Browsing by Author "Walz, John Y."

Now showing 1 - 20 of 32
  • Thumbnail Image
    AFM surface force measurements between hydrophobized gold surfaces
    Wang, Jialin (Virginia Tech, 2008-09-08)
    In 1982, Israelachvili and Pashley reported the first measurements of a hitherto unknown attractive force between two mica surfaces hydrophobized in cetyltrimethylammonium bromide (CTAB) solutions. Follow-up experiments conducted by many investigators confirmed their results, while others suggested that the "hydrophobic force" is an artifact due to nanobubbles (or cavitation). Evidences for the latter included the discontinuities (or steps) in the force versus distance curves and the pancake-shaped nano-bubbles seen in atomic force microscopic (AFM) images. Recent measurements conducted in degassed water showed, however, smooth force versus distance curves, indicating that the hydrophobic force is not an artifact due to nanobubbles.1, 2 Still other investigators3, 4 suggested that the long-range attraction observed between hydrophobic surfaces is due to the correlation between the patches of adsorbed ionic surfactant and the patches of unoccupied surface. For this theory to work, it is necessary that the charged patches be laterally mobile to account for the strong attractive forces observed in experiment. In an effort to test this theory, AFM force measurements were conducted with gold substrates hydrophobized by self-assembly of alkanethiols and xanthates of different chain lengths. The results showed long-range attractions despite the fact that the hydrophobizing agents chemisorb on gold and, hence, the adsorption layer is immobile. When the gold surfaces were hydrophobized in a 1 Ã 10-3 M thiol-in-ethanol solution for an extended period of time, the force curves exhibited steps. These results indicate that the long-range attractions are caused by the coalescence of bubbles, as was also reported by Ederth.5 The steps disappeared, however, when the species adsorbed on top of the chemisorbed monolayer were removed by solvent washing, or when the gold substrates were hydrophobized in a 1 Ã 10-5 M solution for a relatively short period of time. AFM force measurements were also conducted between gold substrates coated with short-chain thiols and xanthates to obtain hydrophobic surfaces with water contact angles (ï ±) of less than 90o. Long-range attractions were still observed despite the fact that cavitation is thermodynamically not possible. Having shown that hydrophobic force is not due to coalescence of pre-existing bubbles, cavitation, or correlation of charged patches, the next set of force measurements was conducted in ethanol-water mixtures. The attractive forces became weaker and shorter-ranged than in pure water and pure ethanol. According to the Derjaguin's approximation6, an attractive force arises from the decrease in the excess free energy (ï §f) of the thin film between two hydrophobic surfaces.7 Thus, the stronger hydrophobic forces observed in pure water and pure ethanol can be attributed to the stronger cohesive energy of the liquid due to stronger H-bonding. Further, the increase in hydrophobic force with decreasing separation between two hydrophobic surfaces indicates that the H-bonded structure becomes stronger in the vicinity of hydrophobic surfaces. The force measurements conducted at different temperatures in the range of 10-40C showed that the hydrophobic attraction between macroscopic surfaces causes a decrease in film entropy (Sf), which confirms that the hydrophobic force is due to the structuring of water in the thin film between two hydrophobic surfaces. The results showed also that the hydrophobic interaction entails a reduction in the excess film enthalpy (Hf), which may be associated with the formation of partial (or full) clathrates formed in the vicinity of hydrophobic surfaces. The presence of the clathrates is supported by the recent finding that the density of water in the vicinity of hydrophobic surfaces is lower than in the bulk.8
  • Thumbnail Image
    Albumin Adsorption: Inferences of Protein Interactions Measured by Sedimentation both Between Species and Induced by Denaturing
    McKeon, Kristin Dianne (Virginia Tech, 2008-04-18)
    Biological development and progression are managed by a diverse macromolecular group called proteins. Protein structure results from a complex folding process that leads to a final active form. This protein state is susceptible to changes in the surrounding environment and an incorrect structure can be produced. Changes in the protein conformation can lead to the formation of protein aggregates. Adsorption of proteins onto surfaces is utilized in many research analyses, but is capable of irreversibly changing the protein structure and causing aggregation. Albumin is a plasma protein that adsorbs on many different surfaces because the structure easily rearranges. The structure of albumin once adsorbed has been shown to deteriorate; however, outcomes of both stabilization and aggregation have been found. A dynamic laser light scattering instrument will be utilized to measure the differences in size and determine the amount of aggregation. Our lab has developed a z-axis translating laser light scattering device (ZATLLS) that has been used to measure the sedimentation velocity of several different materials in solution. In this case, bovine serum albumin (BSA) will be adsorbed onto polystyrene particles and the particle settling velocity determined. The settling solution viscosity and density will also be ascertained, so Stoke's law can infer the average aggregate size of each experiment. BSA-coated polystyrene particles displayed a more controlled settling behavior compared to non-coated polystyrene particles. Although the BSA-coated particles had a smaller sedimentation velocity, a larger aggregate size was found due to the greater solution viscosity. Therefore, the ZATLLS instrument can be employed to measure sedimentation velocities of multiple interactions and the aggregation level inferred. Although most albumin molecules are remarkably similar, there are subtle differences in amino acid residues, length, and charge. Sedimentation velocities for human serum albumin (HSA) coated polystyrene particles and BSA-coated polystyrene particles only had a small difference. However an almost 50% higher solution viscosity was measured in BSA experiment solutions, and resulted in the slower settling of the larger aggregates compared to HSA-coated particles. Viscosity calibration curves for each albumin species were used to determine the amount of protein desorbed from the particles during the settling process. The larger solution viscosity for BSA-coated particle experiments led to a much larger degree of desorption. HSA was shown to be the more stable albumin species when adsorbed onto polystyrene particles. Temperature denaturing was performed to aid in the determination of the stability of BSA. Reversible and irreversible conformational changes in BSA were produced at 46ºC and 76ºC respectively. The solutions were cooled to room temperature before adsorption ontopolystyrene particles and the sedimentation velocities measured. A 50% difference in average viscosity between the reversibly and irreversibly changed BSA was found. This caused the larger aggregates formed in the 76ºC BSA experiments to have an almost equivalent sedimentation velocity to those in the reversibly denatured BSA experiments. Average aggregate size for reversibly denatured BSA was well within the ranges found for non-denatured BSA. In conclusion, irreversibly denatured BSA formed larger aggregates and was more likely to desorb from the polystyrene particles than reversibly changed BSA.
