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.

Intentional amendment of soil with charcoal (called biochar) is a promising new approach to sequester atmospheric carbon dioxide and increase soil fertility. However, the environmental properties of biochars can vary with production conditions, making it challenging to engineer biochars that are simultaneously optimized for carbon sequestration, nutrient storage, and water-holding capacity. For this reason, I have undertaken a systematic study to (a) determine the pyrolysis conditions that lead to biochars with desired chemical and physical properties, and (b) find how these properties affect the water-holding capacity and nutrient adsorption in biochar-soil mixtures. First, a library of biochars was produced in a custom-built pyrolysis reactor under precisely controlled conditions. The chemical and physical structures of the produced biochars were characterized with various analytical techniques including 13C NMR, XPS, EA and BET pore surface analysis. My results suggest that the chemical composition and pore structure of biochars are determined not just by the maximum heat treatment temperature, but also by several other factors that include the pyrolysis heating rate, treatment time at the maximum temperature and particle size. I also tested a new approach that combines thermogravimetric reactivity measurements, diffusion-reaction theory and structural models to achieve a better characterization of the complicated multi-scale pore structure of biochars. The structural models treat biochars as porous solids having micro- and macropores of different shapes and exhibiting widely ranging pore-size distributions. Simulations results are then compared to experimental data to identify the presence of ordered or random pore networks and test their size distributions and connectivity. I then developed a multi-solid one-dimensional model that can use experimentally determined biochar properties to predict their field performance in beds packed with soil/biochar mixtures. The model used a system of coupled partial differential equations to describe the dynamic adsorption/elution of ammonium nitrate, a model fertilizer, in columns packed with biochar/soil mixtures and perfused with aqueous solutions of the fertilizer. The PDE system was solved using orthogonal collocation on finite elements. My chromatographic model accounted for all the important processes occurring in this system, including external mass transfer between the fluid phase and the solid particles, as well as intraparticle diffusion and adsorption of the solute on the pore surface area of the sorbents. To our knowledge, this is the first chromatographic model that accounted explicitly for the presence of two solid phases with widely different pore structures and adsorption capacities. A systematic parametric study was carried out to determine the importance of each system parameter. The adsorption equilibrium parameters and the intraparticle effective diffusivity of ammonium had the most significant effect on environmental performance. To complete the theoretical analysis, I also developed a model to describe the saturation and drainage of water from the packed column. The model accounted for all the important processes occurring in this system: (a) water exchange between the interstitial pore region and two different smaller pore regions and (b) water flow inside the larger pore region and the two different smaller pore regions. The transient mass balances led to a system of partial differential equations that was solved using block centered finite difference.

Degassing and in situ formation of a mobile gas phase takes place when an aqueous phase equilibrated with a gas at a pressure higher than the subsurface pressure is injected in water-saturated porous media. This process, which has been termed supersaturated water injection (SWI), is a novel and hitherto unexplored means of introducing a gas phase into the subsurface. Herein is a first macroscopic account of the SWI process on the basis of continuum scale simulations and column experiments with CO2 as the dissolved gas. A published empirical mass transfer correlation (Nambi and Powers, Water Resour Res, 2003) is found to adequately describe the non-equilibrium transfer of CO2 between the aqueous and gas phases. Remarkably, the dynamics of gas-water two-phase flow, observed in a series of SWI experiments in homogeneous columns packed with silica sand or glass beads, are accurately predicted by traditional two-phase flow theory which allows the corresponding gas phase relative permeability to be determined. A key consequence of the finding, that the displacement of the aqueous phase by gas is compact at the macroscopic scale, is consistent with pore scale simulations of repeated mobilization, fragmentation and coalescence of large gas clusters (i.e., large ganglion dynamics) driven entirely by mass transfer. The significance of this finding for the efficient delivery of a gas phase below the water table in relation to the alternative process of in-situ air sparging and the potential advantages of SWI are discussed. SWI has been shown to mobilize a previously immobile oil phase in the subsurface of 3-phase systems (oil, water and gas). A macroscopic account of the SWI process is given on the basis of continuum-scale simulations and column experiments using CO2 as the dissolved gas and kerosene as the trapped oil phase. Experimental observations show that the presence of oil ganglia in the subsurface alters gas phase mobility from 2-phase predictions. A corresponding 3-phase gas relative permeability function is determined, whereas a published 3-phase relative permeability correlation (Stone, Journal of Cana Petro Tech, 1973) is found to be inadequate for describing oil phase flow during SWI. A function to predict oil phase relative permeability is developed for use during SWI at high aqueous phase saturations with a disconnected oil phase and quasi-disconnected gas phase. Remarkably, the dynamics of gas-water-oil 3-phase flow, observed in a series of SWI experiments in homogeneous columns packed with silica sand or glass beads, are accurately predicted by traditional continuum-scale flow theory. The developed relative permeability function is compared to Stone’s Method and shown to approximate it in all regions while accurately describing oil flow during SWI. A published validation of Stone’s Method (Fayers and Matthews, Soc of Petro Eng Journal, 1984) is cited to validate this approximation of Stone’s Method.

