Alternative view of anodic surface oxidation of noble metals

The idea of underpotential oxidation of water, taking place on the surface of noble metals in the range of potentials preceding molecular oxygen evolution, is more than 40-years old. Chemisorbed oxygen atom—O_chem is considered to be the main intermediate in the underpotential oxidation of H₂O, leading eventually to chemical oxidation of noble metals and formation of anhydrous surface oxides of MeO type. This concept is still used for the evaluation of the real surface area of the noble metal electrodes and also for the interpretation of new experimental results.The existence of reversible metal-oxide electrodes demonstrated experimentally for Pt, Pd, Rh, Ir and Au electrodes, oxidized anodically in the range of potentials preceding O₂ evolution, shows that noble metals do have electrochemistry of their own. Nanometric layers of amorphous, slightly soluble hydroxides, hydrous oxides or oxides can form electrochemically on the electrode surface during the anodic process and be reduced during the cathodic one. Such alternative concept admits the reversibility of anodic and cathodic processes and changes essentially the understanding and interpretation of the phenomena of anodic oxidation of noble metals.     

Resistivity and thermal reproducibility of carbon black and metallic powder filled silicone rubber heaters

Flexible heaters were prepared by extruding platinum‐catalyzed silicone rubber composites with conductive carbon black (CB) and metallic fillers. The conductor resistivity of the extruded heaters decreased in order of conductive titanium dioxide (TiO₂) > aluminum powder ≈ zinc powder > copper powder. Thermoelectric switching phenomena were investigated for the silicone rubber/CB/metallic powder systems. The positive temperature coefficient effect was dependent mainly on the CB content rather than on the content of the metallic powders. Resistivity and thermal reproducibility of the extruded heaters were also investigated by periodically applying AC voltage of 110 V. The heaters containing copper and TiO₂ powders exhibited excellent electrical reproducibility. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1122–1128, 2005     

Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.     

Viscoelastic Effects in a Phosphate Glass-Metal Seal

A family of phosphate glasses has been developed with thermal expansion behavior in the elastic range that nearly matches the response of 304 stainless steel. Attempts to make concentric pin-shell seals consistently have yielded fractures between 400° and 300°C during cooling. Elastic stress analyses which neglect glass transitional behavior and utilize constant glassy ("elastic") thermal expansion coefficients predict a residual stress state that is compressive. However, viscoelastic computations which include the effects of structural relaxation during glass transtion show that tensile stresses sufficient to cause failure arise during cooldown of the seal.     

Effect of the use of mineral filler on the properties of concrete

Engineers of the concrete technology are increasingly concerned with the material passing through a sieve of the size under 0.149 mm. Materials called very fine aggregate or mineral filler may affect the performance of concrete in an either positive or a negative way. Discussions on aggregate containing very fine material are vitally important. Washing the aggregate residue has been the sole way to solve this matter to date. This is mainly based on the debatable opinion that materials of this kind are regarded as clay material. The goal of the study was to determine how the content of mineral filler might affect properties of concrete. Two types of aggregates with different amounts of cement and mineral filler were used. Basically, mineral filler replaced sand. The effect of applying different amounts of mineral filler on concrete was then determined. The addition of 7-10% of mineral filler to fine aggregate (0-2 mm) was found to considerably improve the properties of concrete.     

填料对反-1,4-聚异戊二烯性能的影响

研究了填料对反－1，4－聚异戊二烯（TPI）硫化胶和混炼胶的物理机械性能和结晶性能的影响。结果表明，在TPI中加入填料后，其硫化胶的300％定伸应力随填料用量的增加而增加，拉伸强度则在填料用量为20份时达到最大值；加入填料同时能降低TPI混炼胶的结晶度，填料用量增加，TPI混炼胶的结晶下降；且填料增强效果越好，结晶度下降越大。     

Investigation of allyl‐capped carbosilane dendrimers used as crosslinker for silicone rubber

High‐temperature vulcanized silicone rubber was prepared by using allyl‐capped carbosilane dendrimers, in which the core molecules were Si(CH₂CH?CH₂)₄ and Ph₂Si(CH₂CH?CH₂)₂ as crosslinker and nanoscale reinforcing filler, respectively. Allyl‐capped carbosilane dendrimers improved the mechanical properties of silicone rubber. The optimum tensile strength and tear strength were 9.6 MPa and 31.0 kN/m, respectively, when using SiG_n(allyl)m as the crosslinker and 10.1 MPa and 32.0 kN/m, respectively, when using Ph₂SiG_n(allyl)m as the crosslinker. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1772–1775, 2006     

Effect of alkali and alkaline earth metals on nitrogen release during temperature programmed pyrolysis of coal

Formation of HCN, NH₃, and N₂ during fixed-bed pyrolysis at 10K min⁻¹ has been studied using coal samples after partial demineralization followed by addition of metal hydroxides from aqueous systems. Without additives, NH₃ is the predominant product at ≤ 700°C, showing the two peaks in the formation rate profile, whereas N₂ is the only product at ≥ 800°C. The presence of NaOH, KOH and Ca(OH)₂ promotes considerable NH₃ formation between 450 and 600°C, but in contrast suppresses HCN formation in this region. The Ca shows the largest effect on both the promotion and suppression. It is likely that the NH₃ increased by Ca addition arises partly from HCN, but mainly from secondary reactions of tar-N. These hydroxides affect N₂ formation in quite different manners: the Na decreases the rate between 700 and 950°C, and the K changes it less significantly than the Na, but the Ca remarkably increases the rate in a low temperature region of 550–700°C. These different features are discussed in terms of solid-phase reactions of alkali metal carbonates with char-N and secondary decomposition reactions of tar-N on CaO particles. As a result, total conversion of coal-N to HCN, NH₃ and N₂ up to 1000°C increases in the sequence of Na < none < K < Ca.     

CacO3在PP和PP/mPE共混物基体中的作用比较

研究CaCO3填料在取丙烯（PP）和茂金属聚乙烯（mPE)弹性体增韧PP共混物（PP／mPE)2种基体中的不同作用。结果表明：在PP基体中，填料显著提高其刚性，而在共混物基体中，由于弹性体的存在，填料的增强作用减弱；弹性体能够改善填料粒子和基体的界面粘合，增大弹性体分散相的尺寸，使PP/mPE共混物的拉伸断裂韧性提高。低温下（－30℃）的Charpy缺口冲击实验表明：少量的CaCO3即可导致PP/mPE体系冲击强度的迅速下降。     

炭黑填充硬聚氯乙烯的改性

为使聚氯乙烯具有抗静电性能,采用加入具有导电性填料的方法,但加入大量的填料,会使硬聚氯乙烯的冲击性能降低,加工性能变差。本文是在以炭黑为填料的基础上,研究不同的改性剂和加工助剂改进硬聚氯乙烯的效果,结果表明,加入冲击改性剂和加工助剂后,大大增加了硬聚氯乙烯的冲击强度,且加工性能也得到改善,同时由于炭黑具有补强效果,其拉伸强度和弯曲强度在加入改性剂后也能满足使用要求。