Synthesis,characterization, and thermal properties of phosphorus‐containing,wholly aromatic thermotropic copolyesters

A series of phosphorus‐containing, wholly aromatic thermotropic copolyesters from acetylated 2‐(6‐oxide‐6H‐dibenz〈c,e〉〈1,2〉oxa phosphorin‐6‐yl)‐1,4‐dihydroxy phenylene, p‐acetoxybenzoic acid, terephthalic acid, and isophthalic acid were prepared by melting polycondensation. The structure and basic properties of the polymers, such as the glass‐transition temperature (T_g), melting temperature (T_m), thermal stability, crystallinity, and liquid crystallinity, were investigated with Fourier transform infrared, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray diffraction, and hot‐stage polarizing optical microscopy. The copolyesters had relatively high T_g values ranging from 183 to 192°C. The T_m values obtained from DSC curves for samples P‐20 and P‐25 were 290 and 287°C, respectively (where the number in the sample name indicates the molar fraction of the phosphorus‐containing monomer in the reactants). The initial flow temperatures of other samples observed with hot‐stage polarizing microscopy were 271–290°C. The 5% degradation temperatures in nitrogen ranged from 431 to 462°C, and the char yields at 640°C were 41–52%. All the copolyesters, except P‐40, were thermotropic and nematic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1278–1284, 2002     

SIS-g-AN热降解性能的研究

采用热重分析法和差示热重分析法研究丙烯腈(AN)接枝热塑性弹性体SIS(SIS g AN)的热降解性能。结果得出,SIS g AN的平衡起始降解温度、平衡最大降解速率温度和平衡终止降解温度分别为659. 17, 713. 94 和740.05 K;热降解反应活化能为195.2 kJ·mol-1;热降解机理是Deceleration中的D3 降解机理;不同质量损失率下的热寿命与温度呈线性关系。     

Improvement of polymer blend properties by changing sequence of mixing

The basic objective of this article is to improve the polymer blend properties by changing mixing sequence. Blending of two elastomers does not lead to a molecularly homogeneous blend (true solution), but to a heterogeneous system in which both polymer phases are present. In this article, the detailed study of heterogeneous distribution of carbon black as well as blend inhomogenity and the physicomechanical including dynamic mechanical properties of the blend has been carried out. The choice of the blend was natural rubber/polybutadiene rubber as 85:15. Heterogeneous carbon black distribution study was also performed in differential scanning calorimeter. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2735–2742, 2007     

Crystallization behavior of dry‐brush PEO‐PS block copolymer and PEO homopolymer blend

The crystallization behavior of semicrystalline PEO homopolymer/triblock PS‐PEO‐PS copolymer blend system, which exhibited “Dry‐Brush” in the melt. A symmetric polystyrene–poly(ethylene oxide)–polystyrene triblock copolymer was blended with PEO homopolymer (h‐PEO) having the same molecular weight as that of the PEO block in the copolymer. Considering the composition of the blend (W_ps ≥ 0.8), PEO spheres were formed in the blend. Because of the dry‐brush phase behavior of this blend, h‐PEO added was localized in the PEO microdomains, which increases the domain size without changing the microdomain morphology. The crystallization of PEO block was confined within the microdomains and the crystallization temperature was about 60°C lower than normal. Self‐seeding tests were performed to clarify the nucleation mechanism of the blend. Because the droplets size varies greatly, multicrystallization peaks were witnessed in the self‐seeding process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

全自动污泥脱水离心机的电气控制系统

介绍了采用恒差速恒力矩控制方案克服卧螺离心机处理城市污泥时容易产生的堵料问题,介绍了絮凝剂自动制备和添加装置。     

羧基化高纯单壁碳纳米管修饰电极对乙酰甲喹的高灵敏检测

采用羧基化高纯单壁碳纳米管(c SWCNTs)固载于金电极表面来构筑乙酰甲喹电化学传感器。运用循环伏安法(CV)、差分脉冲伏安法(DPV)和电化学交流阻抗法(EIS)测定传感器的性能。结果显示,该传感器对乙酰甲喹的电化学还原具有显著的催化性能,修饰电极的峰电流达到-128.40μA,是裸电极峰电流的1167倍。通过对传感器性能影响因素的考察,得到最优制备条件为cSWCNTs涂覆量为4μL(质量分数0.10%分散液),搅拌速度1000 r/min,pH=7.0的PBS浓度为0.2 mol/L,-0.5V电压下富集30 min。在该条件下制备的传感器峰电流与乙酰甲喹在1～500nmol/L范围内呈良好的线性关系,相关系数为0.998,方法的检出限为0.76nmol/L。该传感器被成功地应用于实际样品检测,加标回收率在81.7%～124.0%。     

Jet bundle formulation of infinite-dimensional port-Hamiltonian systems using differential operators

We consider infinite-dimensional port-Hamiltonian systems described on jet bundles. Based on a power balance relation we introduce the port-Hamiltonian system representation using differential operators regarding the structural mapping, the dissipation mapping and the input mapping. In contrast to the well-known representation on the basis of the underlying Stokes–Dirac structure our approach is not necessarily based on using energy-variables which leads to a different port-Hamiltonian representation of the analyzed partial differential equations. The presented constructions will be specialized to mechanical systems to which class also the presented examples belong.     

Bi2—xPbxSr2Ca2Cu3Oy系高Tc超导体相变的研究

用DSC研究了高T_e超导体B_(2-r)Pb_rSr_2Ca_2Cu_sO_v(x=0,0.2,0.4,0.6)从室温至600℃范围内的相变。在320℃和440℃附近有二个吸热蜂,每一个峰对应一个相变过程。440℃附近的相变是不可递的,其原子激活能为1.37eV,是由高T_e相向低T_e相的转变。而320℃附近的相变则与超结构的形成有关。     

Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. II. Network‐forming DGEBA + MDA

Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (T_g) rises above the cure temperature (T_cure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of T_cure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E_1OH = 44 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and T_cure. The relation between x, r, and T_g, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in C_p in the glassy region with x and T_cure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004     

Curing process of powdered phenol–formaldehyde resol resins and the role of water in the curing systems

The curing behavior of two kinds of commercial powdered resol phenolic resins was studied by differential scanning calorimetry. Liquid‐state ¹³C‐NMR spectroscopy was used to aid in understanding the curing behavior by detecting the structure of powdered resins. The reaction mechanism was interpreted with the dependency of activation energy on the degree of conversion. The results indicate that there are differences in the curing mechanism between core and face phenolic resins. The curing process of core resin was faster than that of face resin at the same reaction temperature. The water added in the curing system played an important role of plasticizer or diluent according to different curing stages and water content. In the initial curing stage, water mainly diluted the system and retarded the curing reactions. However, at the higher degrees of conversion, water played the role of plasticizer to decrease the effect of diffusion on the curing reactions to make the curing reactions more complete. The excess water added in the curing system played the role of diluent at almost all stages during the curing process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1371–1378, 2003