Nowadays, the development of novel materials involves diverse branches of science as a consequence of the new requirements imposed by modern society. This includes aspects ranging from the optimization of the manufacturing processes to the durability of the materials themselves. Ideally, some synergism should exist between the durability, the properties of interest in the material. Although metals in their pure state are often desired, the best properties or combination of properties often cannot be satisfactorily achieved with a single metal. In these situations, the desired properties can be attained by the formation of alloys of these metals with others. Ni-Co alloys are no exceptions and so have received considerable attention especially in microsystem technology due to the magnetic properties of cobalt and the corrosion and wear resistance of nickel. Moreover, this interest has been further stimulated by its use in the manufacture of sensors, magnetic devices, microrelays, inductors, actuators, memory devices and hard drives. The fabrication of these alloys (particularly coatings) via electroplating has been shown to be techno-economically feasible in comparison with other processes: capability of high volume production, low cost and the ability to coat thin layers on non-planar substrates. In addition, the materials fabricated by this technology exhibit excellent characteristics such as refined grain structure, smoothness, low residual stress and coercivity, etc., making them advantageous to materials produced by other physical methods of deposition. Nevertheless, one of the biggest problems faced during the formation of Ni-Co alloys is its anomalous behavior whereby cobalt preferentially deposits over nickel under most conditions, even when the Ni(II) concentration is significantly higher than that of Co(II). This problem has complicated the prediction and control of the metal composition in these alloys during their production and as a consequence the ability to obtain the desirable properties associated with high nickel content. Although this problem is not recent, the studies that have been carried out so far to analyze this system have not always been as comprehensive as they could be in terms of the experimental conditions investigated or the reaction mechanisms and mathematical models developed to describe its behavior. Consequently, the origin of this behavior is still not completely understood. Thus, this work presents a contribution in terms of the analysis of the reaction mechanisms for single metal deposition of nickel and cobalt and for the formation of Ni-Co alloys in sulphate media with the intention of gaining a better understanding of the phenomena controlling the anomalous behavior of this system. Analyses of the single metal deposition of nickel and cobalt are first carried out to better understand their reaction mechanisms. Such an approach should allow the contributions of the reduction of each metal ion and interactions between the two systems during alloy co-deposition to be more clearly understood. In order to analyse the aforementioned systems, both steady state and transient techniques are employed. Among these techniques, electrochemical impedance spectroscopy (EIS) is employed since it is a robust and powerful method to quantitatively characterize the various relaxation phenomena occurring during the electrodeposition of metals. The experimental data acquired from this technique are analyzed with comprehensive physicochemical models and the electrochemical processes are quantified by fitting the models to these data to determine the kinetic parameters. During the development of the physicochemical models, several assumptions (e.g. neglect of convection, homogeneous reactions and single electron-transfer steps) made in former models are relaxed in order to investigate their combined impact on the predicted response of the system. Estimates of the kinetic parameters determined by EIS for the deposition of the single metals reveals that the first step of Co(II) reduction is much faaster tha the corresponding step of Ni(II) reduction. Some limitations of the EIS technique (i.e. analysis at high overpotentials) are exposed and compared in the case of the nickel deposition using linear sweep voltammetry (LSV). Likewise, physicochemical models accounting for most of the important phenomena are derived and fitted to experimental data. Ni-Co alloy formation is analyzed using LSV and steady state polarization experiments for different pH, current density and electrolyte composition. Current efficiencies for metal depsoition and alloy composition are also evaluated. To date, no experimental study considering all these variables has been reported in the literature. Then a steady state model is presented to describe the electrode response during alloy formation and used to provide insight into the anomalous behavior of this system. This model is based on information obtained from previous studies reported in the literature and from the current research. After being fitted to the experimental data, the model reveals that the anomalous behavior observed for this alloy is likely caused by the much faster charge-transfer of Co(II) reduction than that of Ni(II) reduction and not by other previously proposed mechanisms such as competition between adsorbed species for surface sites, formation of aqueous hydroxides (MeOH+) or mixed intermediate species (NiCo(III)ads) on the surface of the electrode.

