KINETIC-STUDY OF ELECTROCATALYTIC REDUCTION OF HYDROGEN-PEROXIDE AT IRON(III) PORPHYRIN MODIFIED GLASSY-CARBON ELECTRODE IN ALKALINE-MEDIUM USING THE ROTATION-SCAN METHOD

Reduction of hydrogen peroxide at a glassy carbon (GC) electrode modified with sigma-bonded pyrrole iron(III) octaethylporphyrin complex, (OEP)Fe(Pyr), was studied by cyclic voltammetry and a rotating disk electrode. In 0.1N NaOH solution, it is shown that such an (OEP)Fe(Pyr)/GC electrode has a significant catalytic activity towards hydrogen peroxide reduction (E(D) = -0.80 V, k = 0.066 cm s(-1)); however, the electrode stability is low. The deactivation is observed when the reaction charge (Q) is passing through the (OEP)Fe(Pyr)/GC disk electrode. A linear rotation scan method is applied to study the kinetic process by determining the disk electrochemical response (i(D)) to rotation rate (omega) at a definite disk potential (E(D)). Considering that the number of adsorbed electroreduced catalyst molecules (Red) varies according to the disk potential, a factor theta(= Gamma(Red)/(Gamma(Red) + Gamma(Ox))) is introduced to describe the electrode surface area fraction for electroreduced species. The obtained Koutecky-Levich equation is applicable whatever the potential is.

MEDIATORLESS HYDROGEN-PEROXIDE ELECTRODE BASED ON HORSERADISH-PEROXIDASE ENTRAPPED IN POLY(O-PHENYLENEDIAMINE)

A mediatorless H2O2 sensor based on coelectropolymerization of horse radish peroxidase (HRP) and o-phenylenediamine (o-PD) is described. The electrode responds to H2O2 in a few seconds and gives a current density of 73.3 nA 1 mu mol(-1) cm(-2) at -100 mV

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF BENZOYL PEROXIDE - A RADICAL AROMATIC-SUBSTITUTION RESULTING IN BIPHENYLCARBOXYLIC ACID IN THE GAS-PHASE

A radical aromatic substitution resulting in biphenylcarboxylic acid is inferred for the decomposition of benzoyl peroxide from the chemical ionization and collision-induced dissociation mass spectra. The thermolysis of benzoyl peroxide gives rise to a benzoyloxy radical, which undergoes rapid decarboxylation and hydrogen abstraction leading to phenyl radical and benzoic acid, respectively. Attack of the resulting phenyl radical on the benzoic acid results in bipbenylcarboxylic acid. On the other hand, the phenyl radical abstracts a hydrogen atom to yield benzene, which is then subjected to the attack of a benzoyloxy radical, affording phenyl benzoate. This substitution reaction rather than the recombination of benzoyloxy and phenyl radicals is found to be responsible for the formation of phenyl benzoate under the present conditions.

Electrochemical measurement of hydrogen peroxide in plasma: Evaluation of freshwater prawn (Macrobrachium rosenbergii) and crucian carp (Cyprinus carpio) phagocytes under natural conditions

An electrochemical technique for the real-time detection of hydrogen peroxide (H2O2) was employed to describe respiratory burst activity (RBA) of phagocytes in plasma which can be used to evaluate the ability of immune system and disease resistance. The method is based upon the electric current changes, by redox reaction on platinum electrode of extracellular hydrogen peroxide (H2O2) released from phagocytes stimulated by the zymosan at 680 mV direct current (d.c.). Compared with the control, activation of respiratory burst by zymosan particles results in a high amperometric response, and a current peak was obtained during the whole monitoring process. The peak current was proved by addition Of Cu2+ and other controls, to be the result of intense release of H2O2 from phagocytes. The peak area was calculated and used to evaluate the quantity of effective H2O2, which represents the quantity of H2O2 beyond the clearance of related enzymes in plasma. According to Faraday's law, the phagocytes' ability of prawns to generate effective H2O2 was evaluated from 1.253 x 10(-14) mol/cell to 6.146 x 10(-14) mol/cell, and carp from 1.689 x 10(-15) Mol/Cell to 7.873 x 10(-1)5 mol/cell. This method is an acute and quick detection of extracellular effective H2O2 in plasma and reflects the capacity of phagocytes under natural conditions, which could be applied for selecting species and parents with high immunity for breeding in aquaculture. (c) 2007 Elsevier Ltd. All rights reserved.

Reaction-controlled phase transfer catalysis for styrene epoxidation to styrene oxide with aqueous hydrogen peroxide

The epoxidation of styrene catalyzed by a reaction-controlled phase transfer catalyst [(C18H37(30%)+C16H33(70%))N(CH3)(3))(3)](3)-[PW4O16] with H2O2 in a biphasic medium was investigated. Under certain conditions, the selectivity for styrene oxide was 95%, the conversion of styrene based on H2O2 was 85%, and the reaction time was less than 1 h. During the reaction, this catalyst powder formed soluble active species by the action of H2O2, was recovered as a precipitate, and was reused after H2O2 was used up. After two times recycling, the catalyst kept almost the same activity.

