Magnetic resonance studies of cement based materials in inhomogeneous magnetic fields

Single-sided magnets give hope that Nuclear Magnetic Resonance (NMR) might in future be used for in situ characterisation of hydration and water transport in the surface layers of concrete slabs. Towards that end, a portable NMR-MOUSE (MObile Universal Surface Explorer) has been used to follow the hydration of gypsum based plaster, a Portland cement paste and concrete mortar. The results compare favourably to those obtained using a standard laboratory bench-top spectrometer. Further, stray field imaging (STRAFI) based methods have been used with embedded NMR detector coils to study water transport across a mortar/topping interface. The measured signal amplitudes are found to correlate with varying sample conditions.     

Multidimensional Modelling of Polymer Electrolyte Fuel Cells under a Current Density Boundary Condition

A three‐dimensional numerical model of the polymer electrolyte fuel cell (PEFC) is applied to study current distribution and cell performance under a current density boundary condition. Since the electronic resistance in the along‐channel direction in the current collector plate is much larger than in the other two directions, i.e., 50 mΩ cm² vs. 0.5 mΩ cm², it significantly affects current flow, and current and cell voltage distributions in a PEFC. An identical polarization curve results with two different boundary conditions, constant cell voltage and constant current density, however, the current density profiles in the along‐channel direction differ significantly; it is much flatter for the constant current boundary condition. Increasing the electronic conductivity of the bipolar plate diminishes the difference in the current density distribution under the two boundary conditions. The results also point out that an experimental validation of a PEFC model based on the polarization curve alone is insufficient, and that detailed current density distribution data in the along‐channel direction is essential.     

Microfluidic modeling and simulation of flow in membrane microreactors

We study the development of a mathematical model that describes isothermal microfluidic steady flow in a membrane microreactor, i.e., a silicon microreactor that houses a permeable membrane in one wall. The model employs the Navier-Stokes equation with appropriate boundary conditions for fluid permeation through the membrane and velocity slip at the walls to account for high Knudsen number. The model equations are solved analytically using finite Fourier transforms. The model solution is used to evaluate the effect of fluid permeation through the membrane and the Knudsen number on the velocity profile and pressure drop. For the simplified cases of no permeation and/or no slip, the derived solution is in excellent agreement with published experimental and theoretical results available in the literature. The utility of the model is illustrated by applying the results to a membrane microseparator used to separate hydrogen from the other effluents in a microreformer.     

Transport of lithium through a supported liquid membrane of LIX54 and TOPO in kerosene

A mathematical transport model is developed for the extraction of lithium from dilute synthetic solution, simulating geothermal water, using a supported liquid membrane (SLM) of LIX54 (major component is -acetyl-m-dodecylacetophenone) and TOPO (tri-n-octylphosphine oxide) in kerosene. The model is based on fundamental mass transfer and kinetics mechanisms that account for all possible transport resistances. The model is solved numerically and is used to investigate the effect of various extraction conditions and membrane support characteristics. Reasonable agreement is found between the predicted and the experimental results reported in literature.     

Role of gallium ion on the conducting properties of La0.7(Ba,Sr)0.3Mn1−xGaxO3 (x=0.0, 0.1 and 0.2) perovskite

The transport properties of Ga-doped La_0.7(Ba, Sr)_0.3Mn_1−xGa_xO₃ (x=0.0, 0.1 and 0.2) perovskite materials were investigated by admittance spectroscopy over a wide range of temperatures and frequencies. The electronic conduction was found to be dominated by thermally activated hopping and to depend strongly on Ga-content. Results have shown samples with x=0.0 and 0.1 exhibit a metallic behavior at low temperature and a semiconducting one at high temperature. The temperature (T_MI) of the metal–insulator transition was found to be about 180 and 120 K for samples with x=0.0 and 0.1, respectively. Ga doping leads to a depletion in the number of hopping electrons, which suppresses metallicity and pushes the system in semiconductor side. Besides, the activation energy (E_a) deduced from the variation of conductance as a function of temperature, was found to increase from 89 to 165 meV when x increased from 0.0 to 0.2. This increase can be explained by the decrease of charge carriers with increasing Ga-content.     

