Oligomer and Polymer Formation in Hexamethylcyclotrisiloxane (D<Subscript>3</Subscript>) – Hydrosilane Systems Under Catalysis by tris(pentafluorophenyl)borane

Summary Reactions of hexamethylcyclotrisiloxane, D₃, with 1,1,3,3-tetramethyldisiloxane, ^HMM^H, 1,1,1,3,3-pentamethyldisiloxane, ^HMM, phenyldimethylsilane and phenylmethylsilane catalyzed by tris(pentafluorophenyl)borane were studied. These reactions lead to ring opening of D₃ by the SiH reactant producing open chain oligomers with hydrosilane functionality at one or both chain ends. The reactivity of the hydrosilanes toward D₃ decreases in the series: PhMeSiH₂ > ^HMM^H > PhMe₂SiH > ^HMM. Competitive self-oligomerization of ^HMM^H and ^HMM also occurs. Primary products of these processes are able to enter into reactions with the SiH and D₃ reactants; some also undergo cyclization. Thus, consecutive and competitive processes lead to a series of various oligohomologues. Gas chromatography in conjunction with chemical ionization mass spectroscopy permitted identification of structure and determination of the basic directions of these oligomerization processes. Polysiloxanes of higher molecular weight may be also formed in some of these systems. The reactions, which occur in the systems studied, are rationalized on the basis of the mechanism involving the hydride transfer from silicon to trivalent boron. This includes the transient formation of tertiary trisilyloxonium borate which decomposes by the hydride transfer to one of the silicon atoms of the trisilyloxonium center. Footnote: This paper is dedicated to Professor Ian Manners in recognition of his significant contributions to the field of organometallic polymers.     

界面改性PA6/TPE共混物的形态结构与性能

通过控制马来酸酐(MAH)的用量制得不同接枝率的马来酸酐接枝热塑性弹性体(TPE-g-MAH),利用其与尼龙6(PA6)在共混过程中的反应增容作用,实现了与PA6的相容共混,并研究了PA6/TPE共混物的结构与性能。结果表明,TPE-g-MAH可有效地提高PA6/TPE共混物的韧性,且随着其接枝率的增加,共混物的韧性提高;TPE-g-MAH有效地改善了PA6/TPE共混物的界面相容性,并且随着其含量的增加,相界面增容效果变好。     

Speech enhancement with an adaptive Wiener filter

This paper proposes an adaptive Wiener filtering method for speech enhancement. This method depends on the adaptation of the filter transfer function from sample to sample based on the speech signal statistics; the local mean and the local variance. It is implemented in the time domain rather than in the frequency domain to accommodate for the time-varying nature of the speech signals. The proposed method is compared to the traditional frequency-domain Wiener filtering, spectral subtraction and wavelet denoising methods using different speech quality metrics. The simulation results reveal the superiority of the proposed Wiener filtering method in the case of Additive White Gaussian Noise (AWGN) as well as colored noise.     

On the Gröbner basis triangularization of constraint equations in natural coordinates

Efficient dynamic simulation code is essential in many situations (including hardware-in-the-loop and model-predictive control applications), and highly beneficial in others (such as design optimization, sensitivity analysis, parameter identification, and controller tuning tasks). When the number of modeling coordinates n exceeds the degrees-of-freedom of the system f, as is often the case when closed kinematic chains are present, the governing dynamic equations consist of n second-order ordinary differential equations (ODEs) coupled with m=n?f algebraic constraint equations. This set of n+m index-3 differential-algebraic equations can be difficult to solve in an efficient yet accurate manner. Embedding (or generalized coordinate partitioning) can be used to obtain f ODEs (one for each independent acceleration), which are generally more amenable to numerical integration; however, the dependent positions are typically computed from the independent positions at each time step. Newton–Raphson iteration is often used for solving the position-level kinematics, but only provides solutions to within a specified tolerance, and can require several iterations to converge. In this work, Gröbner bases are used to obtain recursively solvable symbolic solutions for the dependent positions, which can then be evaluated to within machine precision using a fixed number of arithmetic operations. Natural coordinates are particularly attractive in this context, since the resulting constraint equations are maximally quadratic polynomials and are, therefore, easily triangularized. The proposed approach is suitable for use in an automated formulation procedure and, as demonstrated by three examples, is capable of generating highly efficient simulation code with minimal additional effort required at the formulation stage.     

