Metal-organic frameworks (MOFs) are porous networks of metal-centers connect by organic ligands, which have potential for an array of applications including gas separations and storage, drug delivery, and molecular sensing. A multitude of structures are reported with specific pore geometries and functionalities, but MOFs are not currently implemented in consumer or industrial applications. Two major setbacks have hindered their transition to the applied level. 1) Many MOFs are not stable in the presence of ambient moisture. 2) Most syntheses are costly and take place under batch-style solvothermal conditions. This thesis addresses both of these setbacks and examines the performance potential of water-stable MOFs for selective gas adsorption. A representative set of MOFs are exposed to water, and structural effects are monitored from a before and after comparison to identify properties of water-stable MOFs. A novel continuous-flow MOF synthesis process is reported along with preliminary optimization experiments, which yield direct suggestions for future process improvements. Batch-style scale-up experiments are also conducted for three other MOFs, which provide insight into synthesis phenomena. Application specific results are reported for toxic chemical filtration and carbon dioxide removal from flue gas using MOFs. The thesis concludes by summarizing the experimental findings, discussing the application potential of specific MOFs, and recommending topics for future research projects. Pitfalls observed during this research are also directly discussed along with potential solutions.

This thesis summarizes experimental results on mass transport of small hydrocarbons in micro-porous crystals obtained via interference microscopy (IFM). The transport process has been investigated in three difffferent materials with difffferent pore structures : the metal-organic framework Zn(tbip) with one-dimensional pores, a FER type zeolite with two-dimensional anisotropic pore structure and zeolite A, a LTA type material with isotropic three-dimensional pore structure. Mass transport is described in terms of diffffusivity and surface permeability, both derived from the detected transient concentration profiles. The results on intra-crystalline diffffusion are discussed under consideration of the influences of pore diameter and molecule diameter, which are both found to have a strong influence on the diffffusivity. Based on experimental results measured on the Zn(tbip) material, a new model for the description of surface barriers is developed and proved by experiment. It is demonstrated that the observed surface barrier is created by the total blockage of a large number of pore entrances at the surface and not by a homogeneous surface layer.

Multilayered structures have many application in industry and society: they have peculiar properties and serve a variety of purposes, like structural support, thermal insulation, vibrational and acoustic isolation. This thesis concerns the prediction of sound transmission in multilayered structures. Two problems are herein investigated: the transmission of energy through structures and the transmission of energy along structures. The focus of the analysis is on the mid to high frequency range. To predict sound transmission in these structures, statistical energy analysis (SEA) is used.SEA models are devised for the prediction of the sound reduction index for two kinds of multilayered structures, double-walls used in buildings and trim-panels in vehicles; the double-walls comprise an air cavity in between flat plasterboard or glass plates, whereas the trim-panels a porous layer in between curved aluminium and rubber layers. The SEA models are based upon the wave-types carrying energy. The novelty in these SEAs is an element describing the waves in the air cavity, or in the porous layer, fully coupled to the mass-impeded external layers. Compared to measurements, the proposed SEA performs well: for double-walls, it performs better than previous models; for trim-panels, it is an original result. The parameters of the new SEA element, such as modal density, are derived from the coupling equations describing the fully coupled waves. For double-walls, these equations are derived via Newton's laws. For trim-panels, a variational approach based upon a modified Hamilton's principle valid for non-conservative systems is preferred, because it is a powerful machinery for deriving equations of motion and coupling conditions of a medium as complex as the porous layer. The modified Hamilton's principle for non-conservative systems is based upon a self-adjoint functional analogous to the Lagrangian, inspired by Morse and Feshbach's construction. A self-adjoint variational principle for Biot's equations in the displacement formulation is devised. An equivalent mixed formulation is obtained changing the coordinates of the displacement formulation via Lagrange multipliers. From this mixed formulation, the Lagrangian for a porous material with a limp frame is derived, which yields the continuity of the total displacement of the porous layer. Lagrange multipliers help to obtain the correct coupling functionals between a porous material and a solid. The Lagrange multipliers introducing the continuity of the frame and the solid displacements equal the traction of the in-vacuo frame, thus disappearing if the latter is limp. Measurements to gather material parameters for a Biot model of the porous layer have been conducted.The effects of spatial energy decay in the transmission along structures predicted by SEA is studied: a major effect is the increased relevance of indirect coupling loss factors between SEA elements. This may jeopardize the usefulness of SEA at higher frequencies. / <p>QC 20130218</p>