K418与42CrMo异种金属的激光穿透焊接

实验研究了连续波Nd：YAG激光焊接速度、侧吹保护气流量和离焦量等参量对激光穿透焊接K418和42CrMo焊缝成形的影响。结果表明，K418与42CrMo激光穿透焊接有X形和T形两种典型的焊缝形貌，且焊缝形貌是不对称的。随着焊接速度的提高，焊接线能量降低，焊缝尺寸变小，且焊缝上部尺寸变化比下部尺寸变化慢，焊缝形貌由X形过渡到T形。当离焦量在瑞利长度范围内时，焊缝正面宽度变化很小；当离焦量超出瑞利长度范围时，在足够高的激光功率密度下，焊缝正面宽度快速增加。在激光功率为3kW，侧吹保护气角度为35°条件下，通过优化焊接速度、侧吹保护气流量和离焦量等参量可以得到最佳焊缝质量。

Mechanism on Progressive Failure of a Faulted Rock Slope Due to Slip-Weakening

Slip-weakening is one of the characteristics of geological materials under certain loadings. Non-uniform rock structure may exist in the vicinity of the slip surface for a rock slope. Some portion of the slip surface may be penetrated but the other not. For the latter case, the crack or the fault surface will undergo shear deformation before it becomes a successive surface under a certain loading. As the slipped portion advances,slip-weakening occurs over a distance behind the crack tip. In the weakening zone, the shear strength will decrease from its peak value to residual friction level. The stress will redistribute along the surface of crack and in the weakening zone. Thus the changed local stress concentration leads the crack to extend and the ratio of penetration of the slip surface to increase. From the view of large-scale for the whole slip surface, the shear strength will decrease due to the damage of interior rock structure, and the faulted rock behaves as a softening material. Such a kind of mechanism performs in a large number of practical landslides in the zones experienced strong earthquakes. It should be noted that the mechanism mentioned above is different from that of the breakage of structural clay,in which the geological material is regarded as a medium containing structural lumps and structural bands. In this paper, the softening behavior of a faulted rock should be regarded as a comprehensive result of the whole complicated process including slip-weakening, redistribution of stress, extension of crack tip, and the penetration of the slip surface. This process is accompanied by progressive failure and abrupt structural damage. The size of slip-weakening zone is related to the undergoing strain. Once the relative slide is initiated (local or integrated), the effect of slip-weakening will behave in a certain length behind the crack tip until the formation of the whole slip surface.

静力触探锥头阻力的近似理论与实验研究进展

锥头阻力在静力触探试验中扮演着十分重要的角色．从不同角度，对触探中锥头阻力的研究进行简要阐述，对承载力理论、空洞膨胀理论、应变路径法及运动点位错法等几种理论分析方法进行了回顾．另外，对数值分析和实验研究的进展情况进行了叙述．并对各种方法的适用性进行了比较．承载力理论虽然简单，但忽略了土的压缩性和探杆周围初始应力的增加，所以不能精确地模拟锥头的深层贯入．空洞膨胀理论提供了一个分析锥头阻力的简单而较精确的方法，它考虑了土的压缩性(或膨胀性)和锥头贯入过程中锥杆周围应力增加的影响．但这种方法是将锥头贯入与空洞膨胀之间做了一个等效模拟，所以不同的模拟方法，得到的结果差别较大．应变路径法能够有效解决饱和粘土中的不排水贯入，但不适用于砂土．运动点位错法因为考虑了部分排水，所以能较好地预测固结系数，但采用了线弹性分析，故位错法在其他方面的应用还需要大量的试验验证．有限元法在处理锥头贯入这类慢侵彻问题时缺乏一种很好的处理技术，导致它在进行破坏荷载计算时有显著的误差和数值计算困难．标定槽试验将在验证和建立锥头阻力与土的性能关系方面继续起到一个重要作用，但其结果需经过校正后才可应用到现场．最后对该领域的研究趋势进行了讨论．

Research on laser welding of cast Ni-based superalloy K418 turbo disk and alloy steel 42CrMo shaft

Exploratory experiments of laser welding cast Ni-based superalloy K418 turbo disk and alloy steel 42CrMo shaft were conducted. Microstructure of the welded seam was characterized by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive spectrometer (EDS). Mechanical properties of the welded seam were evaluated by microhardness and tensile strength testing. The corresponding mechanisms were discussed in detail. Results showed that the laser-welded seam had non-equilibrium solidified microstructures consisting of FeCr0.29Ni0.16C0.06 austenite solid solution dendrites as the dominant and some fine and dispersed Ni3Al gamma' phase and Laves particles as well as little amount of MC short stick or particle-like carbides distributed in the interdendritic regions. The average microhardness of the welded seam was relatively uniform and lower than that of the base metal due to partial dissolution and suppression of the strengthening phase gamma' to some extent. About 88.5% tensile strength of the base metal was achieved in the welded joint because of a non-full penetration welding and the fracture mechanism was a mixture of ductility and brittleness. The existence of some Laves particles in the welded seam also facilitated the initiation and propagation of the microcracks and microvoids and hence, the detrimental effects of the tensile strength of the welded joint. The present results stimulate further investigation on this field. (c) 2006 Elsevier B.V. All rights reserved.