  • Thumbnail Image
    Catalytic Hydrodeoxygenation of Bio-Oil Model Compounds (Ethanol, 2-Methyltetrahydrofuran) over Supported Transition Metal Phosphides
    Bui, Phuong Phuc Nam (Virginia Tech, 2013-01-24)
    The objective of this project is to investigate hydrodeoxygenation (HDO), a crucial step in the treatment of bio-oil, on transition metal phosphide catalysts. The study focuses on reactions of simple oxygenated compounds present in bio-oil -- ethanol and 2-methyltetrahydrofuran (2-MTHF). The findings from this project provide fundamental knowledge towards the hydrodeoxygenation of more complex bio-oil compounds. Ultimately, the knowledge contributes to the design of optimum catalysts for upgrading bio-oil. A series of transition metal phosphides was prepared and tested; however, the focus was on Ni2P/SiO2. Characterization techniques such as X-ray diffraction (XRD), temperature-programmed reduction and desorption (TPR and TPD), X-ray photoelectron spectroscopy (XPS), and chemisorption were used. In situ Fourier transform infrared (FTIR) spectroscopy was employed to monitor the surface of Ni2P during various experiments such as: CO and pyridine adsorption and transient state of ethanol and 2-MTHF reactions. The use of these techniques allowed for a better understanding of the role of the catalyst during deoxygenation.
  • Thumbnail Image
    Controlling Colloidal Stability using Highly Charged Nanoparticles
    Herman, David J. (Virginia Tech, 2015-02-27)
    This dissertation focused on the potential use of highly charged nanoparticles to stabilize dispersions of weakly charged microparticles. The experimental components of the project centered on a model colloidal system containing silica microparticles at the isoelectric point where the suspensions are unstable and prone to flocculation. The stability of the silica suspensions was studied in the presence of highly charged nanoparticles. Initial experiments used polystyrene latex with either sulfate or amidine surface groups. Effective zeta potentials were measured with nanoparticle concentrations ranging from 0.001% to 0.5% vol. Adsorption levels were determined through direct SEM imaging of the silica microparticles, showing that the nanoparticles directly adsorbed to the microparticles (amidine more than sulfate), producing relatively large effective zeta potentials. However, stability experiments showed that the latex nanoparticles did not stabilize the silica but merely provided a reduction in overall flocculation rate. It was concluded that the zeta potential was an insufficient predictor of stability as there was still sufficient patchiness on the surface to allow for the silica surfaces to aggregate. Experiments using zirconia and alumina nanoparticles did achieve effective stabilization; both types stabilized the silica suspensions for longer than the observation period of approximately 15 hours. Stability was observed at concentrations of 10^-4% to 1.0% (zirconia) and 10^-2% vol. (alumina). These particles adsorbed directly to the microparticles (confirmed via SEM) and produced increasing effective zeta potentials with increasing nanoparticle concentrations. The adsorption resulted in significant electrostatic repulsion that was determined to be effectively irreversible using colloidal probe AFM. The improved stabilizing ability was attributed to the increased van der Waals attraction between the oxide nanoparticles (compared to polystyrene). Finally, an unexpected result of the CP-AFM force measurements showed that the repulsive forces between a nanoparticle-coated particle and plate lacked the normal dependence on the radius of the probe as predicted by the Derjaguin approximation. The forces observed in nanoparticle suspensions were virtually identical for 5 µm and 30 µm probes. Based on calculations of the shear rate in the gap, it was theorized that this phenomenon may have resulted from the shearing of adsorbed particles from the surfaces, which leads to similar interaction geometries for the two probe sizes.
