Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.

Sandwich propellant combustion: Modeling and experimental comparison

This paper reports reacting fluid dynamics calculations for an ammonium percholrate binder sandwich and extracts experimentally observed features including surface profiles and maximum regression rates as a function of pressure and binder thickness. These studies have been carried out by solving the two-dimensional unsteady Navier-Stokes equations with energy and species conservation equations and a kinetic model of three reaction steps (ammonium perchlorate decomposition flame, primary diffusion flame, and final diffusion flame) in the gas phase. The unsteady two-dimensional conduction equation is solved in the condensed phase. The regressing surface is unsteady and two dimensional. Computations have been carried out for a binder thickness range of 25-125 mum and a pressure range of 1.4 to 6.9 MPa. Good comparisons at several levels of detail are used to demonstrate the need for condensed-phase two-dimensional unsteady conduction and three-step gas-phase reactions. The choice of kinetic and thermodynamic parameters is crucial to good comparison with experiments. The choice of activation energy parameters for ammonium percholrate combustion has been made with stability of combustion in addition to experimentally determined values reported in literature. The choice of gas-phase parameters for the diffusion flames are made considering that (a) primary diffusion flame affects the low-pressure behavior and (b) final diffusion flame affects high-pressure behavior. The predictions include the low-pressure deflagration limit of the sandwich apart from others noted above. Finally, this study demonstrates the possibility of making meaningful comparisons with experimental observations on sandwich propellant combustion.

Study of relaxor behavior of 0.7Pb(Mg1/3Nb2/3)O-3-0.3PbTiO(3) thin films

Relaxor properties of polycrystalline 0.7Pb(Mg1/3Nb2/3)O-3-0.3PbTiO(3) (PMN-PT) thin films were studied in terms of the diffuse nature of phase transition along with the frequency dispersion of temperature (T-m) at which the dielectric constant exhibits maximum value. Existence of remnant polarization (P-r) above the phase transition temperature, which is a characteristic property of typical relaxor ferroelectric has also been observed in the present case. The films exhibited a gradual decrease of remnant polarization with increase of temperature. Among the different models of relaxor ferroelectric, Vogel-Fulcher model has been found to be suitable to describe the frequency dispersion of T-m in this case. Freezing of dipole moment with decrease of temperature was thought to be the origin of the temperature dependence of dielectric dispersion.

An assessment of creep deformation and fracture behavior of 2.25Cr-1Mo

The evaluation of the creep deformation and fracture behavior of a 2.25Cr-1Mo steel base metal, a 2.25Cr-1Mo/2.25Cr-1Mo similar weld joint, and a 2.25Cr-1Mo/Alloy 800 dissimilar weld joint at 823 K over a stress range of 90 to WO MPa has been carried out. The specimens for creep testing were taken from single-V weld pads fabricated by a shielded metal arc-welding process using 2.25Cr-1Mo steel (for similar-joint) and INCONEL 182 (for dissimilar-joint) electrodes. The weld pads were subsequently given a postweld hear treatment (PWHT) of 973 K for I hour. The microstructure and microhardness of the weld joints were evaluated in the as-welded, postweld heat-treated, and creep-tested conditions. The heat-affected zone (HAZ) of similar weld joint consisted of bainite in the coarse-prior-austenitic-grain (CPAG) region near the fusion line, followed by bainite in the fine-prior-austenitic-grain (FPAG) and intercritical regions merging with the unaffected base metal. In addition to the HAZ structures in the 2.25Cr-1Mo steel, the dissimilar weld joint displayed a definite INCONEL/2.25Cr-1Mo weld interface structure present either as a sharp line or as a diffuse region. A hardness trough was observed in the intercritical region of the HAZ in both weld joints, while a maxima in hardness was seen at the weld interface of the dissimilar weld joint. Both weld joints exhibited significantly lower rupture lives compared to the 2.25Cr-1Mo base metal. The dissimilar weld joint exhibited poor rupture life compared to the similar weld joint, at applied stresses lower than 130 MPa. In both weld joints, the strain distribution across the specimen gage length during creep testing varied significantly. During creep testing, localization of deformation occurred in the intercritical HAZ. In the similar weld joint, at all stress levels investigated, and in the dissimilar weld joint, at stresses greater than or equal to 150 MPa, the creep failure occulted in the intercritical HAZ. The fracture occurred by transgranular mode with a large number of dimples. At stresses below 150 MPa, the failure in the dissimilar weld joint occurred in the CPAG HAZ near to the weld interface. The failure occurred by extensive intergranular creep cavity formation.

Compressive behavior and fracture features of rubber bearing glass-epoxy composites exposed to aqueous media

Epoxy systems containing HTBN rubber material and reinforced with E-glass fibres, exposed to a fixed time duration in three separate media were subjected to compressive mode of deformation. The yield stress and fractographic features noted on the compression failed samples are reported in this work. The experiment reveals that the seawater exposed sample exhibits a drop in strength compared to dry (unexposed) sample. This kind of drop is maintained if the media is changed from seawater to distilled water. When HCl is included in seawater. the experiment shows a small rise in strength value. These changes have been attributed to various factors like medium ingress into samples assisting interface failure, the larger-sized Cl- influencing the extent of diffusion of medium into system and finally their participation in the deformation phenomena. The fractographic features reveal interface separations that show either scattered debris or a cleaner surface or display a whitish-coated matrix region depending on whether the tests are done on unexposed samples or on ones following the immersion in the media.