This thesis is devoted to the fabrication of carbon nanotube structures for microelectronics packaging applications with an emphasis on fundamental studies of nanotube growth and assembly, wetting of nanotube structures, and nanotube-based composites. A CVD process is developed that allows controlled growth of a variety of CNT structures, such as CNT films, bundles, and stacks. Use of an Al2O3 support enhances the Fe catalyst activity by increasing the CNT growth rate by nearly two orders of magnitude under the same growth conditions. By introducing a trace amount of weak oxidants into the CVD chamber during CNT growth, aligned CNT ends can be opened and/or functionalized, depending on the selection of oxidants. By varying the growth temperature, CNT growth can be performed in a gas diffusion- or kinetics-controlled regime. To overcome the challenges that impede implementation of CNTs in circuitry, a CNT transfer process was proposed to assemble aligned CNT structures (films, stacks &bundles) at low temperature which ensures compatibility with current microelectronics fabrication sequences and technology. Field emission and electrical testing of the as-assembled CNT devices indicate good electrical contact between CNTs and solder and a very low contact resistance across CNT/solder interfaces. For attachment of CNTs and other applications (e.g. composites), wetting of nanotube structures was studied. Two model surfaces with two-tier scale roughness were fabricated by controlled growth of CNT arrays followed by coating with fluorocarbon layers formed by plasma polymerization to study roughness geometric effects on superhydrophobicity. Due to the hydrophobicity of nanotube structures, electrowetting was investigated to reduce the hydrophobicity of aligned CNTs by controllably reducing the interfacial tension between carbon nanotubes (CNTs) and liquids. Electrowetting can greatly reduce the contact angle of liquids on the surfaces of aligned CNT films. However, contact angle saturation still occurs. Variable frequency microwave (VFM) radiation can greatly improve the CNT/epoxy interfacial bonding strength. Compared to composites cured by thermal heating, VFM-cured composites demonstrate higher CNT/matrix interfacial bonding strength, which is reflected in composite negative thermal expansion. The improved CNT/epoxy interface enhances the thermal conductivity of the composites by 26-30%.

