Studies in crystal engineering: Effect of fluorine substitution in crystal packing and topological photodimerization of styryl coumarins in the solid state

Styryl coumarins generally yield centrosymmetric (alpha-mode, anti-HT) photodimers when subjected to irradiation in the solid state, However, the substitution of fluorine dramatically alters the packing mode and steers the molecules 4-(4-fluorostyryl)coumarin 1 and 4-(2-fluorostyryl)coumarin 2 to form a stereospecific photodimer, beta-mode, syn-HH across the styrenic double bond (yield 78-85%). The stereochemistry of the photodimer 2a has been established by X-ray crystallography. There is no evidence for the presence of C-H ... F interactions. The true nature of the weak atom-atom interactions called into play when fluorine is substituted is not clear, It is observed that the fluoro substituted compounds have greater crystal density than the corresponding unsubstituted ones.

Solid state amorphization in binary Ti---Ni, Ti---Cu and ternary Ti---Ni---Cu system by mechanical alloying

An amorphous phase has been synthesized by mechanical alloying in a planetary mill over a nickel content range of 10�70 at.% in the Ti---Ni system and a copper content range of 10�50 at.% in the Ti---Cu system. In the case of ternary Ti---Ni---Cu alloys the glass-forming composition range has been found to be given by x = 10�20 for Ti60Ni40 ? xCux, x = 10 � 30 for Ti50Ni50 ? xCux and x = 10 � 40 for Ti40Ni60 ? xCux alloys. The difficulty in the amorphization of copper-rich compositions is explained in the light of enthalpy composition diagrams calculated for the ternary solid solution and the amorphous phase.

Solid-state photobehaviour and crystal packing of o-chlorobenzylidene-DL-piperitone: influence of molecular topology on photobehaviour

C17H19ClO, M(r) = 274.7, triclinic, P1BAR, a = 11.154 (3), b = 12.685 (2), c = 12.713 (2) angstrom, alpha = 100.68 (1), beta = 113.58 (1), gamma = 104.50 (2)-degrees, V = 1511.1 (6) angstrom3, Z = 4, D(m) = 1.22, D(x) = 1.215 Mg m-3, Cu K-alpha, lambda = 1.5418 angstrom, mu = 2.16 mm-1, F(000) = 584, T = 293 K, R = 0.057 for 3481 observed reflections. The title compound is photostable in the crystalline state and lattice-energy calculations have been employed to rationalize the photobehaviour. The well-known beta-steering ability of the chloro group is not operative in this system as there are no Cl...Cl interactions in the crystal lattice. All five benzylidene-DL-piperitone structures so far studied are alpha-packed and the molecular topology appears to be a deciding factor even in the presence of steering groups.

The concentration dependent cooperative friction coefficient of dilute polymer solutions at the theta point

We combine multiple scattering and renormalization group methods to calculate the leading order dimensionless virial coefficient k(s) for the friction coefficient of dilute polymer solutions under conditions where the osmotic second virial coefficient vanishes (i.e., at the theta point T-theta). Our calculations are formulated in terms of coupled kinetic equations for the polymer and solvent, in which the polymers are modeled as continuous chains whose configurations evolve under the action of random forces in, the velocity field of the solvent. To lowest order in epsilon=4-d, we find that k(s) = 1.06. This result compares satisfactorily with existing experimental estimates of k(s), which are in the range 0.7-0.8. It is also in good agreement with other theoretical results on chains and suspensions at T-theta. Our calculated k(s) is also found to be identical to the leading order virial coefficient of the tracer friction coefficient at the theta point. We discuss possible reasons for the difficulties encountered when attempting to evaluate k(s) by extrapolating prior renormalization group calculations from semidilute concentrations to the infinitely dilute limit. (C) 1996 American Institute of Physics.