  • Thumbnail Image
    A correlation force spectrometer for single molecule measurements under tensile load
    Radiom, Milad; Honig, Christopher D. F.; Walz, John Y.; Paul, Mark R.; Ducker, William A. (American Institute of Physics, 2013-01-07)
    The dynamical-mechanical properties of a small region of fluid can be measured using two closely spaced thermally stimulated micrometer-scale cantilevers. We call this technique correlation force spectroscopy (CFS). We describe an instrument that is designed for characterizing the extensional properties of polymer molecules that straddle the gap between the two cantilevers and use it to measure the stiffness and damping (molecular friction) of a dextran molecule. The device is based on a commercial atomic force microscope, into which we have incorporated a second antiparallel cantilever. The deflection of each cantilever is measured in the frequency range dc-1 MHz and is used to generate the cross-correlation at equilibrium. The main advantage of cross-correlation measurements is the reduction in thermal noise, which sets a fundamental noise limit to force resolution. We show that the thermal noise in our cross-correlation measurements is less than one third of the value for single-cantilever force microscopy. The dynamics of the cantilever pair is modeled using the deterministic motion of a harmonic oscillator initially displaced from equilibrium, which yields the equilibrium auto and cross-correlations in cantilever displacement via the fluctuation-dissipation theorem. Fitted parameters from the model (stiffness and damping) are used to characterize the fluid at equilibrium, including any straddling molecules. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4772646]
  • Thumbnail Image
    Correlation Force Spectroscopy for Single Molecule Measurements
    Radiom, Milad (Virginia Tech, 2014-07-24)
    This thesis addresses development of a new force spectroscopy tool, correlation force spectroscopy (CFS), for the measurement of the mechanical properties of very small volumes of material (molecular to µm³) at kHz-MHz time-scales. CFS is based on atomic force microscopy (AFM) and the principles of CFS resemble those of dual-trap optical tweezers. CFS consists of two closely-spaced micro-cantilevers that undergo thermal fluctuations. Measurement of the correlation in thermal fluctuations of the two cantilevers can be used to determine the mechanical properties of the soft matter, e.g. a polymeric molecule, that connects the gap between the two cantilevers. Modeling of the correlations yields the effective stiffness and damping of the molecule. The resolution in stiffness is limited by the stiffness of the cantilever and the frequency by the natural frequency of the cantilevers, but, importantly, the damping resolution is not limited by the damping of the cantilever, which has enabled high-resolution measurements of the internal friction of a polymer. The concept of CFS was originally presented by Roukes' group in Caltech [Arlett et al., Lecture Notes in Physics, 2007]; I developed the first practical versions of CFS for experimentation, and have used it in two applications (1) microrheology of Newtonian fluids and (2) single molecule force spectroscopy. To understand the correlation in thermal fluctuations of two cantilevers I initially validated the theoretical approach for analyzing correlation in terms of deterministic model using the fluctuation-dissipation theorem [Paul and Cross, PRL, 2004]. I have shown that the main advantages of such correlation measurements are a large improvement in the ability to resolve stiffness and damping. Use of CFS as a rheometer was validated by comparison between experimental data and finite element modeling of the deterministic vibrations of the cantilevers using the known viscosity and density of fluids. Work in this thesis shows that the data can also be accurately fitted using a simple harmonic oscillator model, which can be used for rapid rheometric measurements, after calibration. The mechanical properties of biomolecules such as dextran and single stranded DNA (ssDNA) are also described. CFS measurements of single molecule properties of ssDNA reveal the internal friction of the molecule in solution.
  • Thumbnail Image
    Correlations between the thermal vibrations of two cantilevers: Validation of deterministic analysis via the fluctuation-dissipation theorem
    Honig, Christopher D. F.; Radiom, Milad; Robbins, Brian A.; Walz, John Y.; Paul, Mark R.; Ducker, William A. (AIP Publishing, 2012-02-01)
    We validate a theoretical approach for analyzing correlations in the fluctuations of two cantilevers in terms of a deterministic model, using the fluctuation-dissipation theorem [M. R. Paul and M. C. Cross, Phys. Rev. Lett. 92, 235501 (2004)]. The validation has been made possible through measurement of the correlations between the thermally stimulated vibrations of two closely spaced micrometer-scale cantilevers in fluid. Validation of the theory enables development of a method for characterizing fluids, which we call correlation force spectrometry. (C) 2012 American Institute of Physics. [doi:10.1063/1.3681141]
  • Thumbnail Image
    The Design of Stable, Well-Defined Polymer-Magnetite Nanoparticle Systems for Biomedical Applications
    Miles, William Clayton (Virginia Tech, 2009-08-10)
    The composition and stability of polymer-magnetite complexes is essential for their use as a treatment for retinal detachment, for drug targeting and delivery, and for use as a MRI contrast agent. This work outlines a general methodology to design well-defined, stable polymer-magnetite complexes. Colloidal modeling was developed and validated to describe polymer brush extension from the magnetite core. This allowed for the observation of deviations from expected behavior as well as the precise control of polymer-particle complex size. Application of the modified Derjaguin-Verwey-Landau-Overbeek (DLVO) theory allowed the determination of the polymer loading and molecular weight necessary to sterically stabilize primary magnetite particles. Anchoring of polyethers to the magnetite nanoparticle surface was examined using three different types of anchor groups: carboxylic acid, ammonium, and zwitterionic phosphonate. As assessed by dynamic light scattering (DLS), the zwitterionic phosphonate group provided far more robust anchoring than either the carboxylic acid or ammonium anchor groups, which was attributed to an extremely strong interaction between the phosphonate anchor and the magnetite surface. Coverage of the magnetite surface by the anchor group was found to be a critical design variable for the stability of the zwitterionic phosphonate groups, and the use of a tri-zwitterionic phosphonate anchor provided stability in phosphate buffered saline (PBS) for a large range of polymer loadings. Incorporation of an amphiphlic poly(propylene oxide)-b-poly(ethyelene oxide) (PPO-b-PEO) diblock copolymer attached to the magnetite surface was examined through colloidal modeling and DLS. The relaxivity of the complexes was related to aggregation behavior observed through DLS. This indicated the presence of a hydrophobic interaction between the PPO layers of neighboring complexes. When this interaction was large enough, the complexes exhibited an increased relaxivity and cellular uptake. Thus, we have developed a methodology that allows for design of polymer-magnetite complexes with controlled sizes (within 8% of predicted values). Application of this methodology incorporated with modified DLVO theory aids in the design of colloidally stable complexes with minimum polymer loading. Finally, determination of an anchor group stable in the presence of phosphate salts at all magnetite loadings allows for the design of materials with minimum polymer loadings in biological systems.
