. Thermogravimetric analysis (TGA) suggested that exfoliation of the clay platelets led to improved thermal stability by increasing the decomposition temperature of the membranes. A small increase in Tg also suggested restricted segmental chain motion within the clay platelets. Overall gas permeation decreased even at low clay content. Phenomenological models such as those of Cussler and Nielsen were used to model the experimental permeation results. These models suggest that although the aspect ratio of the clay platelets is within the specifications provided by the manufacturer, it does not reflect the ideal behavior of the models. The last step of this work was to achieve exfoliation of the modified nanoclay platelets via emulsion polymerization of poly (n-butyl methacrylate). The clay concentration in the emulsion was kept the same as in the in situ polymerization. DLS results suggest a uniform distribution of the polymer/clay nanocomposites particles in the emulsion. Permeation data indicated higher permeation values than the in situ method of synthesis of the nanocomposite membranes. This led us to explore the use of glassy co-polymer of poly(n-butyl methacrylate)-poly(methyl methacrylate) as the matrix. The addition of a more glassy component in the polymer matrix led to improved barrier properties of the nanocomposite membranes. As expected, the copolymer had a higher Tg than the PMMA polymer. Analysis via phenomenological models, also suggested that the chemistry of the co-polymer played an important role in decreasing gas permeability within the polymer/clay nanocomposite membranes, although the effect of the glassy component in the matrix was not quantified by the phenomenological models.
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    Self-Assembled Host-Guest Thin Films for Functional Interfaces
    Erdy, Christine (Virginia Tech, 2008-12-08)
    The functionalization of surfaces has received attention because the process allows the design and tailoring of substrate surfaces with a new or improved function. "Host-guest" thin film complexes are composed of "host" molecules attached the substrate surface, either through physisorption or covalent bonds, with cavities for the inclusion of desired "guest" molecules for the functionalization of the surface. Two methods for fabricating functional "host-guest" thin films were investigated: Langmuir-Blodgett (LB) deposition and self-assembly monolayer (SAM). Langmuir films were created at the air-water interface using octadecanesulfonic acid (C18S) as the amphiphilic "host" molecules separated by hydrophilic guanidinium (G) spacer molecules, which created a cavity allowing the inclusion of desired "guest" molecules. Surface pressure-area isotherms of the (G)C18S, with and without guests, are characterized by the lift-off molecular areas and are use to determine the proper deposition surface pressure. "Host-guest" Langmuir films are deposited onto silicon substrates using the LB deposition technique. The LB films were then subjected to stability testing using different solvents over increasing periods of time. Grazing-angle incidence X-ray diffraction (GIXD), specular X-ray reflectivity (XRR) and transfer ratio measurements were used to characterize the crystallinity, film thickness, overall film stability and film coverage. The GIXD data revealed that the crystallinity of the deposited film varies with the "guest" molecules and can be disrupted by the functional group on the "guest" molecule through hydrogen bonding. After modeling the XRR data using StochFit, it was discovered that the more polar solvent, tetrahydrofuran (THF), removed the film completely while the nonpolar solvent, hexane, compacted the thin film and increased the electron density. With transfer ratios around 0.95 to 1.05, the deposited films were homogenous. The second method used was self-assembly monolayers, which differs from Langmuir films in that they are created by a spontaneous chemical synthesis from immersing a substrate into a solution containing an active surfactant. Octadecyltrichlorosilane (OTS) was used initially as a molecule to study the self-assembled monolayer procedure. To study a "host-guest" self-assembled monolayer system, a compound is being synthesized from 9-bromoanthracene. This compound would already contain the cavity necessary for the inclusion of "guest" molecules. The solution that contained OTS was composed of a 4:1 mixture of anhydrous octadecane: chloroform. Silicon substrates with a deposited oxide layer were hydroxylated for the surfactant binding chemical reaction to occur. The OTS SAMs were exposed to the same stability tests as the LB films. Surface contact angle measurements were taken of the OTS SAMs before and after the stability tests. The contact angle prior to the stability tests was 110° (±2°). The contact angle after immersion in THF was 101° (±2°) while the contact angle resulting from immersion in hexane was 105° (±2°). From the contact angle measurements, the degradation of the OTS SAMs was less extensive than that of the (G)C18S LB films.
