Combined Cryo and Room-Temperature Ball Milling to Produce Ultrafine Halide Crystallites

The combined milling at cryogenic temperature as well as room temperature (RT) has been carried out to prepare ultrafine NaCl crystallites. The milling has been done in evacuated tungsten carbide vials backfilled with high-purity Ar. The results indicate the effect duration of cryomilling prior to RT milling has a strong effect on the final crystallite size. The deformation aided sintering of NaCl crystallites during RT milling and leads to the formation of bimodal distribution of crystallites. The cuboidal-shaped NaCl crystallite undergoes a roughening transition due to plastic deformation. The experimental results are explained using the temperature-dependent mechanical properties of NaCl single crystals and plastic-deformation-induced roughening.

Influence of grain size on high temperature fracture in a Mg AZ31 alloy

Tensile experiments at 673 K and grain sizes from similar to 8 to 17 mu m revealed large ductility at a low strain rate and a reduced ductility at a high strain rate, corresponding to a change from a high to a low value for the strain rate sensitivity. High strain rate deformation led to fracture by flow localization, whereas low strain rate deformation involved fracture by cavity nucleation and growth. Analysis revealed that grain boundary migration can assist significantly in reducing the stress concentrations caused by grain boundary sliding, thereby retarding cavity nucleation. Calculations demonstrate that the interlinkage of voids parallel and perpendicular to the tensile axis occurs significantly, so that it is not always possible to use the cavity shapes to distinguish between diffusion and plasticity controlled growth. Cavitation damage evolves slowly in materials with a coarser grain size because of reduced nucleation related to a reduction in the strain rate sensitivity and associated grain boundary sliding. (C) 2011 Elsevier B.V. All rights reserved.

Effect of strain rate on the high-temperature low-cycle fatigue properties of a nimonic PE-16 superalloy

Strain-rate effects on the low-cycle fatigue (LCF) behavior of a NIMONIC PE-16 superalloy have been evaluated in the temperature range of 523 to 923 K. Total-strain-controlled fatigue tests were per-formed at a strain amplitude of +/-0.6 pct on samples possessing two different prior microstructures: microstructure A, in the solution-annealed condition (free of gamma' and carbides); and microstructure B, in a double-aged condition with gamma' of 18-nm diameter and M23C6 carbides. The cyclic stress response behavior of the alloy was found to depend on the prior microstructure, testing temperature, and strain rate. A softening regime was found to be associated with shearing of ordered gamma' that were either formed during testing or present in the prior microstructure. Various manifestations of dynamic strain aging (DSA) included negative strain rate-stress response, serrations on the stress-strain hysteresis loops, and increased work-hardening rate. The calculated activation energy matched well with that for self-diffusion of Al and Ti in the matrix. Fatigue life increased with an increase in strain rate from 3 x 10(-5) to 3 x 10(-3) s-1, but decreased with further increases in strain rate. At 723 and 823 K and low strain rates, DSA influenced the deformation and fracture behavior of the alloy. Dynamic strain aging increased the strain localization in planar slip bands, and impingement of these bands caused internal grain-boundary cracks and reduced fatigue life. However, at 923 K and low strain rates, fatigue crack initiation and propagation were accelerated by high-temperature oxidation, and the reduced fatigue life was attributed to oxidation-fatigue interaction. Fatigue life was maximum at the intermediate strain rates, where strain localization was lower. Strain localization as a function of strain rate and temperature was quantified by optical and scanning electron microscopy and correlated with fatigue life.

Xenon in sodium Y zeolite. 2. Arrhenius relation, mechanism, and barrier height distribution for cage-to-cage diffusion

Various geometrical and energetic distribution functions and other properties connected with the cage-to-cage diffusion of xenon in sodium Y zeolite have been obtained from long molecular dynamics calculations. Analysis of diffusion pathways reveals two interesting mechanisms-surface-mediated and centralized modes for cage-to-cage diffusion. The surface-mediated mode of diffusion exhibits a small positive barrier, while the centralized diffusion exhibits a negative barrier for the sorbate to diffuse across the 12-ring window. In both modes, however, the sorbate has to be activated from the adsorption site to enable it to gain mobility. The centralized diffusion additionally requires the sorbate to be free of the influence of the surface of the cage as well. The overall rate for cage-to-cage diffusion shows an Arrhenius temperature dependence with E(a) = 3 kJ/mol. It is found that the decay in the dynamical correction factor occurs on a time scale comparable to the cage residence time. The distributions of barrier heights have been calculated. Functions reflecting the distribution of the sorbate-zeolite interaction at the window and the variations of the distance between the sorbate and the centers of the parent and daughter cages are presented.

