Development of the Oxide Ion Conductor Na0.5Bi0.5TiO3 (NBT) for Solid Oxide Cells

Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material with potential to replace lead zirconate titanate (PZT),1 however high leakage conductivity for the material has been widely reported.2 Through a combination of Impedance Spectroscopy (IS), O2- ion transference (EMF) number experiments and O18 tracer diffusion measurements, combined with Time-of-flight Secondary Ion Mass Spectrometry (TOFSIMS), it was identified that this leakage conductivity was due to oxygen ion conductivity. The volatilization of bismuth during synthesis, causing oxygen vacancies, is believed to be responsible for the leakage conductivity.3 The oxide-ion conductivity, when doped with magnesium, exceeds that of yttria-stabilized zirconia (YSZ) at ~500 °C,3 making it a potential electrolyte material for Intermediate Temperature Solid Oxide Cells (ITSOCs). Figure 1 shows the comparison of bulk oxide ion conductivity between 2 at.% Mg-doped NBT and other known oxide ion conductors.

As part of the UK wide £5.7m 4CU project, research has concentrated on trying to develop NBT for use in Intermediate Temperature Solid Oxide Cells (ITSOCS). With the aim of achieving mixed ionic and electronic conduction, transition metals were chemically doped on to the Ti-site. A range of experimental techniques was used to characterize the materials aimed at investigating both conductivity and material structure (Scanning Electron Microscopy (SEM), IS, X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS)). The potential for NBT as an ITSOC material, as well as the challenges of developing the material, will be discussed.

(1) Takenaka T. et al. Jpn. J. Appl. Phys 1999, 30, 2236.

(2) Hiruma Y. et al. J. Appl. Phys 2009, 105, 084112.

(3) Li. M. et al. Nature Materials 2013, 13, 31.

Cork structural characteristics and their influence on the oxygen ingress through wine stoppers

Doutoramento em Engenharia Florestal e dos Recursos Naturais - Instituto Superior de Agronomia - UL

Measurements of neutral atom diffusion and electron-ion recombination by laser enhanced ionisation and planar laser induced fluorescence in an air-acetylene flame

The spatial and temporal evolution of a depleted atomic distribution created by laser enhanced ionisation (LEI) was employed to determine both a diffusion coefficient for sodium (Na) and an electron (e(-)) and sodium ion recombination rate coefficient in an analytical air-C2H2 flame. A depleted distribution of neutral sodium atoms was produced in a flame by ionising approximately 80% of the irradiated sodium atoms in a well defined region using a two step LEI excitation scheme. Following depletion by ionisation, planar laser induced fluorescence (PLIF) images of the depleted region recorded the diffusion and decay of the depleted Na distribution for different depletion-probe delays. From measurements of the diffused width of the distribution, an accurate diffusion coefficient D = (1.19 +/- 0.03) x 10(-3) m(2) s(-1) for Na was determined in teh burnt gases of the flame. Measurements of the integrated fluorescence intensity in the depleted region for different depletion-probe delays were related to an increase in atomic sodium concentration caused by electron-ion recombination. At high concentrations (greater than or equal to 50 mu g ml(-1)), where the electron and ion concentrations in the depleted region were assumed equal, a recombination rate coefficient of 4.2 x 10(-9) cm(3) s(-1) was calculated. (C) 1997 Elsevier Science B.V.

PFG-NMR measurements of the self-diffusion coefficients of water in equilibrium poly(HEMA-co-THFMA) hydrogels

The self-diffusion coefficients for water in a series of copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA, swollen with water to their equilibrium states have been studied at 310 K using PFG-NMR. The self-diffusion coefficients calculated from the Stejskal-Tanner equation, D-obs, for all of the hydrated polymers were found to be dependent on the NMR storage time, as a result of spin exchange between the proton reservoirs of the water and the polymers, reaching an equilibrium plateau value at long storage times. The true values of the diffusion coefficients were calculated from the values of D-obs, in the plateau regions by applying a correction for the fraction of water protons present, obtained from the equilibrium water contents of the gels. The true self-diffusion coefficient for water in polyHEMA obtained at 310 K by this method was 5.5 x 10(-10) m(2) s(-1). For the copolymers containing 20% HEMA or more a single value of the self-diffusion coefficient was found, which was somewhat larger than the corresponding values obtained for the macroscopic diffusion coefficient from sorption measurements. For polyTHFMA and copolymers containing less than 20% HEMA, the PFG-NMR stimulated echo attenuation decay curves and the log-attenuation plots were characteristic of the presence of two diffusing water species. The self-diffusion coefficients of water in the equilibrium-hydrated copolymers were found to be dependent on the copolymer composition, decreasing with increasing THFMA content.

Interobserver and intraobserver variability of the apparent diffusion coefficient in treated malignant hepatic lesions on a 3.0T machine: measurements in the whole lesion versus in the area with the most restricted diffusion.

