Electron spin resonance signature of the oxygen vacancy in HfO 2

The oxygen vacancy has been inferred to be the critical defect in HfO 2, responsible for charge trapping, gate threshold voltage instability, and Fermi level pinning for high work function gates, but it has never been conclusively identified. Here, the electron spin resonance g tensor parameters of the oxygen vacancy are calculated, using methods that do not over-estimate the delocalization of the defect wave function, to be g xx = 1.918, g yy = 1.926, g zz = 1.944, and are consistent with an observed spectrum. The defect undergoes a symmetry lowering polaron distortion to be localized mainly on a single adjacent Hf ion. © 2012 American Institute of Physics.

A high performance oxygen storage material for chemical looping processes with CO2 capture

Chemical looping combustion (CLC) is a novel combustion technology that involves cyclic reduction and oxidation of oxygen storage materials to provide oxygen for the combustion of fuels to CO2 and H2O, whilst giving a pure stream of CO2 suitable for sequestration or utilisation. Here, we report a method for preparing of oxygen storage materials from layered double hydroxides (LDHs) precursors and demonstrate their applications in the CLC process. The LDHs precursor enables homogeneous mixing of elements at the molecular level, giving a high degree of dispersion and high-loading of active metal oxide in the support after calcination. Using a Cu-Al LDH precursor as a prototype, we demonstrate that rational design of oxygen storage materials by material chemistry significantly improved the reactivity and stability in the high temperature redox cycles. We discovered that the presence of sodium-containing species were effective in inhibiting the formation of copper aluminates (CuAl2O4 or CuAlO 2) and stabilising the copper phase in an amorphous support over multiple redox cycles. A representative nanostructured Cu-based oxygen storage material derived from the LDH precursor showed stable gaseous O2 release capacity (∼5 wt%), stable oxygen storage capacity (∼12 wt%), and stable reaction rates during reversible phase changes between CuO-Cu 2O-Cu at high temperatures (800-1000 °C). We anticipate that the strategy can be extended to manufacture a variety of metal oxide composites for applications in novel high temperature looping cycles for clean energy production and CO2 capture. © The Royal Society of Chemistry 2013.

Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion

Chemical looping combustion (CLC) uses a metal oxide (the oxygen carrier) to provide oxygen for the combustion of a fuel and gives an inherent separation of pure CO2 with minimal energy penalty. In solid-fuel CLC, volatile matter will interact with oxygen carriers. Here, the interaction between iron-based oxygen carriers and a volatile hydrocarbon (n-heptane) was investigated in both a laboratory-scale fluidised bed and a thermogravimetric analyser (TGA). Experiments were undertaken to characterise the thermal decomposition of the n-heptane occurring in the presence and in the absence of the oxygen carrier. In a bed of inert particles, carbon deposition increased with temperature and acetylene appeared as a possible precursor. For a bed of carrier consisting of pure Fe2O3, carbon deposition occurred once the Fe2O3 was fully reduced to Fe. When the Fe2O3 was doped with 10 mol % Al2O3 (Fe90Al), deposition started when the carrier was reduced to a mixture of Fe and FeAl2O4, the latter being very unreactive. Furthermore, when pure Fe2O3 was fully reduced to Fe, agglomeration of the fluidised bed occurred. However, Fe90Al did not give agglomeration even after extended reduction. The results suggest that Fe90Al is promising for the CLC of solid fuels. © 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

外源Ca~(2+)对模拟微重力环境中鱼腥藻细胞质膜透性和光合特性的影响

以鱼腥藻为材料 ,研究了外源Ca2 +对模拟微重力环境中微藻细胞膜透性的影响。实验结果表明 :提高培养基中的Ca2 +浓度可减轻由模拟微重力造成的膜透性增大 ,有助于稳定细胞膜结构和功能。同时 ,外源Ca2 +降低了藻细胞光系统Ⅱ (PSⅡ )的光化学效率 (以荧光参数Fv/Fm表示 )下降的幅度 ,表明外源Ca2 +对模拟微重力环境下鱼腥藻细胞光合作用的损伤 ,有良好的防护效应。

Composite electrospun gelatin fiber-alginate gel scaffolds for mechanically robust tissue engineered cornea.