<p>Rechargeable batteries play an important role as energycarriers in our modern society, being present in wirelessdevices for everyday use such as cellular phones, video camerasand laptops, and also in hybrid electric cars. The batterytechnology dominating the market today is the lithium-ion(Li-ion) battery. Battery developments, in terms of improvedcapacity, performance and safety, are major tasks for bothindustry and academic research. The performance and safety ofthese batteries are greatly influenced by transport andstability properties of the electrolyte; however, both haveproven difficult to characterise properly.</p><p>The specific aim of this work was to characterise and modelthe electrolytes used in Li-ion batteries. In particular, themass transport in these electrolytes was studied throughcharacterisation and modelling of electrolyte transport in bulkand in porous electrodes. The characterisation methodology assuch was evaluated and different models were tested to find themost suitable. In addition, other properties such aselectrochemical stability and thermal properties were alsostudied.</p><p>In the study of electrochemical stability it wasdemonstrated that the electrode material influenced thevoltammetric results significantly. The most versatileelectrode for probing the electrolyte stability proved to beplatinum. The method was concluded to be suitable for comparingelectrolytes and the influences of electrolyte components,additives and impurities, which was also demonstrated for a setof liquid and polymer containing electrolytes.</p><p>A full set of transport properties for two binary polymerelectrolytes, one binary liquid and the corresponding ternarygel were achieved. The transport was studied both in the bulkand in porous electrodes, using different electrochemicaltechniques as well as Raman spectroscopy. In general, theconductivity, the salt and solvent diffusivity decreasedsignificantly when going from liquid to gel, and to polymerelectrolyte. Additionally, low cationic transport numbers wereachieved for the polymer and gel and significant salt activityfactor variations were found. The results were interpreted interms of molecular interactions. It was concluded that both theionic interactions and the influences from segmental mobilitywere significant for the polymer containing electrolytes. Thecharacterisation methods and the understanding were improved bythe use of a numerical modelling using a model based on theconcentrated electrolyte theory. It was concluded thatelectrochemical impedance spectroscopy and Raman spectroscopywere insufficient for determining a full set of transportproperties. It was demonstrated that the transport is veryinfluential on electrochemical impedance as well as batteryperformance.</p><p><b>Keywords:</b>lithium battery, electrolyte, mass transport,stability, modelling, characterisation, electrochemical, Ramanspectroscopy, impedance</p>

<p>In the chlorate process, natural convection arises thanks to the hydrogen evolving cathode. This increases the mass transport of the different species in the chlorate electrolyte. There is a strong connection between mass transport and the kinetics of the electrode reactions. A better knowledge about these phenomena and their interactions is desirable in order to understand e.g. the reasons for deactivation of anode coatings and what process conditions give the longest lifetime and the highest efficiency.</p><p>One of the aims of his work was to understand how the chlorate process has to be run to avoid exceeding the critical anode potential (<em>E</em>_cr) in order to keep the potential losses low and to achieve a long lifetime of the DSAs. At <em>E</em>_cr anodic polarisation curves in chlorate electrolyte bend to higher Tafel slopes, causing increasing potential losses and accelerated ageing of the anode. Therefore the impact on the anode potential and on <em>E</em>_cr of different electrolyte parameters and electrolyte impurities was investigated. Additionally, the work aimed to investigate the impact of an addition of chromate on oxygen evolution and concentration profiles under conditions reminiscent of those in the chlorate process (high ionic strength, 70 °C, ruthenium based DSA, neutral pH), but without chloride in order to avoid hypochlorite formation. For this purpose a model, taking into account mass transport as well as potential- and concentration-dependent electrode reactions and homogeneous reactions was developed. Water oxidation is one of the side reactions considered to decrease the current efficiency in chlorate production. The results from the study increase the understanding of how a buffer/weak base affects a pH dependent electrode reaction in a pH neutral electrolyte in general. This could also throw light on the link between electrode reactions and homogeneous reactions in the chlorate process.</p><p>It was found that the mechanism for chloride oxidation is likely to be the same for potentials below <em>E</em>_cr as well as for potentials above <em>E</em>_cr. This was based on the fact that the apparent reaction order as well as α_a seem to be of the same values even if the anode potential exceeds<em> E</em>_cr. The reason for the higher slope of the polarisation curve above <em>E</em>_cr could then be a potential dependent deactivation of the active sites. Deactivation of active ruthenium sites could occur if ruthenium in a higher oxidation state were inactive for chloride oxidation.</p><p>Concentration gradients of H⁺, OH^-, CrO₄ ^2- and HCrO₄ ^-during oxygen evolution on a rotating disk electrode (RDE) were predicted by simulations. The pH dependent currents at varying potentials calculated by the model were verified in experiments. It was found that an important part of the chromate buffering effect at high current densities occurs in a thin (in the order of nanometers) reaction layer at the anode. From comparisons between the model and experiments a reaction for the chromate buffering has been proposed. Under conditions with bulk pH and chromate concentration similar to those in the chlorate process, the simulations show that the current density for oxygen evolution from OH^- would be approximately 0.1 kA m^-2, which corresponds to about 3% of the total current in chlorate production.</p>