核电工程项目调试工期的影响因素与优化

调试启动工作是核电工程项目进度控制中非常重要的环节,对整个工程的顺利投入运行有着重要的作用。如果调试工期过长,则会导致核电工程不能按期交付使用,从而对整个核电工程的进度造成影响。主要探讨了核电工程项目调试工期的影响因素和优化措施。     

Matching ratio between positive and negative electrodes for double-layer capacitors

For double-layer capacitors in alkaline electrolyte, the specific capacitance of the positive electrode is not equal to that of the negative one. Thus, capacitor performance cannot be optimal with a positive/negative electrode matching ratio of 1. In this study nanoporous glassy carbons (NPGCs) were employed as the electrodes of capacitors, and the influence of matching ratio between positive and negative electrode on capacitor performance was systematically investigated. In aqueous KOH, the specific capacitance of the positive electrode is lower than that of the negative electrode. The matching ratio at which a maximum capacitance is obtained is dependent on the values of the positive and negative electrode capacitance. At low current rate, the highest specific capacitance is achieved at a matching ratio slightly higher than 1. At high current rate, a capacitor has the highest specific capacitance with the lowest resistance at a matching ratio of 1.5. This indicates that an optimum matching relationship between positive and negative electrodes is attained.     

Synthesis,characterization, and thermal properties of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane

Hexamethyldisilazane was used as the starting material to synthesize N,N′‐bis(hydroxydiphenylsilanyl)tetraphenylcyclodisilazane (BHPTPC). By condensation polymerization of BHPTPC with α,ω‐bis(dialkylamino)dimethylsiloxane, a series of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane was synthesized. GPC studies show that the highest molecular weight was obtained at a ratio of 1.005 : 1 (BHPTPC: α,ω‐bis(dimethyl amino)dimethylsiloxane). Data of DSC indicate that the temperature of glass transition (T_g) and temperature of melting point (T_m) decreased with the increasing of dimethylsiloxane segments units. Three stages of degradation were found in the thermogravimetric analysis curves. The activation energy of the copolymer (with m = 2, 3, and 7) was calculated by using Flynn–Wall–Ozawa method. The activation energy of the copolymer with m = 2, 3, and 7 at second stage is 214, 211, and 184 kJ/mol, respectively. Isothermal gravimetric analysis shows that for the same temperature and the same time, the weight loss of the alternate copolymer was greatly less than that of common polydimethylsiloxane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 611–617, 2007     

Morphologies-Controlled Synthesis and Optical Properties of Bismuth Tungstate Nanocrystals by a Low-Temperature Molten Salt Method

Well-crystallized bismuth tungstate (Bi₂WO₆) powders with different morphologies were successfully synthesized via a low-temperature molten salt method. The powders were characterized by X-ray diffraction, transmission electron microscopy, and UV-Vis, respectively. It was found that the variation of morphology of the obtained Bi₂WO₆ powder mainly depends on the different reaction temperatures and the weight ratio of LiNO₃–NaNO₃ salt to precursor. In addition, the UV-Visible absorption spectra showed that the synthesized powders had strong light absorption properties not only in the ultraviolet light but also in the visible light region.     

An ensemble evolutionary constraint-based approach to understand the emergence of metabolic phenotypes

Constraint-based modeling is largely used in computational studies of metabolism. We propose here a novel approach that aims to identify ensembles of flux distributions that comply with one or more target phenotype(s). The methodology has been tested on a small-scale model of yeast energy metabolism. The target phenotypes describe the differential pattern of ethanol production and O₂ consumption observed in “Crabtree-positive” and “Crabtree-negative” yeasts in changing environment (i.e., when the upper limit of glucose uptake is varied). The ensembles were obtained either by selection among sampled flux distributions or by means of a search heuristic (genetic algorithm). The former approach provided indication about the probability to observe a given phenotype, but the resulting ensembles could not be unambiguously partitioned into “Crabtree-positive” and “Crabtree-negative” clusters. On the contrary well-separated clusters were obtained with the latter method. The cluster analysis further allowed identification of distinct groups within each target phenotype. The method may thus prove useful in characterizing the design principles underlying metabolic plasticity arising from evolving physio-pathological or developmental constraints.     

Supported Vanadia Catalysts for Dehydrogenation of Ethylbenzene with CO2

Alumina supported vanadia catalysts (V/Al) for selective oxidehydrogenation of ethylbenzene with CO₂ were prepared by impregnation method. During preparation the effect of promoters and calcined temperature was investigated, it was found these two items had a strong influence on the activity of V/Al catalysts. Dehydrogenation reaction with CO₂ was happened in the fixed-bed reactor at 450 °C. Results showed that 15.2% ethylbenzene conversion and 99.2% styrene selectivity were acquired when V₂K/Al catalyst was used.