A severe shortage of good quality donor cornea is now an international crisis in public health. Alternatives for donor tissue need to be urgently developed to meet the increasing demand for corneal transplantation. Hydrogels have been widely used as scaffolds for corneal tissue regeneration due to their large water content, similar to that of native tissue. However, these hydrogel scaffolds lack the fibrous structure that functions as a load-bearing component in the native tissue, resulting in poor mechanical performance. This work shows that mechanical properties of compliant hydrogels can be substantially enhanced with electrospun nanofiber reinforcement. Electrospun gelatin nanofibers were infiltrated with alginate hydrogels, yielding transparent fiber-reinforced hydrogels. Without prior crosslinking, electrospun gelatin nanofibers improved the tensile elastic modulus of the hydrogels from 78±19 kPa to 450±100 kPa. Stiffer hydrogels, with elastic modulus of 820±210 kPa, were obtained by crosslinking the gelatin fibers with carbodiimide hydrochloride in ethanol before the infiltration process, but at the expense of transparency. The developed fiber-reinforced hydrogels show great promise as mechanically robust scaffolds for corneal tissue engineering applications.

Spin-cluster effect and lattice-deformation-induced Kondo effect, spin-glass freezing, and strong phonon scattering in La 0.7 Ca 0.3Mn 1-xCr xO 3

Besides the Kondo effect observed in dilute magnetic alloys, the Cr-doped perovskite manganate compounds La0.7 Ca0.3 Mn1-x Crx O3 also exhibit Kondo effect and spin-glass freezing in a certain composition range. An extensive investigation for the La0.7 Ca0.3 Mn1-x Crx O3 (x=0.01, 0.05, 0.10, 0.3, 0.6, and 1.0) system on the magnetization and ac susceptibility, the resistivity and magnetoresistance, as well as the thermal conductivity is done at low temperature. The spin-glass behavior has been confirmed for these compounds with x=0.05, 0.1, and 0.3. For temperatures above Tf (the spin-glass freezing temperature) a Curie-Weiss law is obeyed. The paramagnetic Curie temperature θ is dependent on Cr doping. Below Tf there exists a Kondo minimum in the resistivity. Colossal magnetoresistance has been observed in this system with Cr concentration up to x=0.6. We suppose that the substitution of Mn with Cr dilutes Mn ions and changes the long-range ferromagnetic order of La0.7 Ca0.3 MnO3. These behaviors demonstrate that short-range ferromagnetic correlation and fluctuation exist among Mn spins far above Tf. Furthermore, these interactions are a precursor of the cooperative freezing at Tf. The "double bumps" feature in the resistivity-temperature curve is observed in compounds with x=0.05 and 0.1. The phonon scattering is enhanced at low temperatures, where the second peak of double bumps comes out. The results indicate that the spin-cluster effect and lattice deformation induce Kondo effect, spin-glass freezing, and strong phonon scattering in mixed perovskite La0.7 Ca0.3 Mn1-x Crx O3. © 2005 American Institute of Physics.

Effects of silicon addition on the electrical and magnetic properties of copper-doped (La,Ca)MnO3 compounds

In this paper we report about the electrical properties of La 0.7Ca0.3MnO3 compounds substituted by copper on the manganese site and/or deliberately contaminated by SiO2 in the reactant mixture. Several phenomena have been observed and discussed. SiO2 addition leads to the formation of an apatite-like secondary phase that affects the electrical conduction through the percolation of the charge carriers. On the other hand, depending on the relative amounts of copper and silicon, the temperature dependence of the electrical resistivity can be noticeably modified: our results enable us to compare the effects of crystallographic vacancies on the A and B sites of the perovskite with the influence of the copper ions substituted on the manganese site. The most original result occurs for the compounds with a small ratio Si/Cu, which display double-peaked resistivity vs. temperature curves. © 2003 Elsevier B.V. All rights reserved.

Composite electrospun gelatin fiber-alginate gel scaffolds for mechanically robust tissue engineered cornea

A severe shortage of good quality donor cornea is now an international crisis in public health. Alternatives for donor tissue need to be urgently developed to meet the increasing demand for corneal transplantation. Hydrogels have been widely used as scaffolds for corneal tissue regeneration due to their large water content, similar to that of native tissue. However, these hydrogel scaffolds lack the fibrous structure that functions as a load-bearing component in the native tissue, resulting in poor mechanical performance. This work shows that mechanical properties of compliant hydrogels can be substantially enhanced with electrospun nanofiber reinforcement. Electrospun gelatin nanofibers were infiltrated with alginate hydrogels, yielding transparent fiber-reinforced hydrogels. Without prior crosslinking, electrospun gelatin nanofibers improved the tensile elastic modulus of the hydrogels from 78±19. kPa to 450±100. kPa. Stiffer hydrogels, with elastic modulus of 820±210. kPa, were obtained by crosslinking the gelatin fibers with carbodiimide hydrochloride in ethanol before the infiltration process, but at the expense of transparency. The developed fiber-reinforced hydrogels show great promise as mechanically robust scaffolds for corneal tissue engineering applications. © 2013 Elsevier Ltd.

Creep and oxygen diffusion in magnetite

The creep rate of polycrystalline Fe3O4 has been measured as a fonction of stress and oxygen partial pressure in the temperature range 480-1100°C. A regime of power law creep is found at high stress, with a stress exponent of ≈- 3.1 and an activation energy of 264 kJ/mol. A regime of diffusional flow is found at lower stresses and is interpreted as Nabarro-Herring creep. The data for the two regimes are combined to deduce an oxygen diffusion coefficient of ≈-10-5 exp(-264 kJ/mol/RT) m2s-1, with oxygen vacancies suggested as the mobile species. © 1990.

Gelatin nanofiber-reinforced alginate gel scaffolds for corneal tissue engineering.

A severe shortage of donor cornea is now an international crisis in public health. Substitutes for donor tissue need to be developed to meet the increasing demand for corneal transplantation. Current attempts in designing scaffolds for corneal tissue regeneration involve utilization of expensive materials. Yet, these corneal scaffolds still lack the highly-organized fibrous structure that functions as a load-bearing component in the native tissue. This work shows that transparent nanofiber-reinforced hydrogels could be developed from cheap, non-immunogenic and readily available natural polymers to mimic the cornea's microstructure. Electrospinning was employed to produce gelatin nanofibers, which were then infiltrated with alginate hydrogels. Introducing electrospun nanofibers into hydrogels improved their mechanical properties by nearly one order of magnitude, yielding mechanically robust composites. Such nanofiber-reinforced hydrogels could serve as alternatives to donor tissue for corneal transplantation.

Oxygen carrier dispersion in inert packed beds to improve performance in chemical looping combustion

Various packed beds of copper-based oxygen carriers (CuO on Al2O3) were tested over 100 cycles of low temperature (673K) Chemical Looping Combustion (CLC) with H2 as the fuel gas. The oxygen carriers were uniformly mixed with alumina (Al2O3) in order to investigate the level of separation necessary to prevent agglomeration. It was found that a mass ratio of 1:6 oxygen carrier to alumina gave the best performance in terms of stable, repeating hydrogen breakthrough curves over 100 cycles. In order to quantify the average separation achieved in the mixed packed beds, two sphere-packing models were developed. The hexagonal close-packing model assumed a uniform spherical packing structure, and based the separation calculations on a hypergeometric probability distribution. The more computationally intensive full-scale model used discrete element modelling to simulate random packing arrangements governed by gravity and contact dynamics. Both models predicted that average 'nearest neighbour' particle separation drops to near zero for oxygen carrier mass fractions of x≥0.25. For the packed bed systems studied, agglomeration was observed when the mass fraction of oxygen carrier was above this threshold. © 2013 Elsevier B.V.