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    Separation of Colloidal Particles in a Packed Column using Depletion Forces
    Guzman, Francisco J. (Virginia Tech, 2012-08-27)
    Depletion forces were used to separate an equinumber density binary dispersion of 1.5 and 0.82 µm polystyrene sulfate (PS) particles. Experiments consisted of injecting a pulse of a binary dispersion of PS particles into the inlet of a packed bed of 0.5 mm silica collector beads. Prior to injection, a carrier fluid of either KCl and KOH electrolyte or a silica nanoparticle dispersion was flowing through the column at steady state. When the carrier fluid was a dispersion of silica nanoparticles, the ratio of PS particles in the column outlet would change from 1:1 big to small particles to slightly over 2:1. This implies that more of the smaller 0.82 µm particles were being trapped on the surface of the collector beads due to depletion forces. Experiments with a single particle type (either 1.5 or 0.82 µm PS particle) were also done and correlated with the binary dispersion measurements. Potential energy profiles between a PS particle and a flat silica plate were calculated. The secondary energy barrier for the 1.5 µm particles was two times greater than for the 0.82 µm particles. Hence, the 0.82 µm particles were more likely to overcome the energy barrier and get trapped on the surface of the collector beads. Although the potential energy profiles were calculated at equilibrium, they can be used as a tool in finding the optimal conditions for separation.
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    Simulation study of carbon dioxide and methane permeation in hybrid inorganic-organic membrane
    Wang, Zhenxing (Virginia Tech, 2012-09-05)
    In this dissertation the gas permeation process within four hybrid inorganic-organic membranes is modeled at the micro level using molecular dynamics (MD) and at the meso scale level using a diffusion mechanism. The predicted permeances and relative selectivity of CO₂ and CH₄ are compared with the experimental results. In the MD simulation a single-pore silica crystal framework model with and without inserted phenyl groups are used to define two membrane structures. We designate the two cases as PSPM and SPM respectively. To mimic the diffusion of gas across the membrane, a three-region system with a repulsive wall potential on the edge is employed. Results from the SPM model indicate that the pore size affects the permeance but not the selectivity. In the PSPM model the permeance decreases significantly when the pore size is below a critical value. The extent of decrease varies with the type of gas and this is reflected in the large selectivity in the PSPM model. When the initial diameter is 0.4 nm the model shows a selectivity of 17.3, which is very close to experimental results. At this selectivity the CO₂ permeance is 2.87 Ã 10-4 mol m⁻²s⁻¹Pa⁻¹ and the CH₄ permeance is 1.66 Ã 10⁻⁵ mol m⁻²s⁻¹Pa⁻¹. For different gases we also studied the motions of the phenyl groups in the pore during the permeation process. The results show that in CO₂ diffusion the phenyl groups moves in a larger range than in CH₄ diffusion. The density profile of gas molecules that the phenyl groups see is analyzed using double layer phenyl groups . The results show that the number of phenyl groups cannot affect the permeation. In the meso scale study a mixed mechanism model with a grid framework is developed to model the permeation process. In the model the membrane is assumed to consist of various grids which follow three major diffusion mechanisms. Models with different grid sizes are employed for the four membranes. Parameters in each model are estimated from the permeance results of the two gases. By comparing the estimated parameters in the surface diffusion mechanism with the reported values, the acceptable grid models are determined and the models with the minimum number of grids are studied. The diffusion is dominated by the activated Knudsen diffusion mechanism at lower temperatures and follows the surface diffusion mechanism when the temperature is above a critical value. In the diffusion of both gases within the four membranes the surface diffusion portion is very close but the activated Knudsen diffusion portion is not. This explains why the permeation with high selectivity occurs at lower temperatures. By comparing the results it shows the two studies can validate each other. On the other hand the two methods can be complementary as the diffusion model is able to predict the permeance within the right range and the MD model is able to predict the selectivity more accurately.