Structural and vibrational studies of the layered structure solid Fe1 ? xNixPS3 (1 greater-or-equal, slanted x greater-or-equal, slanted 0)

We report here the results of structural and vibrational studies on the solid solution Fe1 ? xNixPS3 (1 greater-or-equal, slanted x greater-or-equal, slanted 0) systems. From the structural analysis, we show that there is a lattice compaction as the composition x is varied from 0 to 1, the basic lattice symmetry being maintained. We find that the compaction is more in the basal plane. These subtle structural changes are also reflected in the vibrational bands. We observed splitting of certain bands due to these small changes in the lattice constants, which we explained as arising from a correlation splitting. These changes in the vibrational bands have also been seen on cooling where there is a preferential thermal compaction in the basal plane compared to that perpendicular to the plane.

Evaluation of relative growth limitation due to depletion of glucose and oxygen during fungal growth on a spherical solid particle

A mathematical model for glucose and oxygen consumption, and cell growth during fungal growth on a single solid particle is developed. A moving biofilm is assumed to be present on the surface of the solid particle. Initially only glucose is assumed to be growth limiting and later oxygen transferred from the gas phase on to the biofilm is also assumed to be growth limiting. Glucose is found to be severely growth limiting when assumed to be the only growth limiting factor and its limiting levels far less severe when oxygen limitation is also included. The objective of the model is to gain a better understanding of the mass transfer and relative growth limiting characteristics of glucose and oxygen in fungal growth systems. The results obtained from the model proposed here will be the subject of future work.

Organic Additive-Mediated Synthesis of Novel Cobalt(II) Hydroxides

Electrochemical precipitation of cobalt(II) hydroxide from nitrate solutions containing organic molecules, such as glucose, fructose, lactose, glycerol, and citric acid, yields a new modification of cobalt (II) hydroxide (a = 3.09 +/- 0.03 Angstrom, c = 23.34 +/- 0.36 Angstrom) that is isostructural with cu-nickel hydroxide; precipitation in the absence of organic additives gives the stable, brucite-like, beta-CO (OH)(2). (C) 1995 Academic Press, Inc.

Role of Li+ ions in corrosion behaviour of 8090 Al-Li alloy and aluminium in pH 12 aqueous solutions

The influence of Li+ ions on the corrosion behaviour of the Al-Li alloy 8090-T851 and of commercially pure aluminium in aqueous solutions at pH 12 was studied by weight loss and electrochemical polarisation methods. The inhibiting role of Li+ was concentration dependent, corrosion rate decreasing lineally with log[Li+] in the concentration range 10(-4)-10(-1) mol L(-1). A change from general to pitting corrosion was evident from scanning election microscopy studies. Polarisation studies revealed that Li+ primarily acts as an anodic inhibitor (passivator). Passive film formation and stability also become more feasible with increasing Li+ concentration. Fitting potential was dependent on the Cl- ion concentration in the solution. Both materials were affected similarly by the presence of Li+ ions, the corrosion rate of the alloy being slightly lower. This is attributed to the lithium in the alloy acting as a source of lithium for passive film formation. (C) 1995 The Institute of Materials.

Solid Oxide-Ion Electrolytes

Solid oxide-ion electrolytes find application in oxygen sensors, oxygen pumps and in high-temperature electrolyser-fuel-cell hybrid systems. All the solid electrolytes known so Qr, however, exhibit: tow oxide-ion conductivities below 973 K. Therefore, there is a need for fast oxide-ion conductors operative at temperatures around 673 K, Recently, efforts have been directed towards developing such materials. This article summarizes various type of oxide-ton electrolytes reported in literature and outlines a strategy for the identificatiom/synthesis of improved materials.

Solid-state miscibility gap and thermodynamics of the system BaO–SrO

A solid-state miscibility gap in the pseudo-binary system BaO-SrO is delineated by X-ray diffraction studies on samples equilibrated either in vacuum or under flowing inert gas at temperatures between 1073 and 1423 K. For the SrxBa1-xO solid solution an asymmetric phase boundary, characterized by a critical temperature of 1356 (+/-4) K and composition x=0.55 (+/-0.008), is obtained. Thermodynamic mixing properties of the solid solution, derived from the experimental phase boundary compositions and temperatures, can be represented by the expression: Delta G(E)=x(1-x){33 390-7.09T)x+(29 340-6.23T)(1-x)} J mol(-1)It is necessary to include excess entropy terms to obtain a good fit to the experimental data. The chemical spinodal curve is computed from the thermodynamic parameters