Preparation and electrical conductivity of KTaO3-based proton conductor

KTaO₃ and KTa_0.9M_0.1O_3-α (M = Ti, Hf, Zr) were prepared by solid state reaction at 1330 °C for 2 h and characterized by x-ray diffraction. The AC impedance technique was used to analyze the sintered solid electrolytes in 1%H₂/Ar and dry air atmosphere. Among KTa_0.9M_0.1O_3-α (M = Ti, Hf, Zr), KTa_0.9Zr_0.1O_3-α displays the highest conductivity in 1%H₂/Ar atmosphere. The carriers transport numbers of solid electrolytes were measured by concentration cell method. The results show KTa_0.9Zr_0.1O_3-α is a pure proton conductor below 525 °C. Stability tests show that KTa_0.9Zr_0.1O_3-α has good chemical stability against CO₂ and H₂O.     

Fundamental salt and water transport properties in directly copolymerized disulfonated poly(arylene ether sulfone) random copolymers

Water and sodium chloride solubility, diffusivity and permeability in disulfonated poly(arylene ether sulfone) (BPS) copolymers were measured for both acid and salt form samples at sulfonation levels from 20 to 40 mol percent. The hydrophilicity of these materials, based on water uptake, increased significantly as sulfonation level increased. The water permeability of BPS materials in both the salt and acid forms increases more than one order of magnitude as sulfonation level increases from 20% to 40%, while NaCl permeability increases by two orders of magnitude. The water and salt diffusivity and permeability were correlated with water uptake, consistent with expectations from free volume theory. In addition, a tradeoff was observed between water/salt solubility, diffusivity, and permeability selectivity and water solubility, diffusivity and permeability, respectively. This finding suggests a water/salt permeability/selectivity tradeoff, similar to that operative in gas separation polymers, in this family of polymers.     

Design and characterisation of a close-concentric annular reactor for kinetic studies at high temperatures

A novel annular reactor for kinetic studies at high temperature and flow conditions has been designed to keep eccentricity tolerances below 10%. In a previous work, we have shown that it is very important to keep such low eccentricity values in order to collect reliable kinetic data from this type of reactors. As proposed in this study, a modified reactor with the use of a spacer could guarantee an annular duct with low levels of eccentricity. Manufacturing tolerances or deformation effects giving rise to eccentricity can be significantly minimised when using this apparatus. The reactor has been both experimentally and theoretically characterised. Carbon monoxide oxidation was used as a model reaction under mass-transfer limited conditions revealing an eccentricity of ∼5%. With such small eccentricity levels, a concentric annular form can be assumed in the reactor analysis. Simple 1D or 2D models can therefore be inexpensively used in the evaluation of the kinetic data. Also, prior to the design of the annular reactor, a numerical investigation was carried out to clarify the effects of eccentricity, physical properties of the carrier gas and the annular aspect ratio on mass-transfer limitations. Contrary to expectations, a considerable increase in the fuel mass-diffusivity by carrier gas substitution did not change the mass-transfer rates for cases when eccentricity and aspect ratios were high.     

An analytic solution to the transient diffusion-reaction problem in particles dispersed in a slurry reactor

In this work, we present the solution of the equations that govern the reactant transport in a well mixed system that contains particles where diffusion and first-order reaction occur. The transport equations are coupled by an interfacial boundary condition that includes mass transfer resistance. The statement of the problem allows arbitrary time depending feed functions. The evaluation of the solution obtained by the Laplace method requires the solution of an eigenvalue problem. We discuss the evaluation of the solution, and typical results for three different feed functions: step, pulse and oscillatory functions are presented. The resulting equations are able to show the effect of internal and external mass transfer limitations on the particle and fluid concentrations and on kinetic experimental results.     

Experimental analysis of bubble mode in a plate-type absorber

An experimental analysis of ammonia-water absorption was performed in a plate-type absorber. The flow of water and ammonia gas was performed in the bubble mode. The experiments were made to examine the effects of solution flow rate and gas flow rate on the performance of the absorber. It was found that the increase of solution flow rate rarely affected the mass transfer, but improved the heat transfer. As the gas flow rate increased, slugging occurred in the bubble mode and influenced the thermal boundary layer. Finally, the results were converted into dimensionless numbers to elucidate physical phenomena and plotted as Sherwood number versus Reynolds number for mass transfer performance and Nusselt number versus Reynolds number for heat transfer performance.