Passive and transpassive behaviour of CoCrMo in simulated biological solutions

In this work, the behaviour of a CoCrMo alloy under simulated body conditions was investigated. More specifically, the electrochemical properties of the alloy and the relevant mechanisms in the passive and transpassive states were studied in detail. Electrochemical techniques such as potentiodynamic and potentiostatic polarisation, cyclic voltammetry, rotating disc electrode and electrochemical impedance spectroscopy were employed. Further, ex situ X-ray photoelectron spectroscopy analysis of the passive films was carried out. A good correlation between the results obtained from all the experimental techniques was achieved. Overall, it was found that the passive film on CoCrMo changed in composition and thickness with both potential and time. The passive behaviour of the CrCrMo alloy is due to a formation an oxide film highly enriched with Cr (≈90% Cr oxides) on the alloy surface. The passive and transpassive behaviour of the alloy is hence dominated by the alloying element Cr. In the transpassive region, strong thickening of the oxide film takes place, combined with a change in the composition of the film, and strongly increased dissolution rate. In the transpassive region, all alloying elements dissolve according to the composition of the alloy. The metal ion release is also very strongly enhanced by cyclic variation of the potential between reducing and oxidizing conditions. In this case, during activation/repassivation cycles, cobalt dissolution is greater than expected from the composition of the alloy. Therefore, active dissolution behaviour is mainly dominated by the alloying element Co.     

不同预处理条件下纤维素的结构变化及其在DMAc／LiCI中的溶解

介绍了乙二胺、氢氧化钠和高温等三种不同的纤维素预处理方法。研究预处理后纤维素的结构变化，讨论预处理过程中的转化机理，并通过X射线衍射对纤维素结晶度的变化进行表征，证明乙二胺预处理后纤维素的结晶度下降最大。纤维素经过预处理后可以溶解在DMAc／LiCI中，讨论其溶解机理，通过对比三种预处理纤维素的溶解性能，表明经过乙二胺预处理之后的纤维素在DMAc／LiCI中溶解性能最好，氢氧化钠预处理的纤维素次之，高温预处理的纤维素溶解性能相对较差。     

Nature of PMMA dissolution process by mixtures of acetonitrile/alcohol (poor solvent/nonsolvent) monitored by FTIR-imaging

The dissolution process of poly(methyl methacrylate), PMMA, in mixtures of the binary systems: acetonitrile/alcohol (methanol, ethanol and 1-propanol), individually poor and nonsolvents respectively for the polymer, was studied at 25 °C using FTIR imaging spectroscopy. To investigate this cosolvency phenomenon and the kinetics of the dissolution process, the spatial resolution and sensitivity of FTIR imaging were used. It has been found that the PMMA dissolution rate anomalously increases almost in a parabolic way independently of the solvent system used in this study. These results were interpreted assuming that the dissolution of a polymer by a mixture of solvents is governed by a complex dependence of the solvent molecules size and their thermodynamic characteristics. The kinetics of the PMMA dissolution by AcN/alcohol solvent mixtures were interpreted using conventional Arrhenius behavior in which the activation energy has a simple dependence on the thermodynamic quality and the molecular weight of the solvent mixture.     

Development and evaluation of an improved soil test for phosphorus: 1. The influence of phosphorus fertilizer solubility and soil properties on the extractability of soil P