  • Thumbnail Image
    Development of the Evanescent Wave Atomic Force Microscope
    Clark, Spencer C. (Virginia Tech, 2005-07-26)
    The conventional atomic force microscope (AFM) is equipped with a single optical detection system. Probe-sample separation is determined in an independent deflection with respect to AFM z-translation experiment. This method of determining probe-surface separation is relative, susceptible to drift and does not provide real time separation information. The evanescent wave atomic force microscope (EW-AFM) utilizes a second, independent detection system to determine absolute probe-surface separation in real time. The EW-AFM can simultaneously acquire real-time force and probe-sample separation information using the optical lever and evanescent scattering detection systems, respectively. The EW-AFM may be configured with feedback on the optical-lever system for constant force applications or with feedback on evanescent wave scattering intensity for constant height applications. Scattering of the evanescent wave exponential decay profile is used to determine probe-surface separation. Sub-micron sized dielectric and metallic probes show exponential scattering profiles, micron sized polystyrene and borosilicate microspheres show non-exponential profiles when they are affixed beneath the cantilever tip. By affixing the microspheres to the end of the AFM cantilever exponential and non-exponential profiles were observed. The EW-AFM can be used to conduct force-distance and imaging experiments. The EW-AFM was used to measure the thickness of surfactant bilayers formed at the silica-solution interface using silicon nitride AFM tips. The presence of a refractive index difference between the surfactant bilayer and the solution does not influence the accuracy of the surfactant bilayer thickness measurement. The EW-AFM was used to scan a 2 x 2 micron area in constant height mode. The probe was brought to within 6 nanometers of a planar dielectric surface using the evanescent wave intensity as a height reference with accuracy of ± 1 nm. This capability may be utilized to observe charge heterogeneity at the solid-liquid interface with nanometer lateral resolution or to map chemical functional group heterogeneity based on perturbations to the electrical double layer. The EW-AFM evanescent scattering system has an absolute separation resolution of 0.3 nm compared to 1.0 nm relative separation resolution for the optical lever system. In constant scattering (constant height) mode the real time separation precision is about 2 nm.
  • Thumbnail Image
    The Dynamic Behavior of a Concentrated Composite Fluid Containing Non-Brownian Glass Fibers in Rheometrical Flows
    Eberle, Aaron Paul Rust (Virginia Tech, 2008-07-08)
    With this research, we work towards the overall objective of being able to accurately simulate fiber orientation in complex flow geometries of composite fluids of industrial significance. The focus of this work is to understand the rheological behavior of these materials and its connection to fiber orientation as determined in simple shear flow. The work includes the development of a novel approach to characterizing the transient rheology; an experimental study of the relationship between the stress growth functions in startup of flow and the fiber orientation; a critical assessment of the limitations of current fiber suspension theory; and an approach to determining unambiguous model parameters by fitting. A key difference between the rheological studies performed in this work and others is the use of a cone-and-plate device combined with "donut" shaped samples (CP-D) to prevent boundary effects on the measurement. The conventional method for obtaining transient rheological data is to use parallel disk (PP) geometry set at a gap where the measurements are independent of disk spacing. However, this work suggests that the inhomogeneous velocity gradient imposed by the PP geometry induces excessive fiber-fiber contact contributing to exaggerated measurements of the stress growth functions. An experimental study of the transient rheological behavior of a 30 wt% short glass fiber-filled polybutylene terephthalate was performed using the CP-D. Stress growth measurements during startup of flow were performed in combination with direct measurement of the fiber orientation to determine the relationship between the transient rheology and the fiber microstructure. The well defined fiber orientation and rheological experiments allowed for a quantitative assessment of current fiber suspension theory. Comparison between the experimental fiber orientation and predictions based on Jeffery's equation and the Folgar-Tucker model show that the fiber orientation evolves much slower than predicted. In addition, the addition of a "slip" term improved the agreement between the predictions and experimental results. Predictions using the Lipscomb model coupled with the Folgar-Tucker model, with slip, were fit to the transient stresses to determine the feasibility of fitting unambiguous model parameters for a specific composite fluid. Model parameters determined by fitting at a shear rate of 6 s-1 allowed for reasonable predictions of the transient stresses in flow reversal experiments at all the shear rates tested.
