<p>Poly(vinyl alcohol) and polyethylene polymer systems werebuilt in order to study their transport properties (diffusion).First a verification of the AMBER force field was conducted fora poly(vinyl alcohol) system built from a chain with 145repeating units. NPT-molecular dynamics simulations attemperatures between 400 and 527 K were performed. The resultsof the simulations were compared withpressure-volume-temperature data, solubility parameter, X-rayscattering pattern and data for the characteristic ratio. Thefractional free volume distribution was computed and thediffusion characteristics of water in the polymer werestudied.</p><p>Further another poly(vinyl alcohol) system, with 600repeating units, was used to study oxygen diffusion in dry andwet poly(vinyl alcohol). In these systems the focus was toinvestigate the oxygen paths relative to the backbone and alsothe effect of water on the diffusion coefficients. Jump mapsand correlation function between the velocity of the oxygen wascalculated. The water has a huge impact on the oxygen diffusionand the preferred paths.</p><p>A larger molecule (limonene) was studied in a polyethylenematrix consisting of 6000 anisotropic united atoms. A 100 nslong trajectory was recorded and also shortertrajectories atdifferent temperatures, which gave the temperature dependenceof the diffusion coefficients. Correlation functions for thelimonene molecule shows that it rotates and tumbles when movingthru the matrix.</p><p>The main results from the molecular dynamics simulationsshowed that diffusion of larger molecules are possible and alsothat molecular dynamics simulations can predict plasticizationeffects.</p><p>A new fast experimental method for determining diffusioncoefficients with non iso thermal thermogravimetry weredeveloped. The advantage is that the experiments only takesminutes instead of days with a small effect on theaccuracy.</p>

Fibrous porous media are widely used in various industries such as biomedical engineering, textiles, paper, and alternative energy. Often these porous materials are formed into composite materials, using subsequent manufacturing steps, to improve their properties. There is a strong correlation between system performance and the transport and mechanical properties of the porous media, in raw or composite form. However, these properties depend on the final pore structure of the material. Thus, the ability to manufacture fibrous porous media, in raw or composite forms, with an engineered structure with predictable properties is highly desirable for the optimization of the overall performance of a relevant system. To date, the characterization of the porous media has been primarily based on reverse design methods i.e., extracting the data from existing materials with image processing techniques. The objective of this research is to develop a methodology to enable the virtual generation of complex composite porous media with tailored properties, from the implementation of a fibrous medium in the design space to the simulated coating of this media representative of the manufacturing space. To meet this objective a modified periodic surface model is proposed, which is utilized to parametrically generate a fibrous domain. The suggested modeling approach allows for a high-degree of control over the fiber profile, matrix properties, and fiber-binder composition. Using the domain generated with the suggested geometrical modeling approach, numerical simulations are executed to simulate transport properties such as permeability, diffusivity and tortuosity, as well as, to directly coat the microstructure, thereby forming a complex composite material. To understand the interplay between the xxiii fiber matrix and the transport properties, the morphology of the virtual microstructure is characterized based on the pore size, chord length and shortest path length distributions inside the porous domain. In order to ensure the desired properties of the microstructure, the fluid penetration, at the micro scale, is analyzed during the direct coating process. This work presents a framework for feasible and effective generation of complex porous media in the virtual space, which can be directly manufactured.

Intermetallic clathrates have long been of interest for materials science research. The promise these materials hold for useful applications ranges from thermoelectrics to photovoltaics and optoelectronics to potentially ultra-hard materials and magnetic cooling applications. Their unique physical properties are intimately related to their intriguing structural properties. Thus a fundamental understanding of the chemistry and physics of inorganic clathrates offers the possibility to assess their potential for use in the various applications mentioned above. The purpose of the current work is to expand the current knowledge of the synthetic routes for obtaining clathrate materials, their structural, chemical, and physical properties, particularly those that from in the type I, II and VIII crystal structures. New synthesis routes are presented and used for preparation of single crystals of Na 8Si46 and Na 24Si136. Single-crystal X-ray analysis, and resistivity, Seebeck coefficient and thermal conductivity measurements are presented. In addition, two "inverse" clathrates with compositions Sn 24P19.3Br8 and Sn17Zn7P22Br8 have been characterized in terms of their transport properties. Since the magnetic refrigeration based on the magnetocaloric effect is a topic of great interest, type VIII Eu 8Ga16Ge30 clathrates are also explored in terms of their application for magnetic cooling.

