NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies

In this work, the melting-point depression and molecular dynamics of hexamethyldisilane confined within five controlled pore glasses, with mean diameters ranging from 7.9 to 23.9 nm, are studied by high-field (9.4 T) nuclear magnetic resonance (NMR), and the results are discussed with reference to the bulk substance. The melting-point depression in pores with radiusR follows the simplified Gibbs-Thompson equation ΔT=k _p/(R−s) with ak _p value of 74 K · nm and ans value of 1 nm. To our knowledge, this is the first time thek _p value of hexamethyldisilane is reported. Proton spin-lattice relaxation times (T ₁), spin-spin relaxation times (T ₂), and diffusivities (D) are reported as a function of temperature. The confinement in the pores gives rise to substantial changes in the molecular dynamics and the phase behavior. The line-shape measurements reveal a two-phase system assigned to a relatively mobile component at the pore walls and a crystalline solid at the center of the pores. However, theT ₂ measurements show that the mobile phase also embraces a minor component attributed to nonfrozen liquid in pockets or micropores. The diffusivity of the major narrow-line component is approximately three orders of magnitude larger than that in the plastic bulk phase, reflecting fast diffusion of mobile molecules. Below the melting region,T ₁ of the narrow line is significantly shorter thanT ₁ of the broad line, suggesting that the molecular reorientation is more hindered close to the surface than at the center of the pore.     

Use of a range scaling method to determine alanine/water stopping power ratios

A phantom composed of alanine dosimeter material has been constructed and depth–dose measurements made in a 10 MeV electron beam. The results have demonstrated the feasibility of using relative depth–dose measurements to determine stopping power ratios in materials of dosimetric interest. Experimental stopping power ratios for alanine dosimeter material and water agreed with the data of ICRU Report 37 within the uncertainty of the experiment (±1.2% at a 95% confidence level).     

Application of INAA to reveal the chemical evolution of selected volcanic eruptiva from Santorini, Greece

The pumiceous products of the large-scale explosive eruptions at Santorini show a high grade of similarity in their optical appearance as well as in their chemical composition. The demand for a clear classification of these eruption products was raised from archaeological research, where pumice can be interpreted as a “post-eruption” time marker. The aim of this work was to find elements that underwent significant changes because of geochemical processes and that could be indicative for a distinction of pumice produced by the five major explosive eruptions. INAA of 25 elements allows a clear classification and contributes new information to the chemical evolution of Santorini volcano. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polynomial Reproduction in Subdivision

We study conditions on the matrix mask of a vector subdivision scheme ensuring that certain polynomial input vectors yield polynomial output again. The conditions are in terms of a recurrence formula for the vectors which determine the structure of polynomial input with this property. From this recurrence, we obtain an algorithm to determine polynomial input of maximal degree. The algorithm can be used in the design of masks to achieve a high order of polynomial reproduction.     

On Coercive Estimates for Solutions of Linear Systems of Hydrodynamic Type

Local and nonlocal coercive estimates in Lebesgue, Hölder, and Morrey–Campanato spaces are proved for solutions of linear stationary systems of hydrodynamic type. For this purpose, the technique proposed by Italian mathematicians for the study of solutions to equations and systems of elliptic and parabolic types is developed. Bibliography: 14 titles.     

Absorption and propagation of light in quaterthiophene crystals

We examine absorption of light in quaterthiophene crystals for different directions of the ray and wave-normal vector after refraction on the vacuum/crystal interface. Experimental non-normal incidence spectra are reported where different absorption bands show different behaviour as a function of the angle of incidence. This allows to identify those originating from the b_u Frenkel exciton state.     

Miscibility and phase structure of binary blends of polylactide and poly(methyl methacrylate)

Blends of amorphous poly(DL‐lactide) (DL‐PLA) and crystalline poly(L‐lactide) (PLLA) with poly(methyl methacrylate) (PMMA) were prepared by both solution/precipitation and solution‐casting film methods. The miscibility, crystallization behavior, and component interaction of these blends were examined by differential scanning calorimetry. Only one glass‐transition temperature (T_g) was found in the DL‐PLA/PMMA solution/precipitation blends, indicating miscibility in this system. Two isolated T_g's appeared in the DL‐PLA/PMMA solution‐casting film blends, suggesting two segregated phases in the blend system, but evidence showed that two components were partially miscible. In the PLLA/PMMA blend, the crystallization of PLLA was greatly restricted by amorphous PMMA. Once the thermal history of the blend was destroyed, PLLA and PMMA were miscible. The T_g composition relationship for both DL‐PLA/PMMA and PLLA/PMMA miscible systems obeyed the Gordon–Taylor equation. Experiment results indicated that there is no more favorable trend of DL‐PLA to form miscible blends with PMMA than PLLA when PLLA is in the amorphous state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 23–30, 2003     

Study of the dynamic structure factor of strong glasses

The dynamic structure factors (DSFs) of several strong glasses (SF6, SF10, BK7, SUPRASIL) measured by Brillouin light scattering spectroscopy are reported. Spectra have been collected, at and above room temperature, at two scattering angles, θ=90° and θ=180° corresponding to exchanged wavevector q values ranging from 0.0256 to 0.0448 nm⁻¹. In particular we find that the isotropic spectral lineshapes are in all cases well described by the simple hydrodynamic theory of an amorphous solid. The width of the Brillouin peaks are found to be consistent with the predicted q² dependence at both investigated temperatures. This damping is however found to account only partially for the strong asymmetry of the Brillouin line clearly visible on a logarithmic intensity scale. As a matter of fact there is an excess intensity in the very low frequency plateau underlying the central component. The height of this plateau and hence the entire lineshape is well reproduced if a relaxation process is taken into account in the hydrodynamic equations. Owing to the intense elastic scattering we are able to determine unambiguously only the ratio between amplitude and characteristic time of this process which quantifies the sound dispersion to be of the order of a few percent in all samples. The temperature dependence of the parameters indicates that this relaxation cannot be attributed to thermally activated relaxation phenomena. These general findings favorably compare with molecular dynamics simulation results on similar systems.