  • Thumbnail Image
    Fabrication of Ultrathin Palladium Composite Membranes by a New Technique and Their Application in the Ethanol Steam Reforming for H₂ Production
    Yun, Samhun (Virginia Tech, 2011-03-21)
    This thesis describes a new technique for the preparation of ultrathin Pd based membranes supported on a hollow-fiber α-alumina substrate for H₂ separation. The effectiveness of the membranes is demonstrated in the ethanol steam reforming (EtOH SR) reaction in a membrane reactor (MR) for H₂ production. The membrane preparation technique uses an electric-field to uniformly deposit Pd nanoparticle seeds on a substrate followed by deposition of Pd or Pd-Cu layers on the activated surface by electroless plating (ELP). The well distributed Pd nanoparticles allow for enhanced bonding between the selective layer and the substrate and the formation of gas tight and thermally stable Pd or Pd-Cu layers as thin as 1 µm, which is a record in the field. The best Pd membrane showed H₂ permeance as high as 5.0 × 10⁶ mol m²s⁻¹Pa⁻¹ and stable H²/N₂ selectivity of 9000 - 7000 at 733 K for 5 days. The Pd-Cu alloy membrane showed H₂ permeance of 2.5 × 10⁶ mol m⁻²s⁻¹Pa⁻¹ and H₂/N₂ selectivity of 970 at the same conditions. The reaction studies were carried out with a Co-Na/ZnO catalyst both in a packed bed reactor (PBR) and in a MR equipped with the Pd or Pd-Cu membrane to evaluate the benefits of employing membranes. For all studies, ethanol conversion and hydrogen product yields were significantly higher in the MRs compared to the PBR. Average ethanol conversion enhancement and hydrogen molar flow enhancement were measured to be 12 % and 11 % in the Pd MR and 22 % and 19 % in the Pd-Cu MR, respectively. These enhancements of the conversion and product yield can be attributed to the shift in reaction equilibria by continuous hydrogen removal by the Pd based membranes. The comparative low enhancement in the Pd MR was found to be the result of significant contamination of Pd layer by CO or carbon compounds deposition during the reaction. A one-dimensional modeling of the MR and the PBR was conducted using identical conditions and their performances were compared with the values obtained from the experimental study. The model was developed using a simplified power law and the predicted values matched experimental data with only minor deviations indicating that the model was capturing the essential physicochemical behavior of the system. Enhancements of ethanol conversion and hydrogen yield were observed to increase with rise in space velocity (SV), which could be explained by the increase in H₂ flux through the membranes with SV in the MRs.
  • Thumbnail Image
    Forces and Stability in Ternary Colloidal Systems: Evidence of Synergistic Effects
    Ji, Shunxi (Virginia Tech, 2014-05-06)
    Understanding and controlling the forces between colloidal particles in solution, along with the resulting stability of a dispersion of such particles, continues to be at topic of great interest. Although most laboratory studies focus on model systems in which the number of system species is kept to a minimum, real colloidal systems can be much more complex, consisting of multiple components that can vary greatly in size, charge, shape, etc. This dissertation focused on a topic that has received very little prior study, namely synergistic effects that can arise in mixed colloidal systems in which the resulting force and stability of the system cannot be predicted using results obtained in more idealized systems consisting of fewer components. Two specific systems were studied. The first was a ternary system of particles in which micron-sized particles were in a dispersion containing both nanoparticles and submicron particles. It was shown through both computation modeling and direct force measurements that the nanoparticles can create attractive forces between the micron and submicron particles such that a halo of submicron particles is formed. This halo results in long range forces between the microparticles that cannot be predicted from measurements in systems containing only nanoparticles or only submicron particles. In addition, the forces can be large enough to alter the stability of a dispersion of these microparticles. The second system consisted of microparticles in a solution containing nanoparticles and a polyelectrolyte, specifically poly(acrylic) acid. Again, through modeling and experimentation, it was found that complexation of the nanoparticles and polyelectrolyte molecules led to depletion and structural forces between the microparticles that were substantially greater than the sum of the forces measured in systems of only nanoparticles or only polyelectrolyte. It was also found that these greater forces could lead to destabilization of a dispersion of microparticles that was stable when only nanoparticles or only polyelectrolyte was present. While these results clearly demonstrate the difficulty associated with predicting forces and stability in mixed colloidal systems, they also indicate that such systems offer new and interesting opportunities for controlling stability that clearly warrant additional study.
  • Thumbnail Image
    Growth of anodic alumina nanopores and titania nanotubes and their applications
    Chen, Bo (Virginia Tech, 2013-01-07)
    Anodic aluminum oxide (AAO) nanopores are excellent templates to fabricate different nanostructures. However, the pores are limited to a hexagonal arrangement with a domain size of a few micrometers.  In this dissertation, focused ion beam (FIB) is used to create pre-patterned concaves to guide the anodization. Due to the advantage of FIB lithography, highly ordered AAO arrays with different arrangements, alternating diameters, and periodic pore densities are successfully achieved. Anodization window to fabricate ordered AAO is enlarged due to the FIB pre-pattern guidance. AAO has also been successfully used as a template to nanoimprint prepolymer to synthesize vertically aligned and high aspect ratio h-PDMS nanorod arrays with Moiré pattern arrangements. The formation mechanism of anodic TiO2 nanotubes is proposed in this dissertation. Moreover, FIB pre-pattern guided anodization is introduced to synthesize highly ordered TiO₂ nanotubes with different morphologies. The effects of inter-tube distance and arrangement to the structure of TiO₂ nanotubes are investigated. TiO2 nanotubes with branched and bamboo-type structures are achieved by adjusting anodization voltage. The influence of patterned concave depth and surface curvature on the growth of TiO₂ nanotubes and AAO are studied. The efficiency of TiO₂ nanotubes in supercapacitors and photoelectrochemical water splitting are optimized by enlarging surface area and increasing electrical conductivity. Focused ion beam can not only create concave arrays to guide the electrochemical anodization, but also be used for nanoscale sculpting and 3D analysis. When the TiO₂ nanotube surface is bombarded by FIB, there is a mass transfers due to ion-induced viscous flow and sputter milling, thus the TiO₂ nanotubes are selectively closed and opened. By combining FIB cutting and SEM imaging to create a series of 2D cross section SEM images, 3D reconstruction can be obtained by stacking SEM images together. This 3D reconstruction offers an opportunity to directly and quantitatively observe the pore evolution to understand the sintering process.