PURPOSE: To assess the inter/intraobserver variability of apparent diffusion coefficient (ADC) measurements in treated hepatic lesions and to compare ADC measurements in the whole lesion and in the area with the most restricted diffusion (MRDA). MATERIALS AND METHODS: Twenty-five patients with treated malignant liver lesions were examined on a 3.0T machine. After agreeing on the best ADC image, two readers independently measured the ADC values in the whole lesion and in the MRDA. These measurements were repeated 1 month later. The Bland-Altman method, Spearman correlation coefficients, and the Wilcoxon signed-rank test were used to evaluate the measurements. RESULTS: Interobserver variability for ADC measurements in the whole lesion and in the MRDA was 0.17 x 10(-3) mm(2)/s [-0.17, +0.17] and 0.43 x 10(-3) mm(2)/s [-0.45, +0.41], respectively. Intraobserver limits of agreement could be as low as [-0.10, +0.12] 10(-3) mm(2)/s and [-0.20, +0.33] 10(-3) mm(2)/s for measurements in the whole lesion and in the MRDA, respectively. CONCLUSION: A limited variability in ADC measurements does exist, and it should be considered when interpreting ADC values of hepatic malignancies. This is especially true for the measurements of the minimal ADC.

Interobserver and intraobserver variability of apparent diffusion coefficient measurements in treated malignant hepatic lesions: measurements in the whole lesion versus in the area with the most restricted diffusion

Purpose: The increase of apparent diffusion coefficient (ADC) in treated hepatic malignancies compared to pre-therapeutic values has been interpreted as treatment success; however, the variability of ADC measurements remains unknown. Furthermore, ADC has been usually measured in the whole lesion, while measurements should be probably centered on the area with the most restricted diffusion (MRDA) as it represents potential tumoral residue. Our objective was to compare the inter/intraobserver variability of ADC measurements in the whole lesion and in MRDA. Material and methods: Forty patients previously treated with chemoembolization or radiofrequency were evaluated (20 on 1.5T and 20 on 3.0T). After consensual agreement on the best ADC image, two readers measured the ADC values using separate regions of interest that included the whole lesion and the whole MRDA without exceeding their borders. The same measurements were repeated two weeks later. Spearman test and the Bland-Altman method were used. Results: Interobserver correlation in ADC measurements in the whole lesion and MRDA was as follows: 0.962 and 0.884. Intraobserver correlation was, respectively, 0.992 and 0.979. Interobserver limits of variability (mm2/sec*10-3) were between -0.25/+0.28 in the whole lesion and between -0.51/+0.46 in MRDA. Intraobserver limits of variability were, respectively: -0.25/+0.24 and -0.43/+0.47. Conclusion: We observed a good inter/intraobserver correlation in ADC measurements. Nevertheless, a limited variability does exist, and it should be considered when interpreting ADC values of hepatic malignancies.

Speciation and Bioavailability Measurements of Environmental Plutonium Using Diffusion in Thin Films.

The biological uptake of plutonium (Pu) in aquatic ecosystems is of particular concern since it is an alpha-particle emitter with long half-life which can potentially contribute to the exposure of biota and humans. The diffusive gradients in thin films technique is introduced here for in-situ measurements of Pu bioavailability and speciation. A diffusion cell constructed for laboratory experiments with Pu and the newly developed protocol make it possible to simulate the environmental behavior of Pu in model solutions of various chemical compositions. Adjustment of the oxidation states to Pu(IV) and Pu(V) described in this protocol is essential in order to investigate the complex redox chemistry of plutonium in the environment. The calibration of this technique and the results obtained in the laboratory experiments enable to develop a specific DGT device for in-situ Pu measurements in freshwaters. Accelerator-based mass-spectrometry measurements of Pu accumulated by DGTs in a karst spring allowed determining the bioavailability of Pu in a mineral freshwater environment. Application of this protocol for Pu measurements using DGT devices has a large potential to improve our understanding of the speciation and the biological transfer of Pu in aquatic ecosystems.

Inter- and intralaboratory variation of in vitro diffusion cell measurements: An international multicenter study using quasi-standardized methods and materials