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    Solution-casting of Disulfonated Poly(arylene ether sulfone) Multiblock Copolymer Films for Proton Exchange Membranes
    Lee, Myoungbae (Virginia Tech, 2009-04-27)
    The overall objective of the project, on which this thesis is based, is to develop a novel hydrocarbon-based proton exchange membrane (PEM) material that can produce a proton conductivity of 0.1 S/cm at the operating conditions of 50 % relative humidity and 120 oC, which is the performance target set by the U.S. DOE for automotive application. As a part of this project, our efforts have been focused on the investigation of the effects of solution-casting conditions on the final morphology and properties of disulfonated poly(arylene ether sulfone) multiblock copolymer films from the viewpoint of phase separation of block copolymers. Of equal importance to this work, is a possibility of utilizing a rheological technique for monitoring the transformation and kinetics of block copolymers during solvent removal process, which was initially examined in order to provide fundamental quantitative understanding and practical information on the solvent removal process. Our results demonstrated that solvent selectivity and drying temperature as well as the block length had considerable effects on the final morphology and properties. The proton conductivity could be significantly increased by simply utilizing a selective solvent, dimethylacetamide (DMAC), which is good and marginal for the sulfonated and unsulfonated blocks, respectively, rather than N-methyl-2-pyrrolidone (NMP), a neutral solvent for both blocks. The drying temperature was also observed to have considerable effects on the final properties, being coupled with the effects of solvent selectivity. Also, it was shown that the multiblock copolymer consisting of longer blocks was more sensitive to the processing conditions. From the morphological study using transmission electron microscopy and small-angle X-ray scattering, evidences for the above observations were obtained. In the second part of this dissertation, the evolution of GÎ and GË of the solutions of a styrene-butadiene-styrene (SBS) triblock copolymer in toluene was obtained as a function of concentration using a modified parallel-plate device and a rheology test scheme developed in this study in an effort to quantify the phase separation kinetics. Then, the information on the phase transformation and kinetics of the SBS block copolymer in the solution was obtained by analyzing the GÎ and GË data with the Avrami equation. The Avrami exponent was found to be approximately 1, which indicates that the phase transformation occurred by a one-dimensional growth mechanism. The rate constant showed a strong concentration-dependence. After the initial increase up to 45 vol %, the rate constant drastically decreased and, finally, converged to 0 at 70 vol %. It is believed that, at the concentration range below 45 vol %, the phase separation became more intense as the polymer molecules had more chances to interact owing to the concentration increase. However, above 45 vol %, the phase transformation became weaker due to the limited mobility of the polymer molecules, which finally led to a “kinetically frozen-in” structure, in which the polymer molecules could not move any longer. Thus, it can be concluded that the solvent removal rate is one of the dominant factors that decide the final microstructures of solution-cast block copolymer films.
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    Sorption, Transport and Gas Separation Properties of Zn-Based Metal Organic Frameworks (MOFs) and their Application in CO₂ Capture
    Landaverde Alvarado, Carlos Jose (Virginia Tech, 2016-10-13)
    Adsorption, separation and conversion of CO₂ from industrial processes are among the priorities of the scientific community aimed at mitigating the effects of greenhouse gases on the environment. One of the main focuses is the capture of CO₂ at stationary point sources from fossil fuel emissions using porous crystalline materials. Porous crystalline materials can reduce the energy costs associated with CO₂ capture by offering high adsorption rates, low material regeneration energy penalties and favorable kinetic pathways for CO₂ separation. MOFs consist of polymeric inorganic networks with adjustable chemical functionality and well-defined pores that make them ideal for these applications. The objective of this research was to test the potential for CO₂ capture on Zn-based MOFs by studying their sorption, transport and gas separation properties as adsorbents and continuous membranes. Three Zn-based MOFs with open Zn-metal sites were initially studied. Zn4(pdc)4(DMF)2•3DMF (1) exhibited the best properties for CO₂ capture and was investigated further under realistic CO₂ capture conditions. The MOF exhibited preferential CO₂ adsorption based on a high enthalpy of adsorption and selectivity of CO₂ over N₂ and CH₄. Sorption dynamics of CO₂ indicated fast adsorption and a low activation energy for sorption. Diffusion inside the pores is the rate-limiting step for diffusion, and changes in the process temperature can enhance CO₂ separation. Desorption kinetics indicated that CO₂ has longer residence times and lower activation energies for desorption than N₂ and CH₄. This suggests that the selective adsorption of CO₂ is favored. MOF/Polymer membranes were synthesized via a solvothermal method with structural defects sealed by a polymer coating. This method facilitates the permeation measurements of materials that cannot form uniform-defect-free layers. The membrane permeation of CO₂, CH₄, N₂ and H₂ exhibited a linear relation to the inverse square root of the molecular weight of the permanent gases, indicating that diffusion occurs in the Knudsen regime. Permselectivity was well-predicted by the Knudsen model with no temperature dependence, and transport occurs inside the pores of the membrane. MOF (1) exhibits ideal properties for future applications in CO₂ capture as an adsorbent.