  • Thumbnail Image
    Implications of Oxidation on the Colloidal Stability of Magnetite Nanoparticles and Cluster
    Rebodos, Robert Louie Fermo (Virginia Tech, 2010-06-10)
    Synthetic nanomagnetite has been suggested as a potential reactant for the in-situ treatment of contaminated groundwater. Although the application of nanomagnetite for environmental remediation is promising, a full understanding of its reactivity has been deterred by the propensity of the nanoparticles to aggregate and form clusters. To characterize the factors responsible for this aggregation behavior, we determined the magnetic properties of magnetite using a superconducting quantum interference device (SQuID). Importantly, because magnetite readily reacts with O2 to produce maghemite, we analyzed the effect of oxidation on its magnetic properties. We observed that oxidation caused a decrease in the saturation magnetization and the anisotrophic barrier of magnetite resulting in less significant magnetic interactions between particles. Consequently, a decrease in the aggregation of magnetite clusters and a potential increase in stability are expected after oxidation. To support these findings, an extended series of experiments to measure the aggregation and the sedimentation of clusters of unoxidized and oxidized magnetite nanoparticles were conducted. Although the individual particle diameter remained constant after oxidation, the cluster size and the aggregation and sedimentation kinetics of magnetite were determined to be different. Oxidized samples of magnetite tended to have lower aggregation rates and were more resistant to sedimentation. These findings can be used to have a better understanding of the overall fate, transport, and reactivity of nanomagnetite, and to gain new insights on its role as a remediation agent in the subsurface environment.
  • Thumbnail Image
    Improving the Exfoliation of Layered Silicate in a Poly(ethylene terephthalate) Matrix Using Supercritical Carbon Dioxide
    Samaniuk, Joseph Reese (Virginia Tech, 2008-04-29)
    Supercritical carbon dioxide (scCO2) was used as a processing aid to improve the level of exfoliation achievable in a PET-layered silicate nanocomposite produced from melt compounding. Layered silicate and scCO2 were allowed to mix for a period of time before being released into the second stage of a single screw extruder. The rapid expansion forced silicate particles into a modified hopper containing neat PET pellets. The mixture of layered silicate and PET was immediately melt mixed in a single screw extruder, cooled in a water bath and pelletized. Two sets of samples each containing layered silicate with different surface chemistries were produced with this method at 1, 3 and 5 wt% silicate. For comparison, samples of the same weight fraction and type of silicate were produced from a traditional melt compounding method. Wide angle x-ray diffraction (WAXD), mechanical testing and rheological analysis were used in order to characterize the silicate morphology, the composite mechanical properties and the relative amount of degradation between the various samples. Results show that scCO2 processed samples contain a higher degree of layered silicate exfoliation than samples produced with traditional melt compounding. Mechanical property improvements are shown to be dependent on the type of silicate surface modification employed. Finally, degradation of the PET matrix appears to be far less extensive in the scCO2 processed samples as shown from rheological data.
  • Thumbnail Image
    Interfacial Phenomena and Surface Forces of Hydrophobic Solids
    Mastropietro, Dean J. (Virginia Tech, 2014-06-16)
    At the molecular level the entropic “hydrophobic effect” is responsible for high interfacial energies between hydrophobic solids and aqueous liquids, the low solubility of apolar solutes in aqueous solvents, and self-assembly in biological processes, such as vesicle formation and protein folding. Although it is known that a strong attraction between apolar molecules exists at the molecular level, it is not clear how this force scales up to objects with dimensions in the range 100 nm–1 m. This work sets out to measure the forces between particles with a radius of about 10 µm. Because we can only measure the total force, which includes the van der Waals force and the electrostatic forces, it is important to isolate the effect of “hydrophobicity”. We do this by measuring for systems where the particles are very hydrophobic (water contact angle, θ ~110°) and the van der Waals and electrostatic forces are very small. Under these conditions we find that the total force is very small: it is similar to the van der Waals force at separations exceeding 5 nm. Many early works on the hydrophobic force reported surface force at over 100 nm of separation. However, many of these strong, long-ranged attractive forces are likely caused by submicron interfacial bubbles, known as nanobubbles. Nanobubbles were imaged with an atomic force microscope to better understand their stability and dependence on solution properties, such as initial concentration of dissolved gas and changes in gas concentration. We found that nanobubbles still formed in degassed solutions and that lowering the dissolved gas concentration did not reduce the bubble size, implying that nanobubbles do not form from dissolved gas in the liquid phase or do not contain gas and are instead water vapor. Furthermore, addition of an oxygen scavenger agent, sodium sulfite, to a liquid phase that had been pressured with oxygen did not reduce bubble size which could be evidence that nanobubbles are impermeable to gas diffusion across the gas liquid interface, do not form from the dissolved gas in the surrounding liquid, or do not contain gas and are instead water vapor.
