Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Integrable models for vicious and friendly walkers

We consider random walks of two essentially different classes of random walkers, namely, of vicious and friendly ones, on one-dimensional lattices with periodic boundary conditions. The walkers are called vicious since, arriving at a lattice site, they annihilate not only one another but all the remaining walkers as well. On the contrary, an arbitrary number of friendly walkers can share the same lattice sites. It is shown that a natural model describing the behavior of friendly walkers is an integrable model of the boson type. A representation of the generating function for the number of the lattice paths performed by a fixed number of friendly walkers for a certain number of steps is obtained. Bibliography: 22 titles. __________ Translated from Zapiski Nauchnykh Seminarov POMI, Vol. 335, 2006, pp. 59–74.     

Relaxing local modes and the theory of low-frequency Raman scattering in glasses

Raman scattering in glasses is investigated theoretically. The experimental Raman spectra of glasses exhibit a low-frequency peak (at ～10 cm^?1) that, as a rule, is attributed to vibrational modes of nanometer-sized structural units (nanocrystallites). It is established that the elastic moduli of nanocrystallites must necessarily be dependent on their sizes due to the Laplace pressure effect. A theory of the low-frequency peak is constructed using a realistic size distribution function of nanocrystallites with allowance made for the Laplace pressure effect and the dissipation of vibrational energy. Within this theory, the shape of the low-frequency peak and its evolution with temperature can be analyzed quantitatively. The proposed approach offers a physical interpretation of the experimental data and provides insight into the relation of the characteristic nanocrystallite sizes to the elastic moduli and surface tension coefficients of materials.     

Effective thermal conductivity of water-saturated sintered powder-metal plates

An experimental apparatus and related procedures for the determination of the effective thermal conductivity of sintered powder-metal plates saturated with distilled water at temperatures in the range 20–150°C are discussed. The apparatus and procedures are applied to two samples of sintered powder-metal plates, one made of nickel 200 and the other of stainless steel 316, with porosities of 28.10 and 46.45%, respectively, and each of nominal dimensions 127 mm × 127 mm × 6.35 mm. The experimental results are compared with corresponding predictions yielded by several correlations available in the literature. The correlations based on experimental data for packed beds of spherical particles and also porous plates made of cold-pressed (but not sintered) particles of angular shapes do not apply well to sintered powder-metal plates. A new correlation, which is based on extensions of ideas contained in earlier works and provides improved predictions, is proposed.     

General-relativistic cosmology with expansion and rotation

A model of an expanding and rotating universe is constructed in the framework of general relativity. The parameters of the model are compared with the fundamental observables and shown to be in good agreement.Kaluzhsk Branch, N. É. Bauman Moscow State Technical University (MGTU). Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 71–77, June, 1993.     

A shock tube study of the reaction of methyl radicals with hydroxyl radicals

The reaction of CH₃ with OH has been studied near 1200 K and 1 atmosphere pressure in shock tube experiments in which UV absorption was used to monitor [OH]. A rate coefficient of (1.1 ± 0.3) × 10¹³ cm³/mol-s was measured for removal of OH by CH₃. This measured value is compared with previous experimental data and calculations. Several possible reaction channels are discussed, and although products were not monitored, it seems probable, on the basis of other work and theoretical estimates, that the primary mechanism (?75%) for the removal of OH by CH₃ at these conditions is their combination to form CH₃OH. Rate coefficients of (5.3 ± 0.8) × 10¹² and (9.0 ± 1.4) × 10¹² cm³/mol-s were measured for the reactions of OH with acetone and ethane, respectively, at the same temperature and pressure.