A mechanistic investigation of (Me3Si)3SiH oxidation

The interaction of (Me₃Si)₃SiH with O₂ is known to afford (Me₃SiO)₂Si(H)SiMe₃ in which the two oxygen atoms arise from the same oxygen molecule. In order to investigate the mechanism of this unusual reaction, the oxidation rates were measured in the temperature range 30-70 °C by following oxygen uptake in the presence and absence of hydroquinone as inhibitor. The rate constant for the spontaneous reaction of (Me₃Si)₃SiH with O₂ was determined at 70 °C to be ∼3.5 × 10⁻⁵ M⁻¹ s⁻¹. A sequence of the propagation steps is proposed by combining the previous and present experimental findings with some theoretical results obtained at the semiempirical level. These calculations showed that the silylperoxyl radical (Me₃Si)₃SiOO undergoes three consecutive unimolecular steps to give (Me₃SiO)₂Si()SiMe₃. Evidence has been obtained that the rate determining step is the rearrangement of silylperoxyl radical to a dioxirand-like pentacoordinated silyl radical. Our findings are of considerable importance for the understanding of the oxidation of hydrogen-terminated silicon surfaces.     

Molecular distillation

Molecular distillation was studied for the separation of tocopherols from soya sludge, both experimentally and by simulation, under different operating conditions, with good agreement. Evaporator temperatures varied from 100°C to 160°C and feed flow rates ranged from 0.1 to 0.8 kg/h. The process pressure was maintained at 10⁻⁶ bar, the feed temperature at 50°C, the condenser temperature at 60°C, and the stirring at 350 rpm. For each process condition, samples of both streams (distillate and residue) were collected and stored at −18°C before tocopherols analyses. Owing to the differences between molecular weights and vapor pressures of free fatty acids and tocopherols, tocopherols preferentially remained in the residue at evaporator temperatures of 100°C and 120°C, whereas for higher temperatures (140°C and 160°C) and lower feed flow rate, tocopherols tended to migrate to the distillate stream.     

木材溶液中羟基与异氰酸酯反应的研究

以涂料工业广泛应用的新型助剂二元酸酯 (DBE)为液化试剂 ,盐酸为催化剂 ,将苯甲基化木材溶液化后 ,与不同结构的异氰酸酯反应 .利用FT IR及1 3C NMR分析液化苯甲基木质纤维素与不同结构异氰酸酯得到了聚氨酯树脂 ,证明了木材中羟基可以用来作为聚醚多元醇与异氰酸酯制备聚氨酯材料 .通过准确测量体系中游离的NCO含量 ,从而得出不同结构异氰酸酯与木材溶液中羟基的反应规律 .实验结果表明 ,异氰酸酯的存在大大促进了木材结构中羟基的释放 ,由于不同异氰酸酯的活性不同 ,使得羟基值变化亦不相同 ,其顺序为IPDI>HDI>TDI .为了保证最终的材料性能 ,选择TDI和IPDI作为木材溶液制备聚氨酯树脂的异氰酸酯组份较好     

胞嘧啶水溶液体系辐解的瞬态产物研究

Using the ns pulse radolysis, we studied the characteristic absorption spectrum and kinetic decay of cytosine anion radical (Cyt-). Results showed that the characteristic absorption of Cyt- was located at λ=355±5 nm, and decayed following the first order kinetics with τ1/2=265 ns at pH=7.0. The decay became slower and τ1/2 rapidly rised with the increment of pH value, Cyt- protonated at C6 in acidic solution, and the characteristic absorption was located at λ=310±5 nm, and decayed following the second order kinetics: Cyt- protonated at N3 in aqueous solution of pH≥7, and the characteristic absorption was located at λ=295±5 nm, and decayed following the second order kinetics.     

Miscibility and phase separation in SAN/PMMA blends investigated by positron lifetime measurements

Miscibility and phase separation in SAN/PMMA blends have been investigated using DSC, IR spectroscopy and positron lifetime spectroscopy (PLS). Single broad glass transition observed throughout the blend compositions, may be due to overlap of two glass transitions. IR measurements clearly indicate the absence of strong interactions. This supports miscibility is due to intramolecular repulsive forces in the SAN component. On the other hand, free volume data show negative deviation from linear additivity indicating the blends are miscible. The interchain interaction parameter β exhibits a complex behavior and the extent of miscibility is not revealed. Following Wolf’s treatment, we have evaluated the geometry factor γ and hydrodynamic interaction parameter α and found α is a suitable parameter in predicting the miscibility window. The cloud points in SAN/PMMA blends increase with decreasing PMMA content. The change in free volume size correlates well with the observed change in cloud point.     

Convergence of the Finite Difference Scheme for a Fast Diffusion Equation in Porous Media

We are concerned with an implicit scheme for the finite difference solution to a nonlinear parabolic equation with a multivalued coefficient that describes the fast diffusion in a porous medium. The boundary conditions contain the multivalued function as well. We prove the stability and the convergence of the scheme, emphasizing the precise nature of convergence in this specific case, and compute the error level of the approximating solution. The method is aimed to simplify the numerical computations for the solutions to equations of this type, without performing an approximation of the multivalued function. The theory is illustrated by numerical results.     

Bounds for the fundamental solutions of elliptic and parabolic equations

It is shown that any elloptic or parabolic operator in nondivergence form with measurable coefficients has a global fundamental solution verifying certain pointwise bounds.     

Contributions to the Optimization of a Caprolactam Production Plant by Radiotracer Techniques

Residence time spectra and material distributions in an operating caprolactam production plant were measured by means of sodium 24, bromine 82 and technetium 99m. The results of the tracerexperiments contributed to an optimization of the plant.     

Improved efficiency of organic solar cells with modified hole‐extraction layers

The aim of this work has been to study the influence of modified hole‐extraction layers on the performance of organic solar cells (OSCs) based on blends of poly (3‐hexylthiophene) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester. The hole‐extraction layers consist of poly (3,4‐ethylene dioxythiophene):polystyrene sulfonic acid (PEDOT:PSS) doped with different concentrations of bromine. Compared with pristine OSC without adding bromine to the hole‐extraction layer, the bromine‐doped OSCs show a 49% increase in the power conversion efficiency (from 2.12 to 3.16%), which could be attributed to the increase of electrical and optical properties of PEDOT:PSS films after the addition of bromine. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 125–128, 2012     

A free boundary problem related to thermal insulation

We study a free boundary problem arising from the theory of thermal insulation. The outstanding feature of this set optimization problem is that the boundary of the set being optimized is not a level surface of a harmonic function, but rather a hypersurface along which a harmonic function satisfies a Robin condition. We show that minimal sets exist, satisfy uniform density estimates, and, under some geometric conditions, have “locally flat” boundaries.