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     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

Microstructural assessment of InN-on-GaN films grown by plasma-assisted MBE

The structural properties of InN thin films, grown by rf plasma-assisted molecular beam epitaxy on Ga-face GaN/Al₂O₃(0001) substrates, were investigated by means of conventional and high resolution electron microscopy. Our observations showed that a uniform InN film of total thickness up to 1 μm could be readily grown on GaN without any indication of columnar growth. A clear epitaxial orientation relationship of , was determined. The quality of the InN film was rather good, having threading dislocations as the dominant structural defect with a density in the range of 10⁹–10¹⁰ cm⁻². The crystal lattice parameters of wurtzite InN were estimated by electron diffraction analysis to be a=0.354 nm and c=0.569 nm, using Al₂O₃ as the reference crystal. Heteroepitaxial growth of InN on GaN was accomplished by the introduction of a network of three regularly spaced misfit dislocation arrays at the atomically flat interface plane. The experimentally measured distance of misfit dislocations was 2.72 nm. This is in good agreement with the theoretical value derived from the in-plane lattice mismatch of InN and GaN, which indicated that nearly full relaxation of the interfacial strain between the two crystal lattices was achieved.     

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.     

Numerical study of simultaneous natural convection heat transfer from both surfaces of a uniformly heated thin plate with arbitrary inclination

 Numerical studies were conducted to investigate the natural convection heat transfer around a uniformly heated thin plate with arbitrary inclination in an infinite space. The numerical approach was based on the finite volume technique with a nonstaggered grid arrangement. For handling the pressure–velocity coupling the SIMPLE-algorithm was used. QUICK scheme and first order upwind scheme were employed for discretization of the momentum and energy convective terms respectively. Plate width and heating rate were used to vary the modified Rayleigh number over the range of 4.8×10⁶ to 1.87×10⁸. Local and average heat transfer characteristics were compared with regarding to the inclination angle. The empirical expressions for local and average Nusselt number were correlated. It has been found that for inclination angle less than 10^∘, the flow and heat transfer characteristics are complicated and the average Nusselt number can not be correlated by one equation while for inclination angle larger than 10^∘, the average Nusselt number can be correlated into an elegant correlation. Received on 18 April 2001 / Published online: 29 November 2001     

Molecular Complexes of Crown Ethers in Crystals and Solutions

A review of the experimental and theoretical studies of the crown ether complexes with polar molecules in their crystals, solutions, and in a gas phase is given. The type of the molecular bonds in the complexes, their stoichiometry, and the change in the macrocycle conformation during complex formation are considered, as well as the effect of the macrocycle structure and the nature of the medium on the efficiency of the molecular bonding. New data are given on the enthalpies of transfer of the crown ethers from tetrachloromethane into solvents capable of forming hydrogen bonds. The enthalpies of specific interactions of macrocycles with the molecules of the solvents in the medium of the same solvents are characterized. The conformations of the crown ethers in the media under study are discussed.     

A rapid and sensitive extractive spectrophotometric determination of copper(II) in pharmaceutical and environmental samples using benzildithiosemicarbazone.

Benzildithiosemicarbazone (BDTSC) is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of copper(II). BDTSC reacts with copper(II) in the pH range 1.0-7.0 to form a yellowish complex. Beer's law is obeyed in the concentration range 0.5-0.4 microg cm(-3). The yellowish Cu(II)-BDTSC complex in chloroform shows a maximum absorbance at 380 nm, with molar absorptivity and Sandell's sensitivity values of 1.63 x 10(4) dm3 mol(-1) cm(-1) and 0.00389 microg cm(-2), respectively. A repetition of the method is checked by finding the relative standard deviation (RSD) (n = 10), which is 0.6%. The composition of the Cu(II)-BDTSC complex is established as 1:1 by slope analysis, molar ratio and Asmus' methods. An excellent linearity with a correlation coefficient value of 0.98 is obtained for the Cu(II)-BDTSC complex. The instability constant of the complex calculated from Edmond and Birnbaum's method is 7.70 x 10(-4) and that of Asmus' method is 7.66 x 10(-4), at room temperature. The method is successfully employed for the determination copper(II) in pharmaceutical and environmental samples. The reliability of the method is assured by analyzing the standard alloys (BCS 5g, 10g, 19e, 78, 32a, 207 and 179) and by inter-comparison of experimental values, using an atomic absorption spectrometer.