Reversible cation/anion extraction from K2La2Ti3O10: Formation of new layered titanates, KLa2Ti3O9.5 and La2Ti3O9

A new soft-chemical transformation of layered perovskite oxides is described wherein K2O is sequentially extracted from the Ruddlesden-Popper (R-P) phase, K2La2Ti3O10 (I), yielding novel anion-deficient KLa2Ti3O9.5 (II) and La2Ti3O9 (III). The transformation occurs in topochemical reactions of the R-P phase I with PPh4Br and PBu4Br (Ph = phenyl; Bu = n-butyl). The mechanism involves the elimination of KBr accompanied by decomposition of PR4+ (R = phenyl or n-butyl) that extracts oxygen from the titanate. Analysis of the organic products of decomposition reveals formation of Ph3PO, Ph3P, and Ph-Ph for R = phenyl, and Bu3PO, Bu3P along with butane, butene, and octane for R = butyl. The inorganic oxides II and III crystallize in tetragonal structures (II: P4/mmm, a = 3.8335(1) angstrom, c = 14.334(1) angstrom; III: /4/ mmm, a = 3.8565(2) angstrom, c = 24.645(2) angstrom) that are related to the parent R-P phase. II is isotypic with the Dion-Jacobson phase, RbSr2Nb3O10, while III is a unique layered oxide consisting of charge-neutral La2Ti3O9 anion-deficient perovskite sheets stacked one over the other without interlayer cations. Interestingly, both II and III convert back to the parent R-P phase in a reaction with KNO3. While transformations of the R-P phases to other related layered/three-dimensional perovskite oxides in ion-exchange/metathesis/dehydration/reduction reactions are known, the simultaneous and reversible extraction of both cations and anions in the conversions K2La2Ti3O10 reversible arrow KLa2Ti3O9.5 reversible arrow La2Ti3O9 is reported here for the first time.

Soft condensed matter -A special issue of solid state communications -Foreword

It is a policy of Solid State Communications’ Executive Editorial Board to organize special issues from time to time on topics of current interests. The present issue focuses on soft condensed matter, a rapidly developing and diverse area of importance not only for the basic science, but also for its potential applications. The ten articles in this issue are intended to give the readers a snapshot of some latest developments in soft condensed matter, mainly from the point of view of basic science. As the special issues are intended for a broad audience, most articles are short reviews that introduce the readers to the relevant topics. Hence this special issue can be especially helpful to readers who might not be specialists in this area but would like to have a quick grasp on some of the interesting research directions.

Ferroelectricity in Bi26-xMxO40-delta (M = Al and Ga) with the gamma-Bi2O3 structure

We report on the dielectric proper-ties of bismuth aluminate and gallate with Bi:AI(Ga) ratio of 1: 1 and 12:1 prepared at high temperature and ambient pressure. These compounds crystallize in a noncentrosymmetric body-centered cubic structure (space group 123) with a similar to 10.18 angstrom rather than in the perovskite structure.This cubic phase is related to the gamma-Bi2O3 structure which has the actual chemical formula Bi-24(3+) (Bi3+Bi5+)O40-delta. In the aluminates and gallates studied by us, the Al and Ga ions are distributed over the 24f and 2a sites. These compounds exibit ferroclectric hysteresis at room temperature with a weak polarization. (c) 2006 Elsevier Ltd. All rights reserved.

Studies on the ageing behaviour of Polyvinylchloride/ammonium perchlorate composite solid propellant

The effects of ageing on the properties of a complete polyvinyl chloride — dibutyl phthalate — ammonium perchlorate solid propellant have been studied by measurements of burning rates, thermal decomposition rates (by thermogravimetry and DTA) and calorimetric values. Ageing leads to loss of HCl by dehydrochlorination and a corresponding increase in heat of combustion.

Magnetization and magnetoresistive response of LiMn2O4 near the charge ordering transition

We report magnetization and magnetoresistance studies of the geometrically frustrated spinel compound LiMn2O4 near its charge ordering temperature. The effect of a 7 T magnetic field is to very slightly shift the transition in the resistivity to lower temperatures resulting in large negative magnetoresistance with significant hysteresis. This hysteresis is not reflected in the magnetization. These observations are compared with what is found in the colossal magnetoresistance and charge ordering perovskite manganese oxides. The manner in which geometric frustration influences the coupling of charge and spin degrees of freedom is examined.

Nonlinear intrinsic instability of solid propellant combustion including gas-phase thermal inertia

The problem of homogeneous solid propellant combustion instability is studied with a one-dimensional flame model, including the effects of gas-phase thermal inertia and nonlinearity. Computational results presented in this paper show nonlinear instabilities inherent in the equations, due to which periodic burning is found even under steady ambient conditions such as pressure. The stability boundary is obtained in terms of Denison-Baum parameters. It is found that inclusion of gas-phase thermal inertia stabilizes the combustion. Also, the effect of a distributed heat release in the gas phase, compared to the flame sheet model, is to destabilize the burning. Direct calculations for finite amplitude pressure disturbances show that two distinct resonant modes exist, the first one near the natural frequency as obtained from intrinsic instability analysis and a second mode occurring at a much higher driving frequency. It is found that er rn in the low frequency region, the response of the propellant is significantly affected by the specific type of gas-phase chemical heat-release model employed. Examination of frequency response function reveals that the role of gas-phase thermal inertia is to stabilize the burning near the first resonant mode. Calculations made for different amplitudes of driving pressure show that the mean burning rate decreases with increasing amplitude. Also, with an increase in the driving amplitude, higher harmonics are generated in the burning rate.