Porous media flows are encountered in many natural and man-made systems such as gas adsorption, filtration, heat exchangers, combustion, catalytic reactors and groundwater hydrology. This study experimentally investigates these flows as function of pore Reynolds number, Re[subscript pore]. The pore Reynolds number is based on the porous bed hydraulic diameter, D[subscript H] =φD[subscript Β]/(1−φ) where φ is bed porosity and D[subscript B] is solid phase bead diameter and average bed interstitial velocity, V[subscript int]= V[subscript Darcy]/φ, where VDarcy= Q/A[subscript bed], with Q being the volumetric flow rate and A[subscript bed] the bed cross section normal to the flow. The flow characteristics are studied through application of a particle displacement technique called particle image velocimetry, PIV. In the case of PIV, flow fields are estimated by seeding the flow with tracer particles and then evaluating their displacements. Application of quantitative imaging technique such as PIV to a complex flow domain like porous bed requires matching refractive index of liquid phase to that of the solid phase. Firstly, the effect of slight index mismatch, due to experimental uncertainties, on obtaining highly accurate PIV measurements as expressed as an experimental uncertainty was explored. Mismatch of refractive indices leads to error in estimation of particle positions and their displacements due to refraction at solid-liquid interfaces. Slight mismatch, in order of 10⁻³, in refractive indices also leads to reduction in particle density, particle signal peak intensity and degrade the particle image. These effects on velocity field estimation using PIV is studied experimentally and numerically. The numerical model, after validating against experimental results, is used to generate an expression for the error in PIV measurements as a function of refractive index mismatch for a range of bead diameters, bed widths, bed porosity, and optical magnification. After refractive index matching, planar PIV measurements were taken at discrete locations throughout a randomly packed bed with aspect ratio (bed width to bead diameter) of 4.67 for steady, low pore Reynolds number flows, Re[subscript pore] ~ 6, intermediate Re[subscript pore] of 54 and unsteady flow with high Re[subscript pore] ranging from 400-4000. Details of the measurement uncertainties as well as methods to determine local magnification and determination of the dynamic velocity range are presented. The data are analyzed using the PIV correlation averaging method for steady flows and multigrid and multipass correlation methods for unsteady turbulent flows with the largest velocity uncertainties arising from in plane image loss and out of plane motion. Results for low Re[subscript pore] flows show the correspondence of the geometric and velocity correlation functions across the bed, and that the centerline of the bed shows a random-like distribution of velocity with an integral length scale on the order of one hydraulic diameter (or 0.38 bead diameters based on the porosity for this bed). The velocity variance is shown to increase by a factor of 1.8 when comparing the center plane data versus using data across the entire bed. It is shown that the large velocity variance contributes strongly to increased dispersion estimates, and that based on the center plane data of the variance and integral length scales, the dispersion coefficient matches well with that measured in high aspect ratio beds using global data. For unsteady and turbulent flow, velocity data were used to determine the following turbulence measures: (i) turbulent kinetic energy components, (ii) turbulent shear production rate, (iii) integral Eulerian length and time scales, and (iv) energy spectra all for a range of pore Reynolds numbers, Re[subscript pore], from 418 to 3964. These measures, when scaled with the bed hydraulic diameter, DH, and average interstitial velocity, V[subscript int], all collapse for Re[subscript pore], beyond approximately 2800, except that the integral scales collapse at a lower value near 1300-1800. The results show that the pore turbulence characteristics are remarkably similar from pore to pore and that scaling based on bed averaged variables like D[subscript H] and V[subscript int] characterizes their magnitudes despite very different local mean flow conditions. In the case of high Re[subscript pore] flows, large scale structures such as stationary and convected vortices and structures resembling jets were also identified. These structures were analyzed in detail using decomposition techniques like Large Eddy Scale decomposition and critical point analysis like swirl strength analysis. Direct velocity measurements were used to estimate Lagrangian statistics through Eulerian measures and then estimate contribution of flow structures to turbulent mechanical dispersion. Results agree well with those in the literature obtained using global measurements in very high aspect ratio, long test beds. Stationary vortical or recirculation regions were seen to play a dominant role in contributing to overall dispersion in porous beds. / Graduation date: 2013

No description available.

The mechanical properties of the cancellous bone in the laboratory rat animal model are of great interest to the research community for the evaluation of treatments for osteoporosis. Cancellous bone responds rapidly and dramatically to disuse, various pathologies, nutritional deficiencies, and hormonal deficiencies and hence is often a primary focus in animal studies. Previous methods for evaluating the mechanical properties of cancellous bone in rat test specimens included both cortical and cancellous bone. This thesis introduces a new method to core cancellous specimens using a diamond wire saw in concert with specially designed fixtures. This method has been termed Isolated Cancellous Coring (ICC). The location and the geometry of the cored specimens were determined based on uCT analysis. The isolated cancellous specimens were subjected to uni-axial compression testing to evaluate the mechanical properties. Furthermore, the new method is evaluated by directly applying it to a study investigating the effects of estrogen replacement therapy in post-menopausal osteoporosis as simulated by the ovariectomized rat model. The results show that the ICC method can be applied to bone specimens with a large range in density and micro-architecture parameters. The compression testing of the isolated cancellous specimens provides a sensitive indicator of the effects of osteoporosis and treatment on the mechanical properties of the cancellous bone in the distal rat femur. Also, the results indicate a possible discordant relationship between bone mineral density and bone strength with respect to estrogen treatment. Power law regressions show that approximately 50% of the variation in ultimate strength can be accounted for with bone mineral density and the percent of bone volume per total volume.

