Crystal dissolution kinetics and Gibbs free energy

The dependence of dissolution rates on the difference of Gibbs free energy is of critical importance for our understanding of crystal dissolution, reactive flow models and their applications to a variety of environmentally related problems. Here, we review experimental data generated with mineral powders and single crystals to develop a better understanding of apparent inconsistencies between otherwise internally consistent data sets. Additional information from direct surface observations and measurements with vertical scanning interferometry (VSI) and atomic force microscopy (AFM) of albite dissolution at 25, 150 and 185 °C may shed new light on this old but unsolved question. Our discussion is based on the importance of etch pit development, its ΔG dependence, and the pits’ role as a source for steps and step movement in the dissolution process. Results indicate that reaction history may be of critical importance in determining the overall reaction mechanism and its rate. Different rates are observed for systems having otherwise identical ΔG_r acquired from increasing versus decreasing disequilibrium positions.

In this context, we finally discuss the validity of the common application of transition state theory (TST) to elementary and overall reactions governing the dissolution process. In this discussion of crystal dissolution, we contrast TST applications with a stochastic, many-body treatment that has led to the development of a stepwave model. This discussion also focuses on the controversy caused by the rivalry between surface adsorption models and a probabilistic model that seeks to incorporate the full three-dimensional crystal structure.     

Algorithms for finding connected separators between antipodal points

A set (or a collection of sets) contained in the Euclidean space Rm is symmetric if it is invariant under the antipodal map. Given a symmetric unicoherent polyhedron X (like an n-dimensional cube or a sphere) and an odd real function f defined on vertices of a certain symmetric triangulation of X, we algorithmically construct a connected symmetric separator of X by choosing a subcollection of the triangulation. Each element of the subcollection contains the vertices v and u such that f(v)f(u)?0.     

On the moduli spaces of multipolygonal linkages in the plane

One can form a polygonal linkage by identifying initial and terminal points of two free linkages. Likewise, one can form a multipolygonal linkage by identifying initial and terminal points of three free linkages. The geometric and topological properties of moduli spaces of multipolygonal linkages in the plane are studied. These spaces are compact algebraic varieties. Some conditions under which these spaces are smooth manifolds, cross products or disjoint unions of moduli spaces of polygonal linkages, or connected, are determined. Dimensions in smooth manifold cases and some Euler characteristics are computed. A classification of generic multiquadrilateral linkages is also made.     

Separable subgroups of mapping class groups

We investigate separability questions for the mapping class group of a surface. While this group is not subgroup separable in general, we prove a large family of interesting subgroups are separable. This includes many classically studied subgroups such as solvable subgroups, Heegaard and Handlebody groups, geometric subgroups, and all the terms in the Johnson filtration.     

Nonminimal sets,their projections and integral representations of stable processes

New criteria are provided for determining whether an integral representation of a stable process is minimal. These criteria are based on various nonminimal sets and their projections, and have several advantages over and shed light on already available criteria. In particular, they naturally lead from a nonminimal representation to the one which is minimal. Several known examples are considered to illustrate the main results. The general approach is also adapted to show that the so-called mixed moving averages have a minimal integral representation of the mixed moving average type.     

Gamow Vectors in Exactly Solvable Models

Through two examples: the Friedrichs model and a particular case of central potential scattering, we illustrate the way of constructing Gamow vectors.     

Influence of annealing and chain defects on the melting behaviour of poly(vinylidene fluoride)

The melting behaviour of poly(vinylidene fluoride) (PVDF) was investigated by differential scanning calorimetry (DSC) and small- and wide-angle X-ray scattering in order to study the influence of the chain defects content and of the temperature of annealing on the crystallization and melting behaviour.All the DSC scans show a double endotherm and the analysis of the data suggests that the low temperature endotherm is due to the melting of a population of thin lamellae, whose thickness increases during the annealing, but a high content of chain defects prevents the lamellar thickening and the main effect in this case is the crystallization of thin lamellae from a portion of polymer which did not crystallize during the quenching from the melt. Furthermore, the two melting endotherms, which are observed, can be partially ascribed to a melting-recrystallization process.Furthermore, stepwise isothermal cooling was performed in a differential scanning calorimeter followed by melting scans of fractionated PVDF samples to point out the possible presence of a series of endothermic peaks.     

Finite-Dimensional Approximations for Scattering Theory Operators in the Wave-Packet Representation

We consider some types of packet discretization for continuous spectra in quantum scattering problems. As we previously showed, this discretization leads to a convenient finite-dimensional (i.e., matrix) approximation for integral operators in the scattering theory and allows reducing the solution of singular integral equations connected with the scattering theory to some suitable purely algebraic equations on an analytic basis. All singularities are explicitly singled out. Our primary emphasis is on realizing the method practically.     

Effects of vitrification suppression on structure morphology, conductivity and dielectric properties of vanadium phosphate glasses

Vitrification suppression in the (V₂O₅)_1−x (P₂O₅)_x glasses where x=0.10, 0.15, 0.20, and 0.25 was controlled by changing the rate of quenching glasses. The structure variations occurring in the glasses were detected by differential thermal analysis and optical microscope. The results implied the separation and growth of V₂O₅ orthorhombic microcrystal in the samples with x=0.10 and 0.15 whereas other samples did not illustrate remarkable changes in their microstructure. However, in temperature range between 300 and 473 K a semiconducting behavior for all samples appears during the study of electrical conductivity-temperature dependence. A decrease in conductivity values accompanied with some variations in activation energies by reducing quenching rate was observed. The conductivity results suggested that the conduction occurs by the phonon assisted hopping of a small polaron between V⁴⁺ and V⁵⁺ states at relatively higher temperature range above θ_D/2. Whereas at relatively low temperatures the conduction may occur by electron jumping between filled and empty states at Fermi level in the disordered matrix besides polaronic conduction. Reasonable values for the density of localized states, carrier concentration and carrier mobility were estimated and discussed. Also, dielectric constant and dielectric loss were studied as a function of frequency at different temperatures confirming the structure variations in the glass system.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.