  • Thumbnail Image
    Investigation of Hydrodynamic and Depletion Interactions in Binary Colloidal Dispersions
    James, Gregory Keith (Virginia Tech, 2013-12-19)
    Within a colloidal dispersion, the presence of negatively adsorbing material can produce a variety of effects on the dispersion properties and interactions. With increasing concentration, the negatively adsorbing material induces both depletion and structural forces on the dispersion, which can dramatically affect both colloidal stability and near-contact hydrodynamics. This project focused on expanding our understanding of the effects of such negatively adsorbing materials on both equilibrium and dynamic interactions between particles. The effects of charged, hard spheres (silica nanoparticle) on the hydrodynamic drag force a particle experiences as it approaches a flat plate were measured experimentally using colloid probe atomic force microscopy (CP-AFM). Deviation was found between the measured drag force and predictions for the drag force in a simple, Newtonian fluid. The measured drag force was always smaller than the predicted drag force as the particle approached contact with the plate. An effective viscosity, that approached the dispersing fluid viscosity at contact and the bulk viscosity at large separations, was determined for the system. This effective viscosity displayed similar characteristics to those predicted theoretically by Bhattacharya and Blawzdziewicz (J. Chem. Phys. 2008, 128, 214704.). The effects of both anionic and cationic micelles on the depletion and structural forces in a colloidal dispersion were studied both experimentally (with CP-AFM) and theoretically. The depletion and structural forces between a microparticle and a flat plate were measured and compared with the depletion force predicted by the force-balance model of Walz and Sharma (J. Colloid Interface Sci. 1994, 168, 485-496.). Consistent with previous work, the measured depletion force for both micelles was smaller in magnitude than that predicted by the Walz and Sharma model for hard, charged spheres. It is theorized that rearrangement of the micelle surfaces charges or physical deformation of the micelles may be responsible for the observed result. An effective surface potential for the micelles is proposed as a correction to the Walz and Sharma model. Finally, the stability of colloidal dispersions was studied macroscopically in solutions of ionic micelles. The colloidal dispersions displayed clear flocculation behavior in both cationic and anionic micelles. This flocculation behavior was compared with energy profiles determined from CP-AFM experiments between a single particle and a flat plate. A simple phase diagram was proposed for predicting the stability of colloidal dispersions based solely on the depth of the depletion energy well and the height of the repulsive energy barrier.
  • Thumbnail Image
    Linking Rheological and Processing Behavior to Molecular Structure in Sparsely-Branched Polyethylenes Using Constitutive Relationships
    McGrady, Christopher Dwain (Virginia Tech, 2009-05-22)
    This dissertation works towards the larger objective of identifying and assessing the key features of molecular structure that lead to desired polymer processing performance with an ultimate goal of being able to tailor-make specific macromolecules that yield the desired processing response. A series of eight well-characterized, high-density polyethylene (HDPE) resins, with varying degrees of sparse long chain branching (LCB) content, is used to study the effect of both LCB content and distribution on the rheological and commercial processing response using the Pom-pom constitutive relationship. A flow instability known as ductile failure in extensional flow required the development a novel technique known as encapsulation in order to carry out shear-free rheological characterization. Ductile failure prevents the rheological measurement of transient stress growth at higher strains for certain strain-hardening materials. This reduces the accuracy of nonlinear parameters for constitutive equations fit from transient stress growth data, as well as their effectiveness in modeling extensionally driven processes such as film casting. An experimental technique to overcome ductile failure called encapsulation in which the material that undergoes ductile failure is surrounded by a resin that readily deforms homogeneously at higher strains is introduced. A simple parallel model is shown to calculate the viscosity of the core material. The effect of sparse long chain branching, LCB, on the film-casting process is analyzed at various drawdown ratios. A full rheological characterization in both shear and shear-free flows is also presented. At low drawdown ratios, the low-density polyethylenes, LDPE, exhibited the least degree of necking at distances less than the HDPE frostline. The sparsely-branched HDPE resins films had similar final film-widths that were larger than those of the linear HDPE. As the drawdown ratio was increased, film width profiles separated based on branching level. Small amounts of LCB were found to reduce the amount of necking at intermediate drawdown ratios. At higher drawdown ratios, the sparsely-branched HDPE resins of lower LCB had content film-widths that mimicked that of the linear HDPE, while the sparsely-branched HDPE resins of higher LCB content retained a larger film width. Molecular structural analysis via the Pom-pom constitutive model suggested that branching that was distributed across a larger range of backbone lengths serve to improve resistance to necking. As the drawdown ratio increased, the length of the backbones dominating the response decreased, so that the linear chains were controlling the necking behavior of the sparsely-branched resins of lower LCB content while remaining in branched regime for higher LCB content HDPEs. Other processing variables such as shear viscosity magnitude, extrudate swell, and non-isothermal processing conditions were eliminated as contributing factors to the differences in the film width profile. The effect of sparse long chain branching, LCB, on the shear step-strain relaxation modulus is analyzed using a series of eight well-characterized, high-density polyethylene (HDPE) resins. The motivation for this work is in assessing the ability of step-strain flows to provide specific information about a material's branching architecture. Fundamental to this goal is proving the validity of relaxation moduli data at times shorter than the onset of time-strain separability. Strains of 1% to 1250% are imposed on materials with LCB content ranging from zero to 3.33 LCB per 10,000 carbon atoms. All materials are observed to obey time-strain separation beyond some characteristic time, Ï k. The presence of LCB is observed to increase the value of Ï k relative to the linear resin. Furthermore, the amount of LCB content is seen to correlate positively with increasing Ï k. The behavior of the relaxation modulus at times shorter than Ï k is investigated by an analysis of the enhancement seen in the linear relaxation modulus, G0(t), as a function of strain and LCB content. This enhancement is seen to 1) increase with increasing strain in all resins, 2) be significantly larger in the sparsely-branched HDPE resins relative to the linear HDPE resin, and 3) increase in magnitude with increasing LCB content. The shape and smoothness of the damping function is investigated to rule out the presence of wall-slip and material rupture during testing. The finite rise time to impose the desired strain is carefully monitored and compared to the Rouse relaxation time of the linear HDPE resins studied. Sparse LCB is found to increase the magnitude of the relaxation modulus at short times relative to the linear resin. It is shown that these differences are due to variations in the material architecture, specifically LCB content, and not because of mechanical anomalies.