<p>The role of nitric acid (HNO₃) on the atmospheric corrosion of metals has so far received little or no attention. However, the last decades of decreasing sulphur dioxide (SO₂) levels and unchanged HNO₃ levels in many industrialized countries have resulted in an increased interest in possible HNO₃-induced atmospheric corrosion effects. In this study a new method was developed for studying the corrosion effects of HNO₃ on metals at well-defined laboratory exposure conditions. The method has enabled studies to be performed on the influence of individual exposure parameters, namely HNO₃-concentration, air velocity, temperature and relative humidity, as well as comparisons with newly generated field exposure data.</p><p>The corrosion rate and deposition rate of HNO₃ on copper was shown to follow a linear increase with HNO3 concentration. The deposition velocity (Vd) of HNO₃ increased up to an air velocity of 11.8 cm s^-1. Only at a higher air velocity (35.4 cm s^-1) the Vd on copper was lower than the Vd on an ideal absorbent, implying the Vd of HNO3 at lower air velocities to be mass-transport limited.</p><p>Within the investigated temperature range of 15 to 35 ºC only a minor decrease in the HNO₃-induced copper corrosion rate could be observed. The effect of relative humidity (RH) was more evident. Already at 20 % RH a significant corrosion rate could be measured and at 65 % RH the Vd of HNO₃ on copper, zinc and carbon steel reached maximum and nearly ideal absorption conditions.</p><p>During identical exposure conditions in HNO_3-containing atmosphere, the corrosion rate of carbon steel was nearly three times higher than that of copper and zinc. The HNO₃-induced corrosion effect of copper, zinc and steel turned out to be significantly higher than that induced by SO2 alone or in combination with either NO₂ or O₃. This is mainly attributed to the much higher water solubility and reactivity of HNO3 compared to SO₂, NO₂ and O_3. Relative to SO₂, zinc exhibits the highest sensitivity to HNO₃, followed by copper, and carbon steel with the lowest sensitivity.</p><p>Extrapolation of laboratory data to an assumed average outdoor wind velocity of 3.6 m s-1 enabled a good comparison with field data. Despite the fact that ambient SO₂ levels are still much higher than HNO₃ levels, the results show that HNO₃ plays a significant role for the atmospheric corrosion of copper and zinc, but not for carbon steel. The results generated within this doctoral study emphasize the importance of further research on the influence of HNO₃ on degradation of other materials, e.g. stone and glass, as well as of other metals. </p>

No description available.

Collision of the Yakutat Terrane with North America in southern Alaska has driven growth of the Chugach-St. Elias orogen. Glaciation of the St. Elias Range has periodically increased since the Miocene, but began dominating erosion and spurred enhanced exhumation since the mid-Pleistocene transition at ~1 Ma. Ice associated with this glacial intensification carved cross-shelf sea valleys that connect the St. Elias Range to the deep-sea Surveyor Fan. A newly increased terrigenous sediment flux into the fan triggered the formation and growth of the Surveyor Channel. The change in geomorphology observed throughout Fan sequences allows us to characterize the influence that a glaciated orogen can have in shaping margin processes and the sediment pathways from source to sink. Seismic data also reveal an isolated, large, short runout, mass-transport deposit (MTD) buried in the Surveyor Fan. The MTD geometry, size and location on a convergent margin lend support to recent studies suggesting seismic strengthening and infrequent sediment failure on active margins. This study provides insight into the magnitude and scope of events required to cause submarine mega-slides and overcome higher than normal sediment shear strength, including the influence of climate and sea level change. Beneath the Surveyor Fan, integrated geophysical data reveals massive intraplate shearing, and a lack of oceanic crust magnetic lineaments in regions of Pacific Plate crust. We argue that stress from the Yakutat-North America collision transferred outboard to the Pacific Plate is the major driver for the deformation causing these features. This stress would have resulted in significant strain in the NE corner of the Pacific Plate, creating pathways for sill formation in the crust and Surveyor Fan. The collision further intensified as the thickest Yakutat portion began to subduct during the Pleistocene, possibly providing the impetus for the creation of the Gulf of Alaska Shear Zone, a >200 km zone of shear extending out into the Pacific Plate. This study highlights the importance of farfield stress from complex tectonic regimes in consideration of large-scale oceanic intraplate deformation. / text