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    Sustainable Water through Innovation in Membranes & Materials (SWIMM)
    Martin, Stephen M.; Baird, Donald G.; Achenie, Luke E. K.; Deshmukh, Sanket A.; Foster, Earl Johan; He, Jason; Vikesland, Peter J.; Edwards, Marc A.; Deitrich, Andrea; Dillard, David A.; Lesko, John J.; Moore, Robert Bowen; Long, Timothy E.; Riffle, Judy S.; Morris, Amanda J.; Cheng, Shengfeng; Edgar, Kevin J.; Moeltner, Klaus; Xia, Kang; Stewart, Ryan D.; Badgley, Brian D.; Hedrick, Valisa E.; Gohlke, Julia M.; Duncan, Susan E. (Virginia Tech, 2017-05-15)
    Water scarcity is mainly caused by overwhelming human consumption and contamination, from production of water-thirsty meats and vegetables, biofuel crop production, industrial uses, and rapid urbanization. The scale of water scarcity makes it an interconnected global issue and efforts to minimize the gap between water supply and demand are critical...
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    Synthesis and characterization of metallic nanoparticles with photoactivated surface chemistries
    Abtahi, Seyyed Mohammad Hossein (Virginia Tech, 2013-12-19)
    During recent decades metallic nanoparticles have been found very interesting due to their unique characteristics which make them suitable for different applications. In this research, for the very first time, we tried to perform selective surface photo activation chemistry on the targeted facets of nanoparticles while they are in suspension. This technique enabled us to form desired assemblies of nanoparticles. We focused on elongated shaped gold nanorod due to its unique surface plasmon resonance and probable biomedical applications. In this research we formed a dumbbell shape assembly of nanoparticles in suspension. A probable application for these assemblies can be in vivo imaging. Initially, we reproduced gold nanorods using existing techniques in prior papers and optimized them according to our research needs. A low rpm centrifugal separation technique was developed to efficiently separate synthesized gold nanorods from other shapes. Several characterization techniques were utilized to characterize nanoparticles at each step including UV-absorbance, zeta potential, and dynamic light scattering. Different generations of oligomers were synthesized to be used as gold nanorods coating, and each coating was tested and characterized using appropriate techniques. Our two-step coating replacement method using one of these photocleavable oligomers enabled us to achieve, for the very first time, selective UV photo activation of gold nanorod tips. The photo activated tips were then exposed to oppositely charged gold nanospheres to form dumbbell shape assemblies of gold nanorods and nanospheres. Furthermore, dumbbell shape assembly of nanoparticles was investigated and characterized.
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    Temperature-Dependent Gas Transport Behavior in Cross-Linked Liquid Crystalline Polyacrylate Membranes
    Rabie, Feras; Poláková, Lenka; Fallas, Sebastian; Sedlakova, Zdenka; Marand, Eva; Martin, Stephen M. (MDPI, 2019-08-20)
    Stable, cross-linked, liquid crystalline polymer (LCP) films for membrane separation applications have been fabricated from the mesogenic monomer 11-(4-cyanobiphenyl-4′-yloxy) undecyl methacrylate (CNBPh), non-mesogenic monomer 2-ethylhexyl acrylate (2-EHA), and cross-linker ethylene glycol dimethacrylate (EGDMA) using an in-situ free radical polymerization technique with UV initiation. The phase behavior of the LCP membranes was characterized using differential scanning calorimetry (DSC) and X-ray scattering, and indicated the formation of a nematic liquid crystalline (LC) phase above the glass transition temperature. The single gas transport behavior of CO2, CH4, propane, and propylene in the cross-linked LCP membranes was investigated for a range of temperatures in the LC mesophase and the isotropic phase. Solubility of the gases was dependent not only on the condensability in the LC mesophase, but also on favorable molecular interactions of penetrant gas molecules exhibiting a charge separation, such as CO2 and propylene, with the ordered polar mesogenic side chains of the LCP. Selectivities for various gas pairs generally decreased with increasing temperature and were discontinuous across the nematic–sotropic transition. Sorption behavior of CO2 and propylene exhibited a significant change due to a decrease in favorable intermolecular interactions in the disordered isotropic phase. Higher cross-link densities in the membrane generally led to decreased selectivity at low temperatures when the main chain motion was limited by the lack of mesogen mobility in the ordered nematic phase. However, at higher temperatures, increasing the cross-link density increased selectivity as the cross-links acted to limit chain mobility. Mixed gas permeation measurements for propylene and propane showed close agreement with the results of the single gas permeation experiments.
