Phase behavior at low temperature of poly(tetrafluoroethylene) by temperature-modulated calorimetry

Temperature modulated differential calorimetry (TMDSC) is used to examine the crystal-crystal transitions of poly(tetrafluoroethylene). This study gives new information about the dynamic thermal behavior of such transitions. The involvement of reversible and irreversible processes during the phenomenon is observed, which are related to the order-disorder changes occurring during the transition.This study adds a new example to the response of TMDSC during first order transitions.     

Involutions for upper triangular matrix algebras

In this paper we describe completely the involutions of the first kind of the algebra UT_n(F) of n×n upper triangular matrices. Every such involution can be extended uniquely to an involution on the full matrix algebra. We describe the equivalence classes of involutions on the upper triangular matrices. There are two distinct classes for UT_n(F) when n is even and a single class in the odd case.Furthermore we consider the algebra UT₂(F) of the 2×2 upper triangular matrices over an infinite field F of characteristic different from 2. For every involution *, we describe the *-polynomial identities for this algebra. We exhibit bases of the corresponding ideals of identities with involution, and compute the Hilbert (or Poincaré) series and the codimension sequences of the respective relatively free algebras.Then we consider the *-polynomial identities for the algebra UT₃(F) over a field of characteristic zero. We describe a finite generating set of the ideal of *-identities for this algebra. These generators are quite a few, and their degrees are relatively large. It seems to us that the problem of describing the *-identities for the algebra UT_n(F) of the n×n upper triangular matrices may be much more complicated than in the case of ordinary polynomial identities.     

New HPLC-chiral stationary phases for enantiomeric resolution of sulfoxides and selenoxides

Summary Enantiomers of several sulfoxides and some selenoxides can be easily separated by using a new chiral stationary phase (CSP-DACH-DNB) containing the 3,5-dinitrobenzoyl derivative of R,R-(-)1,2-diamino-cyclohexane as selector, covalently bonded to the siliceous matrix. The easy operative conditions and the high enantioselectivity values (α) allow a direct transfer of the analytical separations to a semi-preparative and preparative scale.     

Quantitative Concentration Inequalities for Empirical Measures on Non-compact Spaces

We establish quantitative concentration estimates for the empirical measure of many independent variables, in transportation distances. As an application, we provide some error bounds for particle simulations in a model mean field problem. The tools include coupling arguments, as well as regularity and moment estimates for solutions of certain diffusive partial differential equations.     

Metastable phase in the quantum Hall ferromagnet

Time-dependent capacitance measurements reveal an unstable phase of electrons in gallium arsenide quantum well that occurs when two Landau levels with opposite-spin are brought close to degeneracy by applying a gate voltage. This phase emerges below a critical temperature and displays a peculiar non-equilibrium dynamical evolution. The relaxation dynamics is found to follow a stretched-exponential behaviour and correlates with hysteresis loops observed by sweeping the magnetic field. These experiments indicate that metastable randomly distributed magnetic domains with peculiar excitations are involved in the relaxation process in a way that is equivalently tunable by a change in gate voltage or temperature.     

On a model of phase relaxation for the hyperbolic Stefan problem

In this paper we study a model of phase relaxation for the Stefan problem with the Cattaneo–Maxwell heat flux law. We prove an existence and uniqueness result for the resulting problem and we show that its solution converges to the solution of the Stefan problem as the two relaxation parameters go to zero, provided a relation between these parameters holds.     

Generation of analytic semigroups by degenerate elliptic operators

We consider the generation of analytic semigroups by degenerate elliptic operators satisfying a uniform H?rmander condition under homogeneous Dirichlet boundary conditions. Received January 12, 1996     

Influence of structure and solubility of chain transfer agents on the RAFT control of dispersion polymerisation in scCO2

Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerisation of methyl methacrylate (MMA) is performed in supercritical carbon dioxide (scCO₂) with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. Kinetic studies of the polymerisation in scCO₂ also confirm these data. By contrast, only poor control of MMA polymerisation is obtained in toluene solution, as would be expected for this CTA which is better suited for acrylates. In this regard, we select a range of CTAs and use them to determine the parameters that must be considered for good control in dispersion polymerisation in scCO₂. A thorough investigation of the nucleation stage during the dispersion polymerisation reveals an unexpected “in situ two-stage” mechanism that strongly determines how the CTA works. Finally, using a novel computational solvation model, we identify a correlation between polymerisation control and degree of solubility of the CTAs. All of this ultimately gives rise to a simple, elegant and counterintuitive guideline to select the best CTA for RAFT dispersion polymerisation in scCO₂.

RAFT dispersion polymerisation of methyl methacrylate is performed in scCO₂ with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight.     

Thermodynamic and Dynamic Properties of Micellar Aggregates of Nonionic Surfactants with Short Hydrophobic Tails

The densities and viscosities of binary aqueous mixtures of poly(ethylenoxide)hexanols [C₆H₁₃(OCH₂CH₂)_mOH, C₆E_m] (m= 3, 4, and 5) have been studied in the micellar composition range. For the same surfactants the self-diffusion coefficients in mixtures with heavy water have been determined by the spin-echo pulsed field gradient method. The volumetric data are interpreted by means of the phase separation model, and values of the CMC, volume change, and standard free energy change of micellization are obtained. From the viscosity data the hydration numbers of the surfactant hydrophilic head in the micellar state are computed; they are in agreement with those obtained from HDO self-diffusion data. The surfactant self-diffusion data are used to calculate the apparent micelle radius and the aggregation number. The micellization parameters obtained for the different surfactants are compared and discussed.