From surface science to catalysis: Surface “explosions” observed on Rh crystals and supported catalysts

Phenomena called surface explosions have been reported for decomposition reactions on single crystals, and have been identified by the use of desorption methods. In particular, in TPD, they are manifested by extremely narrow peaks (as little as 3 K in width) and a desorption rate which increases with time in isothermal experiments. In this paper we report such observations for acetate species on Rh single crystals, but extend this to show for the first time that such effects are not restricted to single crystal/UHV experiments, but can also be found on a Rh/Al₂O₃ catalyst under ambient pressure conditions. These reactions can be classified as second order autocatalytic surface processes, where free surface Rh sites are an essential component of the reaction. It is shown that coadsorbed adatoms are also essential for such explosions to be seen and their role is proposed to be that of a template layer acting to order the acetate in self-poisoning configurations.     

Pressureless low temperature sintering of nanocrystalline zirconia ceramics via dry powder processing

Pressureless sintering approaches provide a simple avenue to manufacture dense ceramic parts with minimal processing equipment, but current pressureless sintering techniques have yet to demonstrate capabilities of producing dense ceramics while maintaining sub-50 nm grain sizes. Nanocrystalline yttria stablized zirconia ceramics were process from 4 mol% yttria stablized zirconia (4YSZ) nanopowders with a crystallite size of 7.5 nm using dry cold isostatic pressing (CIP) where powders are dried immediately prior to green compact formation and CIP vacuum bagging. It is shown that CIP pressures >75 000 psi (517 MPa) effectively remove pores larger than 100 nm and that pressureless sintering occurs at reduced temperatures for green densities ≥50%. Though the sintering kinetics are shown to be similar to other zirconia nanopowder sintering studies, the small initial crystallize size and reduced sintering temperature allowed densities as high as 97.2%, while retaining a ceramic grain size at or below 40 nm. Produced nanocrystalline 4YSZ ceramics with a grain size of 30.3 nm and a density of 96.3% had Vicker's hardnesses as high as 14.2 GPa and Vicker's indentation fracture resistance of 3.43 MPa·, demonstrating that simple processing approaches can be refined to fabricate nanocrystalline ceramics while maintaining high hardness and indentation fracture resistance.     

A Thermo-Mechanical Study of Some Epoxy Adhesives Subjected to Combined Dynamic and Static Stresses

The object of the present study was to investigate the effect of superimposed dynamic and static stresses on mechanical and thermal properties of some epoxy adhesives. It was found that combinations of shear creep and torsional oscillations, applied simultaneously to adhesive joints at temperatures within the glassy range of the adhesive, led to strengthening of the joints in shear and to an increase in the glass transition temperature of the adhesive. Similar loading stresses applied at temperatures close to the T_g of the adhesive, led to opposite effects on the above mentioned properties of the joints. The width of the glassy-rubbery transition of the adhesives increased, in the whole range of temperatures used in this study and for all epoxy compositions, as a result of subjecting the joints to superimposed dynamic and static stresses. The broadening of the glass transition was interpreted as a result of the stiffening of polymer network during the combined stressing experiments. A linear relationship was found between the area of endothermal peaks in the first DSC scan of specimens subjected prior to test to superimposed dynamic and static stresses at temperatures below T_g, and the shear strength of the joints. In agreement with this observation and with literature data, a linear relationship was revealed also between the glass transition temperature of the resins (measured in the first DSC scan) and the shear strength of the joints. Based on experimental observations and on some literature information, it was suggested that the strengthening of the joint, as well as the changes in thermal properties of the adhesives, are mainly due to physical processes, such as short-range orientation of network chains and an increase in intermolecular interaction between highly polar sites of the network. The possibility that superimposed stressing led to changes in chemical crosslinking was discussed but it seems that no such reactions occurred.     

Reprint of “Suppressing propylene carbonate decomposition by coating graphite electrode foil with silver”

A method has been developed to suppress the decomposition of propylene carbonate (PC) by coating graphite electrode foil with a layer of silver. Results from electrochemical impedance measurements show that the Ag-coated graphite electrode presents lower charge transfer resistance and faster diffusion of lithium ions in comparison with the virginal one. Cyclic voltammograms and discharge-charge measurements suggest that the decomposition of propylene carbonate and co-intercalation of solvated lithium ions are prevented, and lithium ions can reversibly intercalate into and deintercalate from the Ag-coated graphite electrode. These results indicate that Ag-coating is a good way to improve the electrochemical performance of graphitic carbon in PC-based electrolyte solutions.     