The objective of this work was to develop and evaluate a soil test suitable for estimating the phosphorus status of soils whether they were fertilized with soluble or sparingly soluble P fertilizers or both. Four New Zealand soils of contrasting P sorption capacity and exchangeable Ca content were incubated alone or with monocalcium phosphate (MCP), reactive North Carolina (NC) phosphate rock or unreactive Florida (FRD) rock, at 240 mg P kg^–1 soil, to allow the P sources of different solubilities to react with each soil and provide soil samples containing different amounts of extractable P, Ca and residual phosphate rock. The phosphorus in the incubated soils was fractionated into alkali soluble and acid soluble P fractions using a sequential extraction procedure to assess the extent of phosphate rock dissolution. Eight soil P tests [three moderately alkaline — Olsen (0.5M NaHCO₃) modified Olsen (pretreatment with 1M NaCl) and Colwell; three acid tests — Bray 1, modified Bray 1 and Truog; and two resin tests — bicarbonate anion exchange resin (AER) and combined AER plus sodium cation exchange resin (CER)] were assessed in their ability to extract P from the incubated soils.The 0.5M NaHCO₃ based alkaline tests could not differentiate between the Control and FRD treatments in any soil nor between the Control, NC and FRD treatments in the high P sorption soils. The acid extractants appeared to be affected by the P sorption capacity of the soil probably because of reabsorption of dissolved P in the acid medium. The AER test gave results similar to Olsen. Only the combined AER + CER test extracted P in amounts related to the solubility of the P sources incubated with each soil. Furthermore, when soil samples were spiked with FRD and NC and extracted immediately, the P extracted by the AER + CER test, over and above the control soils, increased with the amount and chemical reactivity of the rocks. There was no extraction of rock P by any of the alkaline extractions.Increases in the amounts of P extracted (P) by each soil test from the fertilized soils, over and above the control soils were compared with the amounts ofP dissolved from the fertilizers during incubation (measured by P fractionation). Soil P sorption capacity had least influence on the amounts of P extracted by the AER + CER and Colwell tests. However, the Colwell test was unable to differentiate between all P sources in all four soils and suffered from the disadvantage of producing coloured extracts. The AER + CER test appeared to have the potential to assess the available P status of soils better than the other tests used because of its ability to extract a representative portion of residual PR (in accordance with the amount and reactivity) and dissolved P, and thus to differentiate between fertilizer treatments in all four soils.     

P_2O_5影响Na_2O-B_2O_3-SiO_2系玻璃结构与性质的特殊性

本文通过不混溶温度的确定,分相玻璃沥滤速率的测定以及NMR定量分析,研究了P_2O_6对Na_2O-B_2O_3-SiO_2系统玻璃结构和沥滤性质的影响。结果表明,P_2O_5在很大程度上促进钠硼硅分相玻璃的沥滤并非压抑“硼反常”所致,而是由以下三种因素综合作用的结果:(1)P_2O_5促进了钠硼硅玻璃的分相,使连通富硅相骨架尺寸增大;(2)P_2O_5的加入使富硅相骨架间隙中沉积的SiO_2量减少,减小了可溶相扩散阻力;(3)P_2O_5也使可溶相的溶解速率加快。     

Electrocatalytic oxidation of ethanol on Pt–Mo bimetallic electrodes in acid medium

Pt–Mo alloy electrocatalysts were prepared by an arc-melting furnace process to investigate the origin of their enhanced activity toward ethanol oxidation. Two Mo contents were chosen in zones of the binary phase diagram where they are supposed to form either a pure alloy mixture or a solid solution. Pt–Mo alloy catalysts were more active than Pt-alone. Gradual Mo dissolution at the electrode surface was observed after voltammetric and chronoamperometric measurements. The dissolved Mo contributed to the catalytic effect of the electrode as underpotentially deposited (upd) adatoms. This dissolution probably also leads to an increase in the electrode surface roughness. Low molybdenum content in the electrode material enhances the activity toward ethanol oxidation when compared to Pt-alone. Ethanol oxidation was also investigated by in situ infrared reflectance spectroscopy in order to determine the presence of adsorbed intermediates like CO species. Acetaldehyde, acetic acid and CO₂ were also found by spectroscopic experiments.     

Mechanistic investigation of hydrogen-enhanced anodic dissolution of X-70 pipe steel and its implication on near-neutral pH SCC of pipelines

The effects of hydrogen-charging on anodic dissolution of pipe steel under near-neutral pH condition were studied by electrochemical techniques. Hydrogen-charging enhances the anodic dissolution rate of the steel. The hydrogen-enhanced dissolution increases with increasing charging current density. The hydrogen effect is attributed to the alteration of chemical potential and exchange current density of steel. Hydrogen-charging affects the corrosion process of the steel. In particular, at a high charging current density, a layer of corrosion product forms on the electrode surface to change corrosion potential and interfacial double-charge layer capacitance as well as charge-transfer resistance. The hydrogen effect factor for enhanced anodic dissolution of steel at an anodic potential of −0.4 V (SCE) is 1.53 only. Hydrogen-enhanced anodic dissolution of steel by itself may not be the major factