High-pressure phase transition in LiBH4

The high-pressure phase transition from ambient pressure α-LiBH₄ to high-pressure β-LiBH₄ was observed by Raman spectroscopy and X-ray diffraction between 0.8 and 1.1 GPa. The phase boundary between these two phases was mapped over a large range of temperatures using thermal conductivity studies and differential thermal analysis. The structure of the high-pressure phase could not be identified due to small number of experimentally observed reflections, but it was shown that it is different from previously reported theoretical predictions.     

Structural evolution of (Ca0.35Sr0.65)TiO3 perovskite at high pressures

Lattice parameters of a synthetic powder sample of Ca_0.35Sr_0.65TiO₃ perovskite have been determined by the method of Le Bail refinement, using synchrotron X-ray diffraction patterns collected at pressures up to 15.5 GPa with a membrane-driven diamond anvil cell. At ambient conditions, diffraction data were consistent with the I4/mcm structure reported previously in the literature for the same composition. Diffraction data collected at high pressures were consistent with tetragonal (or, at least, pseudo-tetragonal) lattice geometry, and no evidence was found for the development of any of the orthorhombic structures identified in other studies of (Ca, Sr)TiO₃ perovskites. Additional weak reflections, which could not be accounted for by the normal I4/mcm perovskite structure, were detected in diffraction patterns collected at pressures of 0.9-2.5 GPa, and above ∼13.5 GPa, however. Small anomalies in the evolution of unit cell volume and tetragonal strain were observed near 3 GPa, coinciding approximately with breaks in slope with increasing pressure of bulk and shear moduli for a sample with the same composition which had previously been reported. The anomalies could be due either to new tetragonal↔tetragonal/pseudo-tetragonal phase transitions or to subtle changes in compression mechanism of the tetragonal perovskite structure.     

The microenvironment in polymer solids with added plasticizers. An attempt to measure the size and distribution of free volume in poly(methyl methacrylate) solids

Various amounts of n-alkylbenzenes (C_n: C₆H₅-C_nH_2n+1 (n = 3-16)) were doped into poly(methyl methacrylate) (PMMA) films, and the emission and thermal properties of each film were measured in detail together with their solid-state ¹³C NMR spectra. The aim of the present work was to estimate the size distribution of free volume in amorphous regions of polymer solids heavily doped with plasticizers by using C_n as models of a plasticizer. The excimer fluorescence yields of C_n in PMMA were found to depend on both the amount of C_n and the length of the alkyl chains of C_n, although the fluorescence spectra of all of the C_ns in dilute fluid solution were almost the same. The quantitative analysis showed: (1) C_n with n ? 12 induces a phase separation in PMMA, in which almost all of the C_n molecules are in a separated phase, and thus they cannot penetrate regions in which PMMA chains are aggregated. This means that C_n with n ? 12 cannot enlarge the space between PMMA chains. (2) Smaller C_n (n < 11) can enter free volumes between PMMA chains that correspond to their molecular size, but they can enlarge them only to a limited extent. Thus, the amount by which plasticization can increase the free volume of PMMA is limited by the size of the dopant and the inherent free volume of the polymer matrix. (3) The efficiency of excimer formation was found to reveal the maximum amount of C_n that could fit in the free volume of PMMA. Thus our fluorescence measurements showed that PMMA solids that were plasticized to their limit had a free volume that was larger than the volume occupied by all the conformers of C₅ and smaller than the volume occupied by almost all the conformers of C₁₂. In conclusion, we were able to obtain information on plasticization and to demonstrate a method of monitoring microenvironments in polymer solids after they have been doped with plasticizers.     

Phasenverhältnisse der Selenate im Dreistoffsystem Tl2O3-SeO3-H2O bei 100°C

Summary The solubility of the system Tl₂O₃-SeO₃-H₂O was studied at 100°C. The compounds obtained were subjected to X-ray and thermal analysis. The symmetry and the crystallographic constants of some of the compounds were determined.

     

Hamiltonian nilpotent saddles of linear plus cubic homogeneous polynomial vector fields

We completely characterize the global phase portraits in the Poincaré disk for all planar Hamiltonian vector fields with linear plus cubic homogeneous terms having a nilpotent saddle at the origin.     

Phase uniqueness and correlation length in diluted-field Ising models

The diluted-field Ising model, a random nonnegative field ferromagnetic model, is shown to have a unique Gibbs measure with probability I when the field mean is positive. Our methods involve comparisons with ordinary uniform field Ising models. They yield as a corollary a way of obtaining spontaneous magnetization through the application of a vanishing random magnetic field. The correlation lengths of this model defined as (lim _n-(1/n) log ₀; _n)^-1, wheren is the site on the first coordinate axis at distancen from the origin and ₀; _n is the origin ton two-point truncated correlation function, is non-random. We derive an upper bound for it in terms of the correlation length of an ordinary nonrandom model with uniform field related to the field distribution of the diluted model.     

Cluster description of water-in-oil microemulsions near the critical and percolation points

The three-component ionic microemulsion system consisting of AOT/water/decane shows an unusual phase behavior in the vicinity of room temperature. The phase diagram in the temperature-volume fraction (of the dispersed phase) plane exhibits a lower consolute critical point at about 40 degrees centigrades and 10% volume fraction. A percolation line, starting from the vicinity of the critical point, cuts across the plane, extending to high volume fraction side at progressively lower temperatures. In this paper we review the evidence that allows to interpret the phase behavior of our system in terms of interacting spherical droplets. We also investigate the dynamics of droplets, below and approaching the critical point by dynamic light scattering. The first cumulant and time evolution of the droplet density correlation function can be quantitatively calculated by assuming the existence of polydispersed fractal clusters formed by the microemulsion droplets due to attraction. The relaxation phenomena observed in an extensive set of measurements of electrical conductivity and permittivity close to percolation is also reviewed and interpreted through the same cluster-forming mechanism, which reproduces the most relevant features of the frequency-dependent complex dielectric constant of this system. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

The O(N) vector model in the large-N limit revisited: multicritical points and double scaling limit

The multicritical points of the O(N)-invariant N vector model in the large-N limit are re-examined. Of particular interest are the subtleties involved in the stability of the phase structure at critical dimensions. In the limit N → ∞ while the coupling g → g_c in a correlated manner (the double scaling limit) a massless bound state O(N) singlet is formed and powers of 1/N are compensated by IR singularities. The persistence of the N → ∞ results beyond the leading order is then studied with particular interest in the possible existence of a phase with propagating small mass vector fields and a massless singlet bound state. We point out that under certain conditions the double scaled theory of the singlet field is non-interacting in critical dimensions.     

Surface properties of ω-perfluorooctyl-alkyl polyacrylates: odd–even effect

A series of ω-perfluorooctyl-alkyl polyacrylates has been prepared and analysed. The odd–even effect, already observed in the case of liquid crystalline polymers has been exhibited for perfluorinated ones. Values of the contact angles to advanced (θ_a), with withdrawal (θ_r), as well as the contact angle hysteresis (Δθ) of various ω-perfluorooctyl-alkyl polyacrylates in water at 20 °C are described. Contrary to the advancing contact angle which is almost independent of spacer length, the receding one varies strongly with it.     

New breathable and waterproof coatings for textiles: effect of an aliphatic polyurethane on the formation of PEEK-WC porous membranes

PEEK-WC is an amorphous polyetheretherketone with high chemical stability, excellent thermal resistance and significant solubility in various solvents. It has been used to prepare flat membranes by the phase inversion technique. The water vapour permeability through a porous PEEK-WC film was 1350 g/m² day at 26 °C and its liquid entry pressure (LEP) of water equivalent to a column of 2.0 m. These values were remarkably improved by addition of an aliphatic ether polyurethane (PU) into the PEEK-WC/DMF dopes: the water vapour flux was increased up to 2000 g/m² day and the LEP was equivalent to 12.5 m. This improvement is correlated to the different structure of the membranes: a spongy, porous and almost symmetric structure for the PEEK-WC/PU membranes, and an asymmetric structure with fingers for PEEK-WC membrane. The presence of PU influences also the mechanical properties of the blend membranes. The role of the PU on the resulting membrane morphology is rationalised on the basis of the mechanism of phase separation.