Role of aluminum-magnesium alloys in humid aging of composite solid propellants

The humid aging of composite propellants containing a terpolymer of polybutadiene, acrylic acid, and acrylonitrile (PBAN) as a binder has been studied as a function of aging temperature, relative humidity, and aging time. Three composite types - AP-PBAN, AP-Al-PBAN, and AP-(Al-Mg) alloy- PBAN - have been studied. The burning rates of all three propellant types were unaffected by aging. The calorimetric values of composites containing aluminum-magnesium alloy decreased on aging, and the lattice parameter of the alloy decreased to a value close to that of aluminum. Water absorption in all of the samples increased with increases in the temperature, relative humidity, and aging time. The compression strength of the nonmetalized and aluminized samples decreased on aging, whereas that of the composites containing the alloy increased. The latter effect has been traced to reaction of residual carboxyl groups on the polymer chains with magnesium, leading to cross-linking. The reaction between the -COOH groups and magnesium has been proved using infrared spectroscopy. (Author)

Drained shear strength of fine-grained soil-solid surface interfaces

Herein are reported the results of an investigation on the effective angle of interfacial friction between fine-grained soils and solid surfaces as influenced by the roughness of the material surface, the soil type and the overconsolidation ratio. The ratio of interfacial friction angle to the angle of internal friction (evaluated at constant overconsolidation ratio) of the soil is independent of the overconsolidation ratio. An empirical correlation between this ratio and the roughness of the interface has been proposed.

Studies on nonisothermal solid state galvanic cells — effect of gradients on EMF

An expression for the EMF of a nonisothermal galvanic cell, with gradients in both temperature and chemical potential across a solid electrolyte, is derived based on the phenomenological equations of irreversible thermodynamics. The EMF of the nonisothermal cell can be written as a sum of the contributions from the chemical potential gradient and the EMF of a thermocell operating in the same temperature gradient but at unit activity of the neutral form of the migrating species. The validity of the derived equation is confirmed experimentally by imposing nonlinear gradients of temperature and chemical potential across galvanic cells constructed using fully stabilized zirconia as the electrolyte. The nature of the gradient has no effect on the EMF.

Nonclassical rotational inertia in a two-dimensional bosonic solid containing grain boundaries

We study the occurrence of nonclassical rotational inertia (NCRI) arising from superfluidity along grain boundaries in a two-dimensionalbosonic system. We make use of a standard mapping between the zero-temperature properties of this system and the statistical mechanics of interacting vortex lines in the mixed phase of a type-II superconductor. In the mapping, the liquid phase of the vortex system corresponds to the superfluid bosonic phase. We consider numerically obtained polycrystalline configurations of the vortex lines in which the microcrystals are separated by liquidlike grain-boundary regions which widen as the vortex system temperature increases. The NCRI of the corresponding zero-temperature bosonic systems can then be numerically evaluated by solving the equations of superfluid hydrodynamics in the channels near the grain boundaries. We find that the NCRI increases very abruptly as the liquid regions in the vortex system (equivalently, superfluid regions in the bosonic system) form a connected, system-spanning structure with one or more closed loops. The implications of these results for experimentally observed supersolid phenomena are discussed.

A simple technique for approximate solutions of the Falkner-Skan equation

A simple, sufficiently accurate and efficient method for approximate solutions of the Falkner-Skan equation is proposed here for a wide range of the pressure gradient parameter. The proposed approximate solutions are obtained utilising a known solution of another differential equation.

Semi-similar solutions of the unsteady compressible second-order boundary layer flow at the stagnation point

Semi-similar solutions of the unsteady compressible laminar boundary layer flow over two-dimensional and axisymmetric bodies at the stagnation point with mass transfer are studied for all the second-order boundary layer effects when the free stream velocity varies arbitrarily with time. The set of partial differential equations governing the unsteady compressible second-order boundary layers representing all the effects are derived for the first time. These partial differential equations are solved numerically using an implicit finite-difference scheme. The results are obtained for two particular unsteady free stream velocity distributions: (a) an accelerating stream and (b) a fluctuating stream. It is observed that the total skin friction and heat transfer are strongly affected by the surface mass transfer and wall temperature. However, their variation with time is significant only for large times. The second-order boundary layer effects are found to be more pronounced in the case of no mass transfer or injection as compared to that for suction. Résumé Des solutions semi-similaires d'écoulement variable compressible de couche limite sur des corps bi-dimensionnels thermique, sont étudiées pour tous les effets de couche limite du second ordre, lorsque la vitesse de l'écoulement libre varie arbitrairement avec le temps. Le systéme d'équations aux dérivées partielles représentant tous les effets est écrit pour la premiére fois. On le résout numériquement á l'aide d'un schéma implicite aux différences finies. Les résultats sont obtenus pour deux cas de vitesse variable d'écoulement libre: (a) un écoulement accéléré et (b) un écoulement fluctuant. On observe que le frottement pariétal total et le transfert de chaleur sont fortement affectés par le transfert de masse et la température pariétaux. Néanmoins, leur variation avec le temps est sensible seulement pour des grandes durées. Les effets sont trouvés plus prononcés dans le cas de l'absence du transfert de masse ou de l'injection par rapport au cas de l'aspiration.

Extension of Darken's Quadratic Formalism to Dilute Multicomponent Solutions

Darken's quadratic formalism is extended to multicomponent solutions. Equations are developed for the representation of the integral and partial excess free energies, entropies and enthalpies in dilute multicomponent solutions. Quadratic formalism applied to multicomponent solutions is thermodynamically consistent. The formalism is compared with the conventional second order Maclaurin series or interaction parameter representation and the relations between them are derived. Advantages of the quadratic formalism are discussed.

Frequency-Dependent Viscosity of Membrane Solutions

It is shown that dilute suspensions of membranes have strongly frequency-dependent viscosities. This behaviour should be seen in a variety of measurements such as capillary flow, mechanical impedance and ultrasound damping.