Clathrate materials comprise compounds in which guest atoms or molecules can be encapsulated inside atomic cages formed by host framework polyhedra. The unique relationship that exists between the guest species and its host results in a wide range of physical phenomena, and offers the ability to study the physics of structure-property relationships in crystalline solids. Clathrates are actively being investigated in fields such as thermoelectrics, superconductivity, optoelectronics, and photovoltaics among others. The structural subset known as type II clathrates have been studied far less than other clathrates, and this forms the impetus for the present work. In particular, the known “composition space” of type II clathrates is small, thus the need for a better understanding of possible compositions is evident. A basic research investigation into the synthesis and characterization of silicon and germanium type II clathrates was performed using a range of synthetic, crystallographic, chemical, calorimetric, and transport measurement techniques. A series of framework substituted type II germanium clathrates has been synthesized for the first time, and transport measurements indicate that these compounds show metallic behavior. In the course of the investigation into type II germanium clathrates, a new zeolite-like framework compound with its corresponding novel crystal structure has been discovered and characterized. This compound can be described by the composition Na 1-xGe3 (0 < x < 1), and corresponds to a new binary phase in the Na-Ge system. One of the most interesting aspects of type II clathrates is the ability to create compounds in which the framework cages are partially occupied, as this offers the unique opportunity to study the material properties as a function of guest content. A series of type II sodium-silicon clathrates Na xSi136 (0 < x < 24) has been synthesized in higher purity than previously reported for as-synthesized products. The transport properties of the Na xSi136 clathrates exhibit a clear dependence on the guest content x. In particular, we present for the first time thermal conductivity measurements on Na xSi136 clathrates, and observe evidence that the guest atoms in type II clathrates affect the thermal transport in these materials. Some of the crystalline Na xSi136 compounds studied exhibit very low thermal conductivities, comparable in magnitude to amorphous materials. In addition, for the first time clear evidence from transport measurements was found that resonance phonon scattering may be present in type II clathrates, as is also the case in the type I subset.

Membrane separation technology has recently emerged as a potential alternative technique for removing higher hydrocarbons (C₃₊) from natural gas. For economic reasons, membranes for this application should be organic vapor selective materials such as poly(dimethylsiloxane) (PDMS) or poly(1-trimethylsilyl-1-propyne) (PTMSP). These polymers, often called solubility selective polymers, sieve penetrant molecules based largely on relative penetrant solubility in the polymer. The sorption and transport properties in such polymers have been reported previously. However, most studies present only pure gas sorption and transport properties. Mixture properties, which are important for estimating membrane separation performance, are less often reported. In addition, mixed gas sorption and diffusion data in such polymers, to the best of our knowledge, have never been investigated before. This research work provides a fundamental database of mixture sorption, diffusion, and permeation data in solubility selective polymers. Two solubility selective polymers were studied: poly(dimethylsiloxane) (PDMS) and poly(1-trimethylsilyl-1-propyne) (PTMSP). The vapor/gas mixture was n-C4H10/CH4. CH4 partial pressures ranged from 1.1 to 16 atm, and [subscript n-]C₄H₁₀ partial pressures ranged from 0.02 to 1.7 atm. Temperatures studied ranged from -20 to 50 oC. The pure and mixed gas [subscript n-]C₄H₁₀ and CH₄ permeability and solubility coefficients in PDMS and PTMSP were determined experimentally using devices constructed specifically for these measurements. The pure and mixed gas diffusion coefficients were calculated from permeability and solubility data. In rubbery PDMS, the presence of [subscript n-]C₄H₁₀ increases CH₄ permeability, solubility, and diffusivity. On the other hand, the presence of CH₄ does not measurably influence [subscript n-]C₄H₁₀ sorption and transport properties. The [subscript n-]C₄H₁₀/CH₄ mixed gas permeability selectivities are lower than those estimated from pure gas measurements. This difference is due to both lower solubility and diffusivity selectivities in mixtures relative to those in pure gas. Plasticization of PDMS by [subscript n-]C₄H₁₀ does little to n-C4H10/CH₄ mixed gas diffusivity selectivity. Increases in mixed gas permeability selectivity with increasing [subscript n-]C₄H₁₀ activity and decreasing temperature were mainly due to increases in solubility selectivity. Unlike PDMS, the presence of [subscript n-]C₄H₁₀ decreases CH₄ permeability, solubility, and diffusivity in PTMSP. The competitive sorption and the blocking effects significantly reduce CH₄ solubility and diffusion coefficients in the polymer, respectively. However, similar to PDMS, the presence of CH₄ has no measurable influence on [subscript n-]C₄H₁₀ sorption and transport properties. [subscript n-]C₄H₁₀ /CH₄ mixed gas permeability selectivities in PTMSP are higher than those determined from the pure gas measurements. This deviation is a result of higher solubility and diffusivity selectivities in mixtures relative to the pure gas values. Mixed gas permeability, solubility, and diffusivity selectivities in PTMSP increased with increasing [subscript n-]C₄H₁₀ activity and decreasing temperature. The partial molar volumes of [subscript n-]C₄H₁₀ and CH₄ in the polymers were determined from sorption and dilation data. The dilation isotherms of PDMS and PTMSP in mixtures agree with estimates based on pure gas sorption and dilation measurements. The partial molar volumes of n-C4H10 and CH4 in PDMS are similar to those in liquids. In contrast, the partial molar volumes of [subscript n-]C₄H₁₀ and CH₄ in glassy PTMSP are substantially lower than those in liquids. Several models were used to fit the experimental data. For instance, the FFV model, the activated diffusion model, and the Maxwell-Stefan model were employed to describe the mixture permeability data in PDMS. Based on the Maxwell-Stefan analysis, the influence of coupling effects on permeation properties in PDMS were negligible. The dual mode sorption and permeation models were used to describe the mixed gas data in PTMSP. The dual mode permeability model must be modified to account for [subscript n-]C₄H₁₀ -induced reductions in CH₄ diffusion coefficients (i.e., the blocking effect). The FFV model provides poor correlations in PTMSP. There seems to be other factors, besides FFV per se, contributing to the temperature and concentration dependence of diffusion coefficients in PTMSP.