Some observations on the ignition of composite solid propellants

Heat-up times derived from studies on the ignition characteristics of a few model composite solid propellants, containing polystyrene, carboxy-terminated polybutadiene, plasticised polyvinyl chloride and polyphenol formaldehyde as binders, show that they are directly proportional to the mass of the sample and inversely proportional to the hear flux. Propellant weight-loss prior to ignition and high pressure ignition temperature data on the propellants, ammonium per chlorate, and binders show that the ignition is governed by the gasification of the binder pyrolysis products. The activation energy for the gasification of the pyrolysed polymer products corresponds to their ignition behaviour suggesting that propellant ignition is controlled by the binder.

Theoretical Analysis of the Electromotive Force of a Cell Incorporating a Composition Gradient Solid Electrolyte

New composition gradient solid electrolytes have been designed for application in high temperature solid-state galvanic sensors and in thermodynamic measurements. The functionally gradient electrolyte consists of a solid solution between two or more ionic conductors with a common ion and gradual variation in composition of the other ionic species. Unequal rates of migration of the ions, caused by the presence of the concentration gradient, may result in the development of space charge, manifesting as diffusion potential. Presented is a theoretical analysis of the EMF of cells incorporating gradient solid electrolytes. An analytical expression is derived for diffusion potential, using the thermodynamics of irreversible processes, for different types of concentration gradients and boundary conditions at the electrode/electrolyte interfaces. The diffusion potential of an isothermal cell incorporating these gradient electrolytes becomes negligible if there is only one mobile ion and the transport numbers of the relatively immobile polyionic species and electrons approach zero. The analysis of the EMF of a nonisothermal cell incorporating a composition gradient solid electrolyte indicates that the cell EMF can be expressed in terms of the thermodynamic parameters at the electrodes and the Seebeck coefficient of the gradient electrolyte under standard conditions when the transport number of one of the ions approaches unity.

Direct Cartesian-Space Solutions of Generalized Bloch Equations in the Rotating Frame

Analytical solutions of the generalized Bloch equations for an arbitrary set of initial values of the x, y, and z magnetization components are given in the rotating frame. The solutions involve the decoupling of the three coupled differential equations such that a third-order differential equation in each magnetization variable is obtained. In contrast to the previously reported solutions given by Torrey, the present attempt paves the way for more direct physical insight into the behavior of each magnetization component. Special cases have been discussed that highlight the utility of the general solutions. Representative trajectories of magnetization components are given, illustrating their behavior with respect to the values of off-resonance and initial conditions. (C) 1995 Academic Press, Inc.

Liquid phase epitaxial growth of pure and doped GaSb layers: morphological evolution and native defects

Undoped and Te-doped gallium antimonide (GaSb) layers have been grown on GaSb bulk substrates by the liquid phase epitaxial technique from Ga-rich and Sb-rich melts. The nucleation morphology of the grown layers has been studied as a function of growth temperature and substrate orientation. MOS structures have been fabricated on the epilayers to evaluate the native defect content in the grown layers from the C-V characteristics. Layers grown from antimony rich melts always exhibit p-type conductivity. In contrast, a type conversion from p- to n- was observed in layers grown from gallium rich melts below 400 degrees C. The electron mobility of undoped n-type layers grown from Ga-rich melts and tellurium doped layers grown from Sb- and Ga-rich solutions has been evaluated.

Moving boundaries due to distributed sources in a slab

Analytical and numerical solutions have been obtained for some moving boundary problems associated with Joule heating and distributed absorption of oxygen in tissues. Several questions have been examined which are concerned with the solutions of classical formulation of sharp melting front model and the classical enthalpy formulation in which solid, liquid and mushy regions are present. Thermal properties and heat sources in the solid and liquid regions have been taken as unequal. The short-time analytical solutions presented here provide useful information. An effective numerical scheme has been proposed which is accurate and simple.