Electrosynthèse des ions peroxodiphosphate sous potentiel constant ou pulsé

Electrosynthesis of peroxodiphosphate ions (P2O84–) was performed in 2m K3PO4, 1m K2HPO4 medium, using a platinum anode. The results showed that under conditions of potentiostatic polarization at constant potential, the reaction rate reaches a maximum value of 125mAcm–2 and a faradaic yield of 30%. From about 1.9V, the reaction kinetics are increasingly inhibited as the potential shifts positively. Rapid scanning potential voltammetry was used to characterize the oxidation state of the electrode surface. This method shows that the growth of (PtO) and (PtO2 or PtO3) oxides depend on the applied potential. It also establishes a correlation between the inhibition of P2O84– ion electrosynthesis and the oxide coating surface. When 2×10–3m KSCN is added to the solution, some oxygen evolution sites are selectively blocked and oxide occurs at more positive potential values. Consequently, the rate of peroxodiphosphate ion formation and the faradaic efficiency are increased to 380mAcm–2 and 75%, respectively. Under pulsed potential conditions it was possible to reach 1200mAcm–2 for P2O84– ion electrosynthesis with a faradaic yield of 82%.     

采用有限元分析法量化不同中空玻璃边缘密封的热位移

间隔条和玻璃板片之间的相对热位移是中空玻璃边缘密封乃至中空玻璃(IGU)本身老化的主要原因之一.作者采用有限元分析法(FEA),建立了发生在大尺寸(1.5 m×2.1 m)的中空玻璃边缘密封的热位移与温差变化之间的模型,这是三种商业化的、不同材质的、不同设计的间隔条,在温度变化为-30～ 60℃范围内的模型.此模型是基于铝间隔条和镀锌钢间隔条与尼龙插角的搭配,不锈钢间隔条和弯曲插角的搭配.尼龙插角假定为实心的并稳固地固定于间隔条上;弯曲插角被建模成实心弯曲的金属插角,并同样稳固地固定于间隔条上.由于实际的弯曲插角是空心的,模型可能高估了这种转角设计的应力.正如预期那样,在低温时,插角会被向内拉,导致弯曲角度大于90°;在高温下,插角会被向外推,导致弯曲角度小于90°.通过检测发生在中空玻璃周边第一道密封的聚异丁烯密封胶厚度的变化,作者发现,到目前为止,不锈钢间隔条对于截面积的变化影响最小;铝制间隔条的影响最大.这个发现与基于间隔条材料与浮法玻璃之间热膨胀系数差异而预期的性能一致.因此,热位移引起的第一道密封的有效扩散横截面变化,可以解释为何具有不同间隔条材料的中空玻璃之间的性能差异.     

NMR imaging and differential scanning calorimetry study on drying of pine,birch, and reed pulps and their mixtures

Drying, water fractions, and water distribution were investigated for pine, birch, and reed pulps and pine–birch, pine–reed, and pine–birch–reed pulp mixtures. Gravimetrically determined drying times showed that the drying rates of the pulps decreased at two to four inflection points. Characterizations of the dried pulps by differential scanning calorimetry (DSC) showed a faster removal of free water than freezing and nonfreezing bound waters; all decreased simultaneously, however. DSC also revealed the critical water contents at which the free water and freezing bound water disappeared. The gravimetrically determined inflection points of the drying curves corresponded with the critical points determined by DSC. NMR line widths and images produced by ¹H‐NMR imaging revealed the nature and regions of the pulp drying. The constant growth rate of the NMR line widths with decreasing water content appeared to change at two inflection points, which fell approximately in the same water content regions as the inflection points of the drying curves. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 937–945, 2006     

Enhanced Photocatalytic Hydrogen Evolution Over CaTi1−x Zr x O3 Composites Synthesized by Polymerized Complex Method

The solid solution of CaTi_1−x Zr _x O₃ (x = 0–0.15) was successfully synthesized by the polymerized complex (PC) method. This study has exhibited the advantage of the PC method to prepare a highly active CaTiO₃ compared with the conventional solid-state reaction (SSR) method. More importantly, further improvement in phase purity and large surface area was achieved by the doping of Zr⁴⁺, leading to remarkable enhancement of photocatalytic activities compared to pure CaTiO₃. The quantum yield for H₂ evolution over the most active photocatalyst, Pt (1.0 wt%)/CaTi_0.93Zr_0.07O₃, was 1.91% and 13.3% in photoreactions from pure water and aqueous ethanol solution, respectively for 0.1 g photocatalyst, which was about 3.3 and 2.5 times compared to that of PC-derived CaTiO₃.     