Influence of martensite content and morphology on the toughness and fatigue behavior of high-martensite dual-phase steels

A series of high-martensite dual-phase (HMDP) steels exhibiting a 0.3 to 0.8 volume fraction of martensite (V m ), produced by intermediate quenching (IQ) of a vanadium and boron-containing microalloyed steel, have been studied for toughness and fatigue behavior to supplement the contents of a recent report by the present authors on the unusual tensile behavior of these steels. The studies included assessment of the quasi-static and dynamic fracture toughness and fatigue-crack growth (FCG) behavior of the developed steels. The experimental results show that the quasi-static fracturetoughness (K ICV ) increases with increasing V m in the range between V m =0.3 and 0.6 and then decreases, whereas the dynamic fracture-toughness parameters (K ID , K D , and J ID ) exhibit a significant increase in their magnitudes for steels containing 0.45 to 0.60 V m before achieving a saturation plateau. Both the quasi-static and dynamic fracture-toughness values exhibit the best range of toughnesses for specimens containing approximately equal amounts of precipitate-free ferrite and martensite in a refined microstructural state. The magnitudes of the fatigue threshold in HMDP steels, for V m between 0.55 and 0.60, appear to be superior to those of structural steels of a similar strength level. The Paris-law exponents (m) for the developed HMDP steels increase with increasing V m , with an attendant decrease in the pre-exponential factor (C).

Novel phase-transition behavior near liquid/liquid critical points of aqueous solutions: Formation of a third phase at the interface

We report a novel phase behavior in aqueous solutions of simple organic solutes near their liquid/liquid critical points, where a solid-like third phase appears at the liquid/liquid interface. The phenomenon has been found in three different laboratories. It appears in many aqueous systems of organic solutes and becomes enhanced upon the addition of salt to these solutions.

Effect of aging on swelling and swell-shrink behavior of a compacted expansive soil

Effect of aging on swelling and swell-shrink behavior of a compacted expansive soil is investigated in this paper. An expansive soil having a liquid limit of 100% is used for this purpose. Compacted specimens were prepared and aged for a predetermined number of days (7, 15, 30, and 90 days) to study their swelling and swell-shrink behavior. It has been shown that aging improves the resistance to compression of compacted specimens. The swelling potentials of specimens also decreased with aging. The dominant factors that influence the aging effects are the water content and degree of saturation at the beginning of the aging process. The changed behavior of aged specimens is attributed to particle rearrangements and formation of bonds, which affect the surface area absorbing water during swelling. The cyclic swell-shrink tests on aged specimens indicated that the differences in vertical displacement during the first swelling were eliminated in the subsequent cycles when specimens were shrunk more, but the aging effect was found to persist with cycles for specimens subjected to lower shrinkage magnitudes.

Universality and scaling behavior of injected power in elastic turbulence in wormlike micellar gel

We study the statistical properties of spatially averaged global injected power fluctuations for Taylor-Couette flow of a wormlike micellar gel formed by surfactant cetyltrimethylammonium tosylate. At sufficiently high Weissenberg numbers the shear rate, and hence the injected power p(t), at a constant applied stress shows large irregular fluctuations in time. The nature of the probability distribution function (PDF) of p(t) and the power-law decay of its power spectrum are very similar to that observed in recent studies of elastic turbulence for polymer solutions. Remarkably, these non-Gaussian PDFs can be well described by a universal, large deviation functional form given by the generalized Gumbel distribution observed in the context of spatially averaged global measures in diverse classes of highly correlated systems. We show by in situ rheology and polarized light scattering experiments that in the elastic turbulent regime the flow is spatially smooth but random in time, in agreement with a recent hypothesis for elastic turbulence.

Revisiting the Mechanism of the Triosephosphate Isomerase Reaction: The Role of the Fully Conserved Glutamic Acid 97 Residue

An analysis of 503 available triosephosphate isomerase sequences revealed nine fully conserved residues. Of these, four residues-K12, H95, E97 and E165-are capable of proton transfer and are all arrayed around the dihydroxyacetone phosphate substrate in the three-dimensional structure. Specific roles have been assigned to the residues K12, H95 and E165, but the nature of the involvement of E97 has not been established. Kinetic and structural characterization is reported for the E97Q and E97D mutants of Plasmodium falciparum triosephosphate isomerase (Pf TIM). A 4000-fold reduction in k(cat) is observed for E97Q, whereas the E97D mutant shows a 100-fold reduction. The control mutant, E165A, which lacks the key catalytic base, shows an approximately 9000-fold drop in activity. The integrity of the overall fold and stability of the dimeric structure have been demonstrated by biophysical studies. Crystal structures of E97Q and E97D mutants have been determined at 2.0 angstrom resolution. In the case of the isosteric replacement of glutamic acid by glutamine in the E97Q mutant a large conformational change for the critical K12 side chain is observed, corresponding to a trans-to-gauche transition about the C gamma-C delta (chi(3)) bond. In the E97D mutant, the K12 side chain maintains the wild-type orientation, but the hydrogen bond between K12 and D97 is lost. The results are interpreted as a direct role for E97 in the catalytic proton transfer cycle. The proposed mechanism eliminates the need to invoke the formation of the energetically unfavourable imidazolate anion at H95, a key feature of the classical mechanism.