  • Thumbnail Image
    Lubrication Forces in Polydimethylsiloxane (PDMS) Melts
    Chatchaidech, Ratthaporn (Virginia Tech, 2011-07-07)
    The flow properties of polydimethylsiloxane (PDMS) melts at room temperature were studied by measurement of lubrication forces using an Atomic Force Microscopy (AFM) colloidal force probe. A glass probe was driven toward a glass plate at piezo drive rates in the range of 12 – 120 μm/s, which produced shear rates up to ~10⁴ s⁻¹. The forces on the probe and the separation from the plate were measured. Two hypotheses were examined: (1) when a hydrophilic glass is immersed in a flow of polymer melt, does a thin layer of water form at the glass surface to lubricate the flow of polymer and (2) when a polymer melt is subject under a shear stress, do molecules within the melt spatially redistribute to form a lubrication layer of smaller molecules at the solid surface to enhance the flow? To examine the effect of a water lubrication layer, forces were compared in the presence and the absence of a thin water layer. The presence of the water layer was controlled by hydrophobization of the solid. In the second part, the possibility of forming a lubrication layer during shear was examined. Three polymer melts were compared: octamethyltrisiloxane (OMTS, n = 3), PDMS (n avg = 322), and a mixture of 70 weight% PDMS and 30 weight% OMTS. We examined whether the spatial variation in the composition of the polymer melt would occur to relieve the shear stress. The prediction was that the trimer (OMTS) would become concentrated in the high shear stress region in the thin film, thereby decreasing the viscosity in that region, and mitigating the shear stress.
  • Thumbnail Image
    The Manufacture and Mechanical Properties of Poly(ethylene terephthalate) Fibers Filled with Organically-Modified Montmorillonite
    Litchfield, David W. (Virginia Tech, 2008-04-21)
    This work is concerned with mechanical property improvements to poly(ethylene terephthalate), PET, fibers by the addition of layered silicate nanoparticles and by drawing the un-oriented nanocomposite filaments in a second step. No previous studies on PET fibers filled with montmorillonite (MMT) nanoclay examined fiber drawability at temperatures above the glass transition. Therefore, the primary objective of this research was to determine 1) if PET nanocomposite fibers could be drawn to finer diameters and 2) whether drawing imparted improved Young's modulus and tenacity (i.e. strength) relative to un-filled PET fibers. Of equal importance to this work, the subsequent objective was to discern and understand the role of nanoclay in 1) the production of improved or reduced mechanical properties and 2) the ability to draw PET to lower or higher than normal draw ratios. In the first part of this thesis, the improvements in Young's modulus and tenacity of PET fibers filled with various types of organically modified montmorillonite is shown and the method to produce them is discussed. Greater improvements in mechanical properties occurred when the MMT stacks were intercalated with PET. A nominal 1 wt% loading of dimethyl-dehydrogenated tallow quaternary ammonium surface modified MMT in drawn PET fiber showed a 28% and 63% increase in Young's modulus and strength, respectively. Relative to an un-filled PET fiber, these results exceeded the upper-bound of the rule of mixtures estimate. Therefore, both the type of surface modification and concentration of MMT were shown to affect the degree of PET orientation and crystallinity. Furthermore, drawability above Tg and elongation-at-break increased upon the addition of organically modified MMT to un-oriented PET fibers, which was a key distinction of this work from others examining similar systems. Interestingly, the mechanical properties of modulus and tenacity showed a maximum with concentration of alkyl modified clay, but drawability did not show significant variation with increasing nanoclay content. Thermal analysis and Raman spectroscopy was used to examine the role of nanoclay in creating this maximum in mechanical properties. At low loadings, nanoclay was shown to intercalate with PET and enhance amorphous orientation. At higher concentrations of nanoclay the presence of large agglomerates prevented efficient orientation to the fiber axis and acted as stress concentrators to aid in cavitation and failure during testing. Raman spectroscopy showed that the as-spun unfilled PET fibers possessed significantly more trans conformer content of the ethylene glycol moiety than the nanocomposite fibers. The greater gauche content of the nanocomposite fibers delayed crystalline development during non-isothermal DSC scans to higher temperatures was associated with the increased drawability.