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    Thermoreversible Gelation, Crystallization and Phase Separation Kinetics in Polymer Solutions under High Pressure
    Fang, Jian (Virginia Tech, 2008-09-10)
    This thesis is an experimental investigation of phase behavior, crystallization, gelation and phase separation kinetics of polymer solutions in dense fluids at high pressures. The miscibility and dynamics of phase separation were investigated in solutions of atactic polystyrene with low polydispersity (Mw = 129,200; PDI = 1.02) in acetone. Controlled pressure quench experiments were conducted at different polymer concentrations to determine both the binodal and the spinodal envelops using time- and angle resolved light scattering techniques. At each concentration, a series of rapid pressure quenches with different penetration depths in a range from 0.1 MPa to 3 MPa were imposed and the time evolution of the angular distribution of the scattered light intensities was monitored. The solution with 11.4 wt % polymer concentration underwent phase separation by spinodal decomposition mechanism for both shallow and deep quenches. Below this critical polymer concentration, phase separation was found to proceed by nucleation and growth mechanism for shallow quenches, but by spinodal decomposition for deeper quenches. Gelation and crystallization processes and the influence of pressure and the fluid [Cho et al. 1993]composition were investigated in solutions of poly(4-methyl-1-pentene) [P4MP1] in n-pentane + CO₂ and in solutions of syndiotactic polystyrene [sPS] in toluene + CO₂, and also in acetophenone + CO₂ fluid mixtures over a pressure range up to 55 MPa and carbon dioxide levels up to 50 wt %. In pure pentane, P4MP1 undergoes crystallization and leads to Form III polymorph at low pressures, but to Form II at high pressures. In n-pentane + CO₂ mixture fluids, the polymorphic state changes from a mixture of Forms III and II to Form II and eventually to Form I with increasing CO₂ content. High level of carbon dioxide (≥40 wt %) in the solution was found to lead to gelation instead of crystallization. No liquid-liquid phase boundaries could be observed in any of the P4MP1 solutions. In contrast to P4MP1 in n-pentane, syndiotactic polystyrene was found to undergo gelation in toluene or acetophenone forming a polymer-solvent compound with the δ crystal form. Also in contrast to P4MP1 systems, addition of carbon dioxide to sPS solutions alters the process from that of gelation to crystallization leading to the β crystal form. In solutions with high CO₂ level, in addition to the gelation or crystallization boundaries, a liquid-liquid phase separation boundary was also observed. The phase separation path followed was found to influence the eventual morphology and the crystal state of the polymer. In sPS solutions in toluene + CO₂, if the sol-gel boundary were crossed first by cooling the solution at a fixed pressure, the resulting morphology was found to be fibrillar and the polymer displayed the δ crystal form. If instead, the liquid—liquid phase boundary were crossed first by reducing pressure at a fixed temperature, the polymer-rich phase leads to a stacked-lamellar morphology with the β crystal form while the polymer-lean phase leads to a mixed morphology with lamellar layers connected by fibrils with the polymer displaying δ + β crystal forms. In solutions in acetophenone + carbon dioxide, when the gelation boundary is crossed first, the resulting structure is the δ form as in the toluene + CO₂ case. At comparable CO₂ levels, when the L-L phase boundary is crossed first, in the acetophenone system, polymer-rich phase was found to generate a mixture of δ + β forms while only the δ form was found in the polymer-lean phase, in contrast to the observations in the toluene + CO₂ systems. Based on crystallographic, spectral and microscopic data, a thermodynamic framework was developed which provides a mechanistic account for the formation of the different polymorphs.