Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds

The catalytic activity of fresh Pd and Pt catalysts supported on γ-alumina in the complete oxidation of CH₄ traces under lean-burn conditions was studied in the presence or the absence of water or H₂S. Steam-aged catalysts were also studied in order to simulate long-term ageing in real lean-burn natural gas fuelled vehicles (NGVs) exhaust conditions. Without water or H₂S added to the feed, Pd catalysts exhibit a superior catalytic activity in methane oxidation compared to Pt ones, whatever the catalysts were fresh or aged. The addition of 10 vol.% water vapour to the feed strongly affects the activity of the fresh Pd catalyst, thus being only slightly more efficient than the fresh Pt one. H₂S has a strong poisoning effect on the catalytic activity of Pd catalysts, while Pt catalysts are more resistant. The fresh H₂S-poisoned Pd/Al₂O₃ catalyst was studied by TPD in O₂/He. Poisoning species decompose above 873 K as SO₂ and O₂ in relative concentrations consistent with the decomposition of surface sulphate species. However, a treatment in O₂/He at temperatures as high as 923 K does not allow the complete regeneration of the catalytic activity of H₂S-poisoned Pd/Al₂O₃. A mechanism involving the poisoning of PdO by sulphate species is proposed. Different diffusion processes by which these sulphate species can migrate back and forth between PdO and the support, depending on the experimental conditions, are suggested.     

Possibilities and extension of XRD material response analysis in failure research for the advanced evaluation of the damage level of Hertzian loaded components

Due to clearly distinguishable damage symptoms, it is differentiated between the surface and sub‐surface failure mode of rolling bearings. Material states red out by X‐ray diffraction (XRD) residual stress measurements point to a variety of loading conditions especially at raceway surfaces that are associated with several competing failure mechanisms. The corresponding lifetime reduction can range from the lower fatigue strength region to material ratcheting in extreme cases. Relevant position of the microstructural changes and nature of the failure mechanisms are characterized. The time alteration of the XRD material parameters measured at or near the surface and at the depth of the maximum equivalent stress correlates, in a different manner, with the statistical parameter of the 10 % bearing life. Both failure modes are illustrated by concrete examples. Contaminated lubricant and boundary lubrication, which represent practically important surface‐induced failures, are discussed in more detail. Gray staining, i.e. shallow pitting, often occurs without distinct indication of global material aging by means of XRD characteristics. Here, scanning electron microscopy observations and electron microprobe analyses point to corrosion fatigue as acting surface failure mechanism. The interaction between material and lubricant under complex loading regimes particularly of mixed friction and corrosion opens further failure research areas in the field of tribology.     

Hydrogen absorption by Pd-coated ZrNi prepared by using Barrel-Sputtering System

To improve the durability of hydrogen storage materials against surface poisoning by impurity gases, effectiveness of Pd-coating layer prepared by using a Barrel-Sputtering System was examined for ZrNi powder. The effectiveness of Pd-coating was evaluated by activation temperature, at which Pd/ZrNi poisoned by air could be activated to absorb hydrogen. Characterization of Pd-coated ZrNi (denoted as Pd/ZrNi) by scanning electron microscopy, electron probe microanalysis and X-ray diffraction showed that a uniform Pd-coating layer was formed with the barrel-sputtering system. It was found that the poisoned Pd/ZrNi sample could be activated even at 423 K to absorb hydrogen at room temperature. This exhibits remarkable contrast to bare ZrNi, which could be only activated appreciably above 1073 K. It is concluded that the Pd-coating by barrel sputtering is quite effective to avoid the effect of surface poisoning of powdery hydrogen storage materials. However, the activation at excessively high temperature resulted in the loss of high activity to absorb hydrogen. It was concluded that this phenomenon was associated with reactions between Pd and ZrNi to form PdZr and other byproducts.     

Phenol novolac/poly(4- hydroxyphenylmaleimide) blend hardeners for DGEBA-type epoxy resin

Phenol novolac/poly (4-hydroxyphenylmaleimide) (PHPMI) blends were used as an epoxy resin hardener. The curing behavior of the above system and the thermal and mechanical properties of the cured epoxy resin were studied. It was not necessary to use a curing accelerator for this system, because PHPMI caused acceleration of the curing reaction. The curing mechanism of this system was investigated by using model compounds. Test pieces from the neat resins and the glass fiber reinforced resins were evaluated in terms of thermal and mechanical properties, respectively. It was found that heat resistance and mechanical properties were improved by increasing the amount of PHPMI in the hardener.     

Observation of atomic steps on CaCO3 crystal surface

By using scanning polarization force microscopy,the deliquescence process and the atomic steps on the cleavage surface of CaCO3 in air were studied in situ.Under an exposure to medium umidity(-57%),the sloiw step movement has been observed.     

Gildes model studies of aqueous chemistry. III. Initial SO2-induced atmospheric corrosion of copper

The GILDES computer model, incorporating Stumm's concept of proton- and ligand-promoted dissolution, has been used to simulate the exposure of copper at room temperature to 210 ppb sulfur dioxide and 80% relative humidity. The agreement is good between the calculations and laboratory exposures performed under these exposure conditions. Surface reactions are relatively more important at lower relative humidities and the dominant corrosion products formed are solid state Cu₂SO₃, CuSO₃ and Cu₂U. Free-radical redox processes are important participants and control the relative distribution of Cu(I)- and Cu(H)-containing corrosion products.     

COIL中BHP浓度对发生O_2(~1△)的影响

本文实验研究了BHP的浓度对产生O2（1△）的影响。实验结果表明：当BHP浓度大于3.5M时，Cl2利用率以及O2（1△）的产率将不依赖于BHP浓度的变化而变化，同时，实验结果表明，使用低浓度的BHP对COIL的操作是可行的。     

Evolution of BET internal surface area in glassy carbon powder during thermal oxidation

It is demonstrated that glassy carbon powder can be thermochemically activated. During activation, a film with open pores is created on the glassy carbon particles. This film has a large internal surface area, which is accessible to liquids and gases. A simple model for the evolution of the internal surface area in glassy carbon powder during thermochemical gas-phase oxidation is also presented and compared with experimental data. Experimental results are in qualitative agreement with the model. We found that a sharp particle size distribution is desirable with regard to potential technical applications.     

Immobilization of an endopectinlyase on γ-alumina: Study of factors influencing the biocatalytic matrix stability

Endopectinlyase (EC 4.2.2.10) from Aspergillus japonicus was immobilized on to γ-alumina. Adsorption performed at pH 5·0 and a subsequent cross-linking phase using 0·1% glutaraldehyde were the chosen immobilization conditions. The comparison between the main biochemical parameters of the immobilized and free form of the enzyme showed that the immobilization procedure used did not affect the enzyme biochemical properties. The interactions between the carrier and the enzyme are essentially secondary bonding. In fact they depend on the pH and on the presence of phosphate ions in the medium. A tentative chemical model of the biocatalytic matrix thus obtained is proposed.     

Electrical characterization of porous BaTiO3 using impedance spectroscopy in humid condition

The humidity response characteristics of La doped BaTiO₃ with different sintered densities and room temperature electrical conductivities were investigated using complex impedance measurement. The samples with low density and high resistivity showed the large and nearly linear sensitivity to the change of humidity. The impedance spectra of samples, when exposed to high humidity, can exhibit microstructure-related features, even though they do not give rise to a noticeable characteristic change when exposed to low humidity. The observed impedance patterns were dependent upon the density, and hence the oxidation kinetics of BaTiO₃.