Experimental study on temperature stress calculation and temperature control optimization of concrete based on early age parameters

Temperature control curve is the key to achieving temperature control and crack prevention of high concrete dam during construction,and its rationality depends on the accurate measurement of temperature stress.With the simulation testing machine for the temperature stress,in the present study,we carried out the deformation process tests of concrete under three temperature curves：convex,straight and concave.Besides,we not only measured the early-age elastic modulus,creep parameters and stress process,but also proposed the preferred type.The results show that at early age,higher temperature always leads to greater elastic modulus and smaller creep.However,the traditional indoor experiments have underestimated the elastic modulus and creep development at early age,which makes the calculated value of temperature stress too small,thus increasing the cracking risk.In this study,the stress values of the three curves calculated based on the strain and early-age parameters are in good agreement with the temperature stress measured by the temperature stress testing machine,which verifies the method accuracy.When the temperature changes along the concave curve,the law of stress development is in consistent with that of strength.Under this condition,the stress fluctuation is small and the crack prevention safety of the concave type is higher,so the concave type is better.The test results provide a reliable basis and support for temperature control curve design and optimization of concrete dams.     

Intergranular oxidation of silicon in 20Cr-25Ni niobium-stabilized stainless steel at 1140–1230 K

The kinetics of intergranular oxidation of silicon in a 20Cr-25Ni Nb-stabilized stainless steel are reported, at temperatures in the range 1140–1230 K, in CO₂ at 40 bar pressure. The depth of attack increased parabolically with respect to time, with an activation energy of 335±30 kJ/mol. The mechanism of growth is discussed in terms of classical internal-oxidation theories, and an alternative explanation based on an available-space theory is developed. The internal oxidation rates in a number of different alloys are compared with diffusivities of metals in the base alloy. It is proposed that intergranular oxidation in the 20–25 Nb steel is controlled by the rate of outward diffusion of iron or chromium in the alloy.     

基于改进Kendall-f算法的发电机定子温度分析

在线监测发电机定子温度可有效发现定子部分过热性故障,如何从检测的温度数据中提取反映定子故障预警的信息是目前国内外研究的热点。该文采用可变窗改进Kendall-f算法处理监测温度数据,提取其变化趋势特征信息;采用偏度分析提取监测温度异常值,从而正确诊断定子过热性故障,仿真分析及实验结果表明该方法有效提高了定子温度监测与预警的准确率。     

Effects of coagulation bath temperature on structure and performance of poly （vinyl butyral） hollow fiber membranes via thermally induced phase separation

Poly （vinyl butyral） （PVB） hollow fiber membranes were fabricated via thermally induced phase separation （TIPS）. The effects of coagulation bath temperature （CBT） on the structure and performance of membranes were investigated in detail. The morphologies of the membranes were studied by scanning electron microscopy （SEM）, the performances of water permeability, rejection, breaking strength and elongation were measured, respectively. The results indicate that all the membranes have the asymmetric morphology and the thickness of the skin layer decreases and the pore size of the outer layer increases with the increase of CBT. The permeability of membranes prepared at air gap 1.0 cm and take-up speed 0.253 m/s increases from 1.047×10-7 to 5.909×10-7 m3/（m2·s-kPa） with the CBT increasing from 20 ℃ to 40℃, and sharply increases to 35.226×10 7 m3/（m2.s.kPa）once the CBT arrives at 50 ℃. While the carbonic ink rejections have no significant decrease, totally exceed 98%, but that of acid-maleic acid copolymer greatly decreases with the increase of CBT. Both the breaking strength and elongation decrease with the increase of CBT.     

Oxidation Performance of Fe-Al/WC Composite Coatings Produced by High Velocity Arc Sprayed at 650 ℃

Fe-Al intermetallics with remarkable high-temperatureintensity and excellent erosion,high-temperatureoxidation and sulfuration resistance are potential lowcost high-temperature structural material.ProducingFe-Al/WC composite coating by high velocity arcspraying(HVAS)on structural materials would notonly obviate the problems faced in fabrication of thesealloys into useful shapes,but also allow the effectiveuse of their outstanding high-temperature performance,which might thus promisingly mak…     

High-temperature oxidation of pure titanium in CO2 and Ar-10%CO2 atmospheres

The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO₂ or Ar-10%CO₂. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO₂) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.