Three types of poly(norbornane carbonate) or PNC oligomers were synthesized and characterized via spectroscopic methods and elemental analyses to validate their chemical structures. Using the results from proton nuclear magnetic resonance (1H NMR) experiments, the degree of polymerization and size of each PNC chain was estimated via end-group analysis. All three types of PNC structures were both thermally-labile and acidolytically-labile, allowing them to be used as sacrificial materials in both direct-write and thermally-processed template systems. Thermogravimetric analysis (TGA) data was used to determine the kinetic parameters for the thermolytic decomposition reactions and evolved-gas analysis via mass spectrometry (TGA-MS) was used to determine the mechanisms for thermolytic degradation. PNC oligomers were freely-mixed with hydrogen silsesquioxane (HSQ) to form solutions that were spin-coated to form templated films. Transmission electron microscopy (TEM) showed that the free-mixing of PNCs with HSQ resulted in the agglomeration of the porogen molecules during the spincoating step. This phase-segregation produced domain sizes much larger than those of the individual chains, and during decomposition large pores were produced. To combat the phase segregation, hydrosilylation reactions were used to covalently bond vinyl end-capped PNC chains to silane-functionalized siloxane and silsesquioxane molecules. These matrix-like materials served as compatibilizers in order to improve the phase-compatibility of the sacrificial polymers in HSQ films. NMR and GPC analyses showed that the solids recovered from the hydrosilylation reactions were binary mixtures of hybrid nanocomposite molecules and residual ungrafted PNC chains. TEM imaging showed that the domains in these nanocomposite films had bimodal size distributions due to the presence of two components in the mixtures. The hybrid molecules produced pores ranging in size from about 6-13 nm as a result of improvements in the phase-compatibility of the grafted oligomers. However, the residual ungrafted oligomers in the blends produced larger domains measuring 30-40 nm. It is believed that separation difficulties can be avoided if the vinyl termination reaction conditions can be adjusted to ensure 100% conversion of all the terminal hydroxyl groups to vinyl groups. Doing so would allow all PNC chains to be grafted during hydrosilylation reaction; thus, avoiding the recovery of free PNC oligomers.

Pipeline natural gas is the primary fuel of choice for distributed fuel cell-based applications. The concentration of sulfur in odorized natural gas is about 30 ppm, with acceptable levels being <1 ppm for catalyst stability in such applications. Packed bed technology for desulfurization suffers from several disadvantages including high pressure drop and slow regeneration rates that require large unit sizes. We describe a novel Rapid Temperature Swing Adsorption (RTSA) system utilizing hollow fibers with polymer 'binder', impregnated with high loadings of sulfur selective sorbent 'fillers'. Steam and cooling water can be utilized to thermally swing the sorbent during the regeneration cycles. An impermeable, thin polymer barrier layer on the outside of fiber sorbents allows only thermal interactions with the regeneration media, thereby promoting consistent sorption capacity over repeated cycles. A simplified flow pattern minimizes pressure drop, porous core morphology maximizes sorption efficiencies, while small fiber dimensions allows for rapid thermal cycles.

Nanoporous (NP) metal foams combine desirable characteristics of metals with unique nanoarchitectural features to yield weight normalized properties far superior than either dense metals or bulk metal foams. Due to their high surface to volume ratios these structures show great promise as components of fuel cells, as sensors and have been suggested for use in biological applications, for example as antimicrobial scaffolds or as platforms on which to explore biological material behavior. While most NP metal foams are isotropic, structures with anisotropic features spanning different length scales can further extend applications. This work examines the parameters controlling the synthesis of transversely isotropic NP Platinum foam by dealloying an amorphous Pt-Si alloy. The structure that is examined in this work is hierarchical with Voronoi polyhedra that form on the free surface and under each polyhedral hyper-structure, nanocrystalline NP Pt foam forms with radial struts of length ~60 nm and grain size of 5 nm. The size of the polyhedra can be tailored by changing the dealloying potential. In turn, the mechanical properties of these structures as assessed by nanoindentation can range from 1 to 3GPa depending on the geometric arrangement of the struts. Finally, the initiation location of these structures and the relationship between electrochemical parameters and dealloying front evolution is examined.

Thesis (Doctoral)--Universität Karlsruhe, 2001. / Abstract in German. Hochschulschrift = Thèse/Mémoire. Includes bibliographical references (p. 109-133). Also available via the World Wide Web. http://www.ubka.uni-karlsruhe.de/indexer-vvv/2002/bio-geo/1