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     

Synthesis and characterization of polyaniline doped with organic acids

Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004     

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.     

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.     

Inverse problems for a mathematical model of redox sorption

We consider a mathematical model of sorption that allows for external diffusion kinetics and a redox reaction. Two inverse problems are considered for this model, uniqueness is proved, and numerical solution methods are proposed. The efficiency of the numerical methods is investigated by computer experiments. __________ Translated from Prikladnaya Matematika i Informatika, No. 23, pp. 15–23, 2006.     

On the Stability of Bifurcation Diagrams of Vanishing Flattening Points

On a smooth surface in Euclidean 3-space, we consider vanishing curves whose projections on a given plane are small circles centered at the origin. The bifurcations diagram of a parameter-dependent surface is the set of parameters and radii of the circles corresponding to curves with degenerate flattening points. Solving a problem due to Arnold, we find a normal form of the first nontrivial example of a flattening bifurcation diagram, which contains one continuous invariant.     

X-ray induced fluorescence spectrometry at grazing incidence for quantitative surface and layer analysis

Summary Single layers and layer systems on diverse substrates were measured by Total Reflection X-Ray Fluorescence (TXRF) spectrometry. The angular dependence of the fluorescence intensities at grazing incidence allows the elemental composition, density and thickness of the layers to be evaluated using model calculations.     

Unoccupied electronic states of epitaxial iron layers on Cu(100)

Inverse photoemission spectra were taken for thin epitaxial iron films on Cu(100). For a film thickness of eight monolayers the observed electronic states are characteristic for a fcc(100) surface. Thed-bands of iron show a ferromagnetic exchange splitting of 1.1 eV, considerably smaller than the bulk value of 1.8 eV, which we observe for film thicknesses above 18 monolayers.