The gas transport properties of side-chain crystalline poly(n-alkyl acrylate) and poly(m-alkyl acrylate) blends are determined as a function of temperature for varying side-chain lengths, n and m, and blend compositions. The side chains of poly(n-alkyl acrylate)s crystallize independently of the main chain for n [is greater than or equal to] 10 which leads to an extraordinary increase in the permeability at the melting temperature of the crystallites. The compatibility of these polymers are examined and macroscopic homogeneity is observed for a small range of n and m when the difference /n - m/ is between 2 - 4 methylene units. Thermal analysis shows that the blend components crystallize independently of one another; at the same time, the crystallization of each component is hindered by the presence the other component. The permeation responses of these blends show two distinct permeation jumps as the crystallites from each component melt at their respective melting temperatures. Blends with continuous permeation responses are found to have higher effective activation energies than observed for common polymers. Thermal analysis proved to be a useful tool to help predict the permeation response for poly(alkyl acrylates); thus the thermal behavior of poly(n-alkyl acrylate) blended with n-aliphatic materials and random copolymers of poly(n-alkyl acrylates) are briefly examined. A bulk modified atmospheric storage design is proposed where produce is stored in a rigid chamber that is equipped with both selective and non-selective membrane modules that help regulate the oxygen entering and the carbon dioxide leaving the produce compartment. The design enables control of the atmosphere inside the chamber by modulating gas flow, i.e. the gas flow rate and composition, through the non-selective membrane by delivering fresh air upstream of the non-selective membrane. The model shows that the choice of materials for the selective and non-selective membranes dictate the range of concentrations achievable; however, the air flow rate allows the control between these ranges. The method to design a practical chamber from this model is also described.

A first principles atomistic calculation and analysis is used to conduct studies on the mechanical and electron transport properties of selected stretched single-wall carbon nanotube segments. The atomic forces, electron densities, current, voltage and total energies are calculated for these carbon nanotube segments using Atomistix's Virtual NanoLab (VNL) and ToolKit (ATK), a software package for electronic structure calculations and molecular dynamics simulations of different molecular systems. Plots of electronic energy spectra, densities of states, force versus length, and current-voltage data, are presented as output results. The mechanical properties of these carbon nanotube segments under a maximum strain of 1% are studied.A speculative atomistic-level stress-strain approach is tried for calculating Young's modulus for a single-wall carbon nanotube segment. The computed total energies are also used to extract the Young's modulus value. Based on the results, the approach is found to work and we were able to calculate the mechanical parameters for single-wall carbon nanotube segments. The electrical conductance is obtained from the current-voltage curves for strained single-wall metallic carbon nanotube segments placed between copper contacts. / Department of Physics and Astronomy

