Comments on the characterisation of oxidation catalysts using TPR/TPO

Temperature programmed reduction (TPR) and oxidation (TPO) are used extensively in catalyst characterisation. In this paper, we examine the use of TPR/TPO cycles for the characterisation of a range of molybdates and single oxides. In particular we observe that the first cycle differs from that of subsequent analyses, even when the maximum temperature is limited to that used in the catalytic reaction. The effect is independent of heating rates and cooling atmospheres and has been demonstrated using different bed configurations. This observation has significance when these oxides are used in periodic flow reactors that involve many cyclical reduction/oxidation.     

High temperature swelling of coal/tetralin mixtures in a high pressure microdilatometer

High pressure microdilatometer experiments were performed on a subbituminous (Wyodak) and a bituminous (Illinois no. 6) coal in helium and hydrogen atmospheres with and without added tetralin. Wyodak coal samples showed no swelling but contractions ranging between 24 and 40 vol% upon heating at 20 and 100 °C min^{− 1} under helium or hydrogen pressures between 150 and 1000 psig (˜1.0–6.9 MPa). Under the same conditions, Illinois no. 6 coals displayed contractions (25–60 vol%) prior to swelling up to 117 vol%. Upon tetralin addition (at 35–190 wt% of the coal), Wyodak coal samples did not swell but showed an increasing contraction with increasing helium or hydrogen pressure due to a slight softening and fusion of the coal particles. In contrast, addition of tetralin at much lower concentrations (5–35 wt%) had a marked effect on the contraction and swelling behaviour of Illinois no. 6. A maximum swelling of 200 vol% was obtained at a tetralin addition of 30 wt%. The increased swelling results from more extensive softening and fusion of coal particles in the presence of tetralin. Both coals showed a decreasing char yield with increasing tetralin concentration. The substantially lower extent of interaction observed between Wyodak coal samples and tetralin compared to Illinois no. 6 coal can be attributed to the differences in pore structure and/or chemical constitution of the two coal samples. Examination of the resultant solids by optical microscopy revealed the microstructural changes produced by thermal treatment in dilatometer experiments.     

Adhesive bonding of stainless steel water tubing

The use of an adhesive to bond stainless steel water tubing, allowing stainless steel fittings to be employed, is considered and compared with the more conventional use of compression or capillary copper fittings together with a soft solder. Tests carried out to determine environmental effects on adhesively bonded stainless steel tubing suitable for domestic water supply, and the strengths of these joints, are described. It has been found that acrylic anaerobic adhesives are suitable for bonding tubing carrying cold water, the joints attaining superior strength to the copper-soldered ones; a reasonable degree of flexing can also be tolerated. It would appear that certain selected adhesives may also be used in joints carrying hot water.     

关于控制氯代烃的政策选择

本文分析了氯代烃的生产所引起的环境问题,并提出了减少氯代烃环境影响的政策选择的基本原则。     

The influence of branch length on the deformation and microstructure of polyethylene

The length and number of side chain branches have a profound influence on the microstructure and physical properties of polyethylene (PE). For a series of linear PE copolymers: environmental stress cracking resistance (ESCR), melting points, creep resistance and modulus, and equilibrium spherulite size were all found to increase with increasing branch length (methyl to hexyl) at a given density and molecular weight. It is proposed that (at a fixed molecular weight) branch length and branch concentration determine spherulite size and, consequently, spherulitic boundary areas, in which the dry crazing/voiding occurs during the incubation period of environmental stress cracking (ESC). At a fixed density, decreased spherulite size contributes to greater spherulite boundary slip and increased creep at low (less than 2 MPa) stresses.     

Light-sensitive elastomers modified by 4-(N-dimethylmaleimido)-benzenesulphenyl chloride

New light-sensitive polymers were prepared by modification of four different elastomers with 4-(N-dimethylmaleimido)-benzenesulphenyl chloride (DMI-BSCI). Polydienes modified by DMI-BSCI form block copolymers. These polymers show a strong increase of the glass transition temperature T_g whereby the T_g increase of modified poly(octenamer) is much smaller. Higher modified polydienes have two T_g. Modified poly(octenamers) show a melting temperature dependence T_m on the content of trans double bonds which is characteristic of statistical copolymers. The ratio of rate constants with which trans- and cis-structures in poly(octenamer) are occupied by DMI-BSCI, is

$\text{k}{}_{\mathrm{trans}}\text{k}{}_{\mathrm{cis}}\text{= 0.34}$

     

Optical properties of high-temperature heat-treated vitrinites

Three vitrinites (C = 80.0, 87.9 wt%, daf and 94.2 wt%, dmmf) have been heat-treated over the temperature range 1000–2400 °C in the presence of argon. The variation of morphological and optical properties of the heat-treated samples is studied systematically using reflected-light microscopy. An optically isotropic, highly reflecting material is formed on the surface of anisotropic particles of two of the vitrinites (C, 80 and 94.2 wt%) during semi-graphitization (1000–1400 °C), which decreases in extent with increasing temperature and is absent at the end of this stage. The development and subsequent disappearance of the isotropic material is probably due to the evolution of volatile matter and subsequent deposition of pyrolytic carbon during semi-graphitization. The continuous increase of bireflectance of these two vitrinite residues, with heat-treatment temperature, indicates progressive improvement in the ordering of the molecular structure. The reflectance of the heat-treated anthracitic vitrinite (C, 94.2 wt%), increases continuously whereas the reflectance of the heat-treated low-rank vitrinite (C, 80 wt% decreases slightly from a maximum during semi-graphitization. The third vitrinite (C, 87.9 wt%) does not develop an optically isotropic highly reflecting material on particle surfaces during semi-graphitization. However, this vitrinite softens during carbonization (25–1000 °C) producing a residue with a mosaictype anisotropic microstructure. The condition of polished surfaces prepared from residues of this vitrinite from the semi-graphitization to crystallization stages (1000–2300 °C) deteriorates, values of bireflectance and reflectance decrease continuously with increasing temperature. This appears to result from a reduction in the surface hardness of particles of this vitrinite residue resulting on transformation from two-dimensional ordering to three-dimensional graphitic ordering.     

Analysis of junction temperatures in high-power GaN-based LEDs

We presented the analysis of the incomplete conduction in bonding medium in high power GaN-based light-emitting diode (LED) packages. A numerical study was carried out with parametric model to understand the junction temperature variation due to bonding medium defects. Transient thermal measurement was performed to evaluate LED’s junction temperature. Thermal resistance from chip to lead frame was 20 K/W in our sample LED. It was suggested that only 60% of the surface area of the bonding medium was involved...     

改善钢桥面铺装层高温作用的有效措施

为了降低钢桥面铺装层内较高的温度,提高铺装材料使用性能,推迟桥面的早期破坏.采用有限元手段,以傅里叶传热定律为理论基础,根据气象部门提供的气象资料,对开放式钢箱梁及封闭式钢箱梁铺装层的温度场进行研究.结果表明:开放式箱梁可以降低桥面铺装层温度,降低高温持续作用时间,改变桥面铺装层高温的作用位置.     

大口径光学透镜瞬态温度场模拟

为考察热辐射效应对光学元件稳、瞬态温度场的影响,给出了考虑辐射和导热耦合换热情况下复杂几何结构光学透镜稳、瞬态热特性的适体坐标下离散坐标法.对喷管形和圆柱形介质进行计算并与其他方法比较表明,建立的适体坐标系下辐射与导热耦合换热计算方法精度较好.对两端为球缺中间为圆柱的大口径透镜内的辐射与导热耦合换热过程进行了数值模拟.计算结果表明,为了精确地预测半透明介质如透镜内的温度分布,应该考虑辐射与导热耦合作用,且应当考虑介质的光谱特性.