Planar and axially symmetric slow shearing granular flows: a comparative evaluation of assembly evolution incorporating wavelet transforms

We demonstrate the enhanced capacities of our analysis toolset for three-dimensional data. In particular, we provide supporting evidence for some of the conclusions reached in our previous studies of two-dimensional avalanching heaps. Segregation by self-diffusion is shown to take place in three-dimensional assemblies and self-diffusion velocities are shown to be of a comparable order of magnitude to those found in plane-strain situations. The effect on assembly evolution by discrete avalanching of the availability of a third dimension for translation is investigated. The discrete wavelet transform is again shown to be a useful component of the toolset in coupling process variables in the context of the discrete defining events associated with assembly evolution. In particular, we move towards the determination of time constants by correlating wavelet coefficients with a time shift.     

Properties and crystallization kinetics of poly(ether ether ketone)‐co‐poly(ether ether ketone ketone) block copolymers

A series of block copolymers composed of poly(ether ether ketone) (PEEK) and poly(ether ether ketone ketone) (PEEKK) components were prepared from their corresponding oligomers via a nucleophlilic aromatic substitution reaction. Various properties of the copolymers were investigated with differential scanning calorimetry (DSC) and a tensile testing machine. The results show that the copolymers exhibited no phase separation and that the relationship between the glass‐transition temperature (T_g) and the compositions of the copolymers approximately followed the formula T_g = T_g1X₁ + T_g2X₂, where T_g1 and T_g2 are the glass‐transition‐temperature values of PEEK and PEEKK, respectively, and X₁ and X₂ are the corresponding molar fractions of the PEEK and PEEKK segments in the copolymers, respectively. These copolymers showed good tensile properties. The crystallization kinetics of the copolymers were studied. The Avrami equation was used to describe the isothermal crystallization process. The nonisothermal crystallization was described by modified Avrami analysis by Jeziorny and by a combination of the Avrami and Ozawa equations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1652–1658, 2005     

自适应混合多目标分布估计进化算法

针对多目标分布估计算法全局收敛性较弱的缺陷,提出了一种自适应混合多目标分布估计进化算法。其基本思想是:在多目标分布估计算法中引入全局收敛性较强的差分进化算法,当函数变化率较大时,用分布估计算法产生新种群;当函数变化率较小即算法可能陷入局部收敛时,用差分进化算法产生新种群。理论分析和数值实验结果表明,这种混合算法不仅具有良好的全局收敛性,而且解的分布性和均匀性较没有考虑目标函数变化率的混合多目标分布估计算法也有了一定程度的提高。     

Condensed combustion products of aluminized propellants. IV. Effect of the nature of nitramines on aluminum agglomeration and combustion efficiency

The condensed combustion products of two model propellants consisting of ammonium perchlorate, aluminum, nitramine, and an energetic binder were studied by a sampling method. One of the propellants contained HMX with a particle size D ₁₀ ≈ 490 μm, and the other RDX with a particle size _{D 10} ≈ 380 μm. The particle-size distribution and the content of metallic aluminum in particles of condensed combustion products with a particle size of 1.2 μm to the maximum particle size in the pressure range of 0.1–6.5 MPa were determined with variation in the particle quenching distance from the burning surface to 100 mm. For agglomerates, dependences of the incompleteness of aluminum combustion on the residence time in the propellant flame were obtained. The RDX-based propellant is characterized by more severe agglomeration than the HMX-based propellant — the agglomerate size and mass are larger and the aluminum burnout proceeds more slowly. The ratio of the mass of the oxide accumulated on the agglomerates to the total mass of the oxide formed is determined. The agglomerate size is shown to be the main physical factor that governs the accumulation of the oxide on the burning agglomerate. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 4, pp. 78–92, July–August, 2006.     

Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm⁻¹. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.     

钒钼酸铵分光光度法快速测定磷酸二铵中有效五氧化二磷

为了快速测定磷铵中P2O5含量,将0.1mol/LEDTA预热至80±2℃作为DAP有效P2O5的提取液,提取时间25min以上。鉴于正磷酸根在酸性介质中与钼酸盐及偏钒酸盐生成稳定的黄色化合物,在400nm波长下,利用示差法测定P2O5仅需50～55min。该方法的相对标准偏差(RSD)为0.13%～0.28%,回收率99.1%～101.1%,精密度和准确度好。