Diffusion in polymers with varying accessibility

This paper considers the problem of describing quantitatively the process of diffusion in polymers attended by plasticization of their amorphous phase. A consequence of such plasticization is that the volume accessible to the penetrant molecules continuously increases during the course of their sorption. Assuming that the rate of relaxation processes is far greater than that of diffusion, an equation has been generated to describe the sorption in a matrix with varying accessibility. A numerical solution of this equation, using experimental data for a polyamide-water system, demonstrates that sorption in a matrix with increasing accessibility is slower than sorption in a hypothetical matrix with constant accessibility and with the same proportion of the amorphous phase. At the same time, the concentration of the penetrant in the former case proves to be higher at any point in the polymer specimen. The results obtained are important for calculating the rate constants for chemical reactions that proceed in a polymer matrix in the diffusion-kinetic mode.     

Electrical double layers at the oil/water interface

This review presents the historical development and current status of the theory of the electrical double layer at a liquid/liquid interface. It gives rigorous thermodynamic definitions of all basic concepts related to liquid interfaces and to the electrical double layer. The difference between the surface of a solid electrode and the interface of two immiscible electrolyte solutions (ITIES) is analyzed in connection to their electrical properties. The most important classical relationships for the electrical double layer are presented and critically discussed. The generalized adsorption isotherm is derived. After a short review of the classical Gouy-Chapman and Verwey-Niessen models, more recent developments of the double layer theory are presented. These include effects of variable dielectric permittivity, nonlocal electrostatics, hydration forces, the modified Poisson-Boltzmann equation and the ion-dipole plasma. The relative merits of different theories are estimated by comparing them with computer simulation of the ITIES and electrical double layer. Special attention is given to the structure of ITIES and its variation due to adsorption of ions and amphiphilic molecules.     

Fullerene complexes with bis(η6-hexamethylbenzene)chromium, hexamethylbenzene, and hexaethylbenzene

The [60]fulleride of bis(η-hexamethylbenzene)chromium(I) [(η⁶-C₆Me₆)₂Cr]^⋅+[C₆₀]^⋅−, and the complexes C₆₀·C₆Me₆ and C₆₀·C₆Et₆ were synthesized. Thermal decomposition of [(η⁶-C₆Me₆)₂Cr]^⋅+[C₆₀]^⋅− was studied. The molecular structures of C₆₀·C₆Me₆ and C₆₀·C₆Et₆ were determined. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 220—224, February, 2006.     

The phase diagram of fullerene C60 at high temperatures and pressures

Experimental and literature data were used to calculate the Gibbs energies of polymerized C₆₀ phases and construct the equilibrium T-p phase diagram of fullerene C₆₀ at temperatures from 0 to 1000 K and pressures from 0 to 8 GPa. The diagram contains stability regions of the orthorhombic, tetragonal, and rhombohedral polymerized C₆₀ phases and primitive cubic (PC) and face-centered cubic (FCC) nonpolymerized C₆₀ phases. The orthorhombic phase (linear polymer) is an equilibrium phase at 298 K and 1 bar and in the adjacent region. The equilibrium line observed experimentally (FCC C₆₀—orthorhombic phase) is well described by the phase diagram. The optimum temperatures and pressures of the synthesis of polymerized phases are determined by kinetic rather than thermodynamic parameters.     

On scalar-type spectral operators and Carleman ultradifferentiable <Emphasis Type="Italic">C</Emphasis><Subscript>0</Subscript>-semigroups

Necessary and sufficient conditions for a scalar-type spectral operator in a Banach space to be a generator of a Carleman ultradifferentiable C ₀-semigroup are found. The conditions are formulated exclusively in terms of the spectrum of the operator. Published in Ukrains'kyi Matematychnyi Zhurnal, Vol. 60, No. 9, pp. 1215–1233, September, 2008.     

Properties of ZnSe films pulse electrodeposited in the presence of phosphotungstic acid

ZnSe films were pulse-electrodeposited on conducting glass substrates with and without the addition of phosphotungstic acid. X-ray diffraction studies indicated the formation of single phase cubic ZnSe. Addition of phosphotungstic acid resulted in films with nanocrystallites. The band gap of the films was found to increase due to addition of phosphotungstic acid. The films had a crystallite size of the order of 15nm and a surface roughness of 1.8nm. Laser Raman studies exhibited the LO phonon peaks of ZnSe. The films were found to possess a slight excess of Se as evident from the energy dispersive X-ray analysis measurements.     

Calorimetric and structural studies of organic compound of tris(pentafluorophenyl)-4-pyridylethylgermane

In the present research, the temperature dependence of heat capacity of tris(pentafluorophenyl)-4-pyridylethylgermane (C₆F₅)₃Ge–CH₂–CH₂–C₅H₄N was studied by precise adiabatic vacuum calorimetry and differential scanning calorimetry over the temperature range from 6 to 450 K. The temperature and enthalpy of fusion of tris(pentafluorophenyl)-4-pyridylethylgermane and the total mole fraction of impurities have been determined. The thermal stability of the sample was investigated by thermogravimetric analysis. The experimental data were used to calculate the standard thermodynamic functions: heat capacity, enthalpy, entropy, and the Gibbs energy over the range from T → 0 to 420 K for crystalline and liquid states. For the compound under study, the standard entropy of formation in the crystalline state was calculated at T = 298.15 K. In addition, the structure of the investigated compound was established, and corresponding structural parameters were determined.

     

Phase Separation in (Ga,Mn)As Layers Obtained by Ion Implantation and Subsequent Laser Annealing

Physics of the Solid State - In this paper, we present the results of studies of the spectral, temperature, and field dependences of the transversal Kerr effect in...     

Finding the elastic strain limit at the tip region of a physical cut with arbitrarily loaded faces

A model describing the stress-strain state in the neighborhood of a physical cut with an arbitrary distribution of external load along its faces is presented. The stress-strain state of a material layer bounded by the continuations of the cut faces is considered. The interaction between the layer and the external half-planes leads to a closed system of integrodifferential equations for the mean stress components in the layer, which splits into two equations for the mean normal stresses and an equation for the mean shear stress. Numerical solutions of the system for the cases of symmetric and antisymmetric loading of the faces by concentrated forces are given. Conditions for the transition of the tip region of the cut to the state of plasticity and fracture are considered.