Non-woven carbon paper is a porous material composed of carbon composite and is the preferred material for use as the gas diffusion layer (GDL) of polymer electrolyte membrane (PEM) fuel cells. This material is both chemically and mechanically stable and provides a free path for diffusion of reactants and removal of products and is electrically conductive for transport of electrons. The transport of species in the GDL has a direct effect on the overall reaction rate in the catalyst layer. Numerical simulation of these transport phenomena is dependent on the transport properties associated with each phenomenon. Most of the available correlations in literature for these properties have been formulated for spherical shell porous media, sand and rock, which are not representative of the structure of the GDL. Hence, the objective of this research work is to investigate the transport properties (diffusion coefficient, thermal conductivity, electrical conductivity, intrinsic and relative permeability and the capillary pressure) of the GDL using experimental and numerical techniques. In this thesis, a three-dimensional reconstruction of the complex, anisotropic structure of the GDL based on stochastic models is used to estimate its transport properties. To establish the validity of the numerical results, an extensive comparison is carried out against published and measured experimental data. It was found that the existing theoretical models result in inaccurate estimation of the transport properties, especially in neglecting the anisotropic nature of the layer. Due to the structure of the carbon paper GDL, it was found that the value of the transport properties in the in-plane direction are much higher than that in the through-plane direction. In the in-plane direction, the fibers are aligned in a more structured manner; hence, the resistance to mass transport is reduced. Based on the numerical results presented in this thesis, correlations of the transport properties are developed. Further, the structure of the carbon paper GDL is investigated using the method of standard porosimetry. The addition of Teflon was found have little effect on the overall pore volume at a pore radius of less than 3 micro meters. A transition region where the pore volume increased with the increase in pore radius was found to occur for a pore radius in the range 3<5.5 micro meters regardless of the PTFE content. Finally, the reduction of the overall pore volume was found to be proportional to the PTFE content. The diffusion coefficient is also measured in this thesis using a Loschmidt cell. The effect of temperature and PTFE loading on the overall diffusibility is examined. It was found that the temperature does not have an effect on the overall diffusibility of the GDL. This implies that the structure of the GDL is the main contributor to the resistance to gas diffusion in the GDL. A comparison between the measured diffusibility and that predicted by the existing available models in literature indicate that these models overpredict the diffusion coefficient of the GDL significantly. Finally, both the in-plane and through-plane thermal conductivity were measured using the method of monotonous heating. This method is a quasi-steady method; hence, it allows the measurement to be carried out for a wide range of temperatures. With this method, the phase transformation due to the presence of PTFE in the samples was investigated. Further, it was found that the through-plane thermal conductivity is much lower than its in-plane counterpart and has a different dependency on the temperature. Detailed investigation of the dependency of the thermal conductivity on the temperature suggests that the thermal expansion in the through-plane direction is positive while it is negative in the in-plane direction. This is an important finding in that it assists in further understanding of the structure of the carbon paper GDL. Finally, the thermal resistance in the through-plane direction due to fiber stacking was investigated and was shown to be dependent on both the temperature and compression pressure.

In this thesis we present three different aspects of spin and spin-dependent transport properties in novel materials. Spurred by the prospect of spintronic devices, which use the spin degree of freedom of electrons instead of, or combined with, the charge degree of freedom, we analyse the spin properties of quantum wires, organic conducting polymers and sheets of graphene. First, we examine a quantum wire that is embedded in a two dimensional electron gas. We consider the Rashba spin-orbit coupling, and include the effect of interaction between the conduction electrons. We construct an analytically solvable low-energy theory for the wire, and explore the interaction between two magnetic impurities in the wire. We find that both the spin-orbit coupling and the electron-electron interaction have an effect on the magnetic interaction, and find the magnetic interaction to be tunable by an electric field. Next, we study an organic conducting polymer, which is contacted to magnetised ferromagnetic leads. In semiconducting organic polymers the current is transported by spinful polarons and spinless bipolarons. We simulate the transport through the system, including both types of charge carriers, and find the current to be insensitive to the presence of bipolarons. In addition, we find the bipolaron density to depend on the relative magnetisation of the ferromagnetic contacts. This constitutes an optical way of measuring the spin accumulation in conducting polymers. Finally, we investigate the optical conductivity of graphene. Symmetry arguments indicate the existence of two kinds of spin-orbit coupling in the two dimensional lattice, but there is no consensus about the actual strength of these couplings. We calculated the microwave optical conductivity of graphene including both possible spin-orbit interactions. We find the low frequency dependence of the optical conductivity to have a unique imprint of the spin-orbit couplings. This opens a possibility to experimentally determine both couplings separately.

Thesis (M. S.)--Mechanical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Sitaraman, Suresh; Committee Member: Peak, Russell; Committee Member: Ume, Charles