In vitro measurements of skin absorption are an increasingly important aspect of regulatory studies, product support claims, and formulation screening. However, such measurements are significantly affected by skin variability. The purpose of this study was to determine inter- and intralaboratory variation in diffusion cell measurements caused by factors other than skin. This was attained through the use of an artificial (silicone rubber) rate-limiting membrane and the provision of materials including a standard penetrant, methyl paraben (MP), and a minimally prescriptive protocol to each of the 18 participating laboratories. Standardized calculations of MP flux were determined from the data submitted by each laboratory by applying a predefined mathematical model. This was deemed necessary to eliminate any interlaboratory variation caused by different methods of flux calculations. Average fluxes of MP calculated and reported by each laboratory (60 +/- 27 mug cm(-2) h(-1), n = 25, range 27-101) were in agreement with the standardized calculations of MP flux (60 +/- 21 mug cm(-2) h(-1), range 19-120). The coefficient of variation between laboratories was approximately 35% and was manifest as a fourfold difference between the lowest and highest average flux values and a sixfold difference between the lowest and highest individual flux values. Intra-laboratory variation was lower, averaging 10% for five individuals using the same equipment within a single laboratory. Further studies should be performed to clarify the exact components responsible for nonskin-related variability in diffusion cell measurements. It is clear that further developments of in vitro methodologies for measuring skin absorption are required. (C) 2005 Wiley-Liss, Inc.

Soot measurements in steady and pulsed ethylene/air diffusion flames using Laser-Induced Incandescence

Combustion-generated carbon black nano particles, or soot, have both positive and negative effects depending on the application. From a positive point of view, it is used as a reinforcing agent in tires, black pigment in inks, and surface coatings. From a negative point of view, it affects performance and durability of many combustion systems, it is a major contributor of global warming, and it is linked to respiratory illness and cancer. Laser-Induced Incandescence (LII) was used in this study to measure soot volume fractions in four steady and twenty-eight pulsed ethylene diffusion flames burning at atmospheric pressure. A laminar coflow diffusion burner combined with a very-high-speed solenoid valve and control circuit provided unsteady flows by forcing the fuel flow with frequencies between 10 Hz and 200 Hz. Periodic flame oscillations were captured by two-dimensional phase-locked LII images and broadband luminosity images for eight phases (0° – 360°) covering each period. A comparison between the steady and pulsed flames and the effect of the pulsation frequency on soot volume fraction in the flame region and the post flame region are presented. The most significant effect of pulsing frequency was observed at 10 Hz. At this frequency, the flame with the lowest mean flow rate had 1.77 times enhancement in peak soot volume fraction and 1.2 times enhancement in total soot volume fraction; whereas the flame with the highest mean flow rate had no significant change in the peak soot volume fraction and 1.4 times reduction in the total soot volume fraction. A correlation (fvRe-1 = a + b·Str) for the total soot volume fraction in the flame region for the unsteady laminar ethylene flames was obtained for the pulsation frequency between 10 Hz and 200 Hz, and the Reynolds number between 37 and 55. The soot primary particle size in steady and unsteady flames was measured using the Time-Resolved Laser-Induced Incandescence (TIRE-LII) and the double-exponential fit method. At maximum frequency (200 Hz), the soot particles were smaller in size by 15% compared to the steady case in the flame with the highest mean flow rate.

Soot Measurements in Steady and Pulsed Ethylene/Air Diffusion Flames Using Laser-Induced Incandescence

Combustion-generated carbon black nano particles, or soot, have both positive and negative effects depending on the application. From a positive point of view, it is used as a reinforcing agent in tires, black pigment in inks, and surface coatings. From a negative point of view, it affects performance and durability of many combustion systems, it is a major contributor of global warming, and it is linked to respiratory illness and cancer. Laser-Induced Incandescence (LII) was used in this study to measure soot volume fractions in four steady and twenty-eight pulsed ethylene diffusion flames burning at atmospheric pressure. A laminar coflow diffusion burner combined with a very-high-speed solenoid valve and control circuit provided unsteady flows by forcing the fuel flow with frequencies between 10 Hz and 200 Hz. Periodic flame oscillations were captured by two-dimensional phase-locked LII images and broadband luminosity images for eight phases (0°- 360°) covering each period. A comparison between the steady and pulsed flames and the effect of the pulsation frequency on soot volume fraction in the flame region and the post flame region are presented. The most significant effect of pulsing frequency was observed at 10 Hz. At this frequency, the flame with the lowest mean flow rate had 1.77 times enhancement in peak soot volume fraction and 1.2 times enhancement in total soot volume fraction; whereas the flame with the highest mean flow rate had no significant change in the peak soot volume fraction and 1.4 times reduction in the total soot volume fraction. A correlation (ƒv Reˉ1 = a+b· Str) for the total soot volume fraction in the flame region for the unsteady laminar ethylene flames was obtained for the pulsation frequency between 10 Hz and 200 Hz, and the Reynolds number between 37 and 55. The soot primary particle size in steady and unsteady flames was measured using the Time-Resolved Laser-Induced Incandescence (TIRE-LII) and the double-exponential fit method. At maximum frequency (200 Hz), the soot particles were smaller in size by 15% compared to the steady case in the flame with the highest mean flow rate.

Feasibility And Reproducibility Of Diffusion-weighted Magnetic Resonance Imaging Of The Fetal Brain In Twin-twin Transfusion Syndrome.