Molecular Dynamics Investigation of Structure and Transport in the K2O-2SiO2 System Using a Partial Charge Based Model Potential

Potassium disilicate glass and melt have been investigated by using a new partial charge based potential model in which nonbridging oxygens are differentiated from bridging oxygens by their charges. The model reproduces the structural data pertaining to the coordination polyhedra around potassium and the various bond angle distributions excellently. The dynamics of the glass has been studied by using space and time correlation functions. It is found that K ions migrate by a diffusive mechanism in the melt and by hops below the glass transition temperature. They are also found to migrate largely through nonbridging oxygenrich sites in the silicate matrix, thus providing support to the predictions of the modified random network model.

High-temperature reactions of alkali and plagioclase feldspars with alkali and alkaline-earth chlorides-formation of celsian

High-temperature reactions (Ca 900-degrees-C) involving albite, K-feldspar or plagioclase and K, Ba-or K, Sr chlorides were experimentally studied. These experiments reveal that the reaction between K-exchanged albite, potash feldspar, or plagioclase and Ba-chloride/Ba-K chloride results in the formation of celsian by the breakdown of the starting feldspar structure above 800-degrees-C. Sr-feldspar does not form under similar conditions. A size-effect of the large M-site cation appears to be responsible for the formation of celsian. The reaction between K-feldspar and barium chloride may be used as a method for synthesizing celsian.

High-temperature stability of Ca2ZrSi4O12

The standard Gibbs free energy of formation of orthorhombic Ca2ZrSi4O12 from component oxides ZrO2 (monoclinic), CaO (rock salt), and SiO2 (quartz) has been determined in the temperature range 973 to 1273 K using a solid-state cell incorporating single-crystal CaF2 as the electrolyte: Delta G(f) degrees = -219930 + 11.77T (+/- 1500) J.mol(-1) This is the only quantitative information now available on the stability of Ca2ZrSi4O12.

Influence of Bi 3+ ions in enhancing the magnitude of positive temperature coefficients of resistance in n-BaTiO3 ceramics

Bi3+ ions substituting at Ba-sites in a limited concentration range with another donor dopant occupying the Ti-sites in polycrystalline BaTiO3 enhanced the positive temperature coefficient of resistance (PTCR) by over seven orders of magnitude. These ceramics did not require normal post sinter annealing or a change to an oxygen atmosphere during annealing. These ceramics had low porosities coupled with better stabilities to large applied electric fields and chemically reducing atmospheres. Bi3+ ions limited the grain growth to less than 8 mum in size, they enhanced the concentration of acceptor-type trap centres at the grain-boundary-layer regions and maintained complete tetragonality at low grain sizes in BaTiO3 ceramics.

Molecular dynamics Investigation of structure and transport in the K2O-2SiO2 system using a partial charge based model potential

Potassium disilicate glass and melt have been investigated by using anew partial charge based potential model in which nonbridging oxygens are differentiated from bridging oxygens by their charges. The model reproduces the structural data pertaining to the coordination polyhedra around potassium and the various bond angle distributions excellently. The dynamics of the glass has been studied by using space and time correlation functions. It is found that K ions migrate by a diffusive mechanism in the melt and by hops below the glass transition temperature. They are also found to migrate largely through nonbridging oxygen-rich sites in the silicate matrix, thus providing support to the predictions of the modified random network model.

Temperature-programmed desorption and surface reaction of thiophene over co-mo/.gamma.-Al2O3 hydrodesulfurization catalysts

The temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) of thiophene over a series of Co-Mo/gamma-Al2O3, hydrodesulfurization (HDS) catalysts with varying Co to Mo ratios have been studied with the objective of understanding the promotional role of Co in the HDS reaction. As part of the study, the desorptions (TPD) and hydrogenations (TPSR) of butane, butene, and butadiene over these catalysts have also been investigated. The TPD of the hydrocarbons over catalysts containing no Co showed a single desorption profile while incorporation of Co created an additional site, with higher heats of desorption, without significantly affecting desorption from the original site. The TPSR measurements showed that the two sites had separate and independent activity for the hydrogenation of the C-4 hydrocarbons. The TPD of thiophene over catalysts with varying Co to Mo ratios showed a single desorption profile with identical heats of desorption, implying that Co does not affect or influence the adsorption sites for thiophene. The TPSR of the HDS of thiophene, however, showed that, although the products of the HDS reaction-butane, butene, and H2S-are the same irrespective of the Co content, the temperature profiles and the activation barriers for the formation of these species show considerable change with the Co/Co+Mo ratio. The results are discussed in light of the existing models for the promotional role of Co in the HDS reaction.

Temperature programmed desorption studies on hydrodesulfurization catalysts

The temperature programmed-desorption (TPD) of butane, butene, butadiene and thiophene over a series of Co-MO/gamma-Al2O3 catalysts with varying Co to Mo ratio has been investigated. The TPD of butane, butene and butadiene over catalysts containing no Co showed a single desorption profile while incorporation of Co created an additional site without significantly affecting desorption from the original site. The TPD of thiophene over a series of catalysts with varying Co content showed identical desorption temperature as well as heat of desorption. It was concluded that thiophene was adsorbed on the ''Mo-S'' component of the catalyst and was unaffected by the presence of Co.

Robust/Optimal Temperature Profile Control of a High-Speed Aerospace Vehicle Using Neural Networks

An approximate dynamic programming (ADP)-based suboptimal neurocontroller to obtain desired temperature for a high-speed aerospace vehicle is synthesized in this paper. A I-D distributed parameter model of a fin is developed from basic thermal physics principles. "Snapshot" solutions of the dynamics are generated with a simple dynamic inversion-based feedback controller. Empirical basis functions are designed using the "proper orthogonal decomposition" (POD) technique and the snapshot solutions. A low-order nonlinear lumped parameter system to characterize the infinite dimensional system is obtained by carrying out a Galerkin projection. An ADP-based neurocontroller with a dual heuristic programming (DHP) formulation is obtained with a single-network-adaptive-critic (SNAC) controller for this approximate nonlinear model. Actual control in the original domain is calculated with the same POD basis functions through a reverse mapping. Further contribution of this paper includes development of an online robust neurocontroller to account for unmodeled dynamics and parametric uncertainties inherent in such a complex dynamic system. A neural network (NN) weight update rule that guarantees boundedness of the weights and relaxes the need for persistence of excitation (PE) condition is presented. Simulation studies show that in a fairly extensive but compact domain, any desired temperature profile can be achieved starting from any initial temperature profile. Therefore, the ADP and NN-based controllers appear to have the potential to become controller synthesis tools for nonlinear distributed parameter systems.

Unsteady nonsimilar two-dimensional and axisymmetric water boundary layers with variable viscosity and prandtl number

The influence of temperature-dependent viscosity and Prandtl number on the unsteady laminar nonsimilar forced convection flow over two-dimensional and axisymmetric bodies has been examined where the unsteadiness and (or) nonsimilarity are (is) due to the free stream velocity, mass transfer, and transverse curvature. The partial differential equations governing the flow which involve three independent variables have been solved numerically using an implicit finite-difference scheme along with a quasilinearization technique. It is found that both the skin friction and heat transfer strongly respond to the unsteady free stream velocity distributions. The unsteadiness and injection cause the location of zero skin friction to move upstream. However, the effect of variable viscosity and Prandtl number is to move it downstream. The heat transfer is found to depend strongly on viscous dissipation, but the skin friction is little affected by it. In general, the results pertaining to variable fluid properties differ significantly, from those of constant fluid properties.

An aqueous-solution based low-temperature pathway to synthesize giant dielectric CaCu3Ti4O12-Highly porous ceramic matrix and submicron sized powder

A simple, cost-effective and environment-friendly pathway for preparing highly porous matrix of giant dielectric material CaCu3Ti4O12 (CCTO) through combustion of a completely aqueous precursor solution is presented. The pathway yields phase-pure and impurity-less CCTO ceramic at an ultra-low temperature (700 degrees C) and is better than traditional solid-state reaction schemes which fail to produce pure phase at as high temperature as 1000 degrees C (Li, Schwartz, Phys. Rev. B 75, 012104). The porous ceramic matrix on grinding produced CCTO powder having particle size in submicron order with an average size 300 nm. On sintering at 1050 degrees C for 5 h the powder shows high dielectric constants (>10(4) at all frequencies from 100 Hz to 100 kHz) and low loss (with 0.05 as the lowest value) which is suitable for device applications. The reaction pathway is expected to be extended to prepare other multifunctional complex perovskite materials. (C) 2010 Elsevier B.V. All rights reserved.

Bloch-Nordsieck thermometers: One-loop exponentiation in finite temperature QED

We study the scattering of hard external particles in a heat bath in a real-time formalism for finite temperature QED. We investigate the distribution of the 4-momentum difference of initial and final hard particles in a fully covariant manner when the scale of the process, Q, is much larger than the temperature, T. Our computations are valid for all T subject to this constraint. We exponentiate the leading infra-red term at one-loop order through a resummation of soft (thermal) photon emissions and absorptions. For T > 0, we find that tensor structures arise which are not present at T = 0. These carry thermal signatures. As a result, external particles can serve as thermometers introduced into the heat bath. We investigate the phase space origin of log (Q/M) and log (Q/T) terms.