The aim of this study is to test the feasibility and reproducibility of diffusion-weighted magnetic resonance imaging (DW-MRI) evaluations of the fetal brains in cases of twin-twin transfusion syndrome (TTTS). From May 2011 to June 2012, 24 patients with severe TTTS underwent MRI scans for evaluation of the fetal brains. Datasets were analyzed offline on axial DW images and apparent diffusion coefficient (ADC) maps by two radiologists. The subjective evaluation was described as the absence or presence of water diffusion restriction. The objective evaluation was performed by the placement of 20-mm(2) circular regions of interest on the DW image and ADC maps. Subjective interobserver agreement was assessed by the kappa correlation coefficient. Objective intraobserver and interobserver agreements were assessed by proportionate Bland-Altman tests. Seventy-four DW-MRI scans were performed. Sixty of them (81.1%) were considered to be of good quality. Agreement between the radiologists was 100% for the absence or presence of diffusion restriction of water. For both intraobserver and interobserver agreement of ADC measurements, proportionate Bland-Altman tests showed average percentage differences of less than 1.5% and 95% CI of less than 18% for all sites evaluated. Our data demonstrate that DW-MRI evaluation of the fetal brain in TTTS is feasible and reproducible.

Upconversion in Nd(3+)-doped glasses: Microscopic theory and spectroscopic measurements

In this work, we report a systematic investigation of upconversion losses and their effects on fluorescence quantum efficiency and fractional thermal loading in Nd(3+)-doped fluoride glasses. The energy transfer upconversion (gamma(up)) parameter, which describes upconversion losses, was experimentally determined using different methods: thermal lens (TL) technique and steady state luminescence (SSL) measurements. Additionally, the upconversion parameter was also obtained from energy transfer models and excited state absorption measurements. The results reveal that the microscopic treatment provided by the energy transfer models is similar to the macroscopic ones achieved from the TL and SSL measurements because similar gamma(up) parameters were obtained. Besides, the achieved results also point out the migration-assisted energy transfer according to diffusion-limited regime rather than hopping regime as responsible for the upconversion losses in Nd-doped glasses. (c) 2008 American Institute of Physics.

Superconducting current path and flux line shape in NbTiTa obtained by inter-diffusion process

This investigation presents a comprehensive characterization of magnetic and transport properties of an interesting superconducting wire, Nb-Ti -Ta, obtained through the solid-state diffusion between Nb-12 at.% Ta alloy and pure Ti. The physical properties obtained from magnetic and transport measurements related to the microstructure unambiguously confirmed a previous proposition that the superconducting currents flow in the center of the diffusion layer, which has a steep composition variation. The determination of the critical field also confirmed that the flux line core size is not constant, and in addition it was possible to determine that, in the center of the layer, the flux line core is smaller than at the borders. A possible core shape design is proposed. Among the wires studied, the one that presented the best critical current density was achieved for a diffusion layer with a composition of about Nb-32% Ti-10% Ta, obtained with a heat treatment at 700 degrees C during 120 h, in agreement with previous studies. It was determined that this wire has the higher upper critical field, indicating that the optimization of the superconducting behavior is related to an intrinsic property of the ternary alloy.

Experimental Measurement of Water Diffusion through Fine Aggregate Mixtures

The water diffusion attributable to concentration gradients is among the main mechanisms of water transport into the asphalt mixture. The transport of small molecules through polymeric materials is a very complex process, and no single model provides a complete explanation because of the small molecule`s complex internal structure. The objective of this study was to experimentally determine the diffusion of water in different fine aggregate mixtures (FAM) using simple gravimetric sorption measurements. For the purposes of measuring the diffusivity of water, FAMs were regarded as a representative homogenous volume of the hot-mix asphalt (HMA). Fick`s second law is generally used to model diffusion driven by concentration gradients in different materials. The concept of the dual mode diffusion was investigated for FAM cylindrical samples. Although FAM samples have three components (asphalt binder, aggregates, and air voids), the dual mode was an attempt to represent the diffusion process by only two stages that occur simultaneously: (1) the water molecules are completely mobile, and (2) the water molecules are partially mobile. The combination of three asphalt binders and two aggregates selected from the Strategic Highway Research Program`s (SHRP) Materials Reference Library (MRL) were evaluated at room temperature [23.9 degrees C (75 degrees F)] and at 37.8 degrees C (100 degrees F). The results show that moisture uptake and diffusivity of water through FAM is dependent on the type of aggregate and asphalt binder. At room temperature, the rank order of diffusivity and moisture uptake for the three binders was the same regardless of the type of aggregate. However, this rank order changed at higher temperatures, suggesting that at elevated temperatures different binders may be undergoing a different level of change in the free volume. DOI: 10.1061/(ASCE)MT.1943-5533.0000190. (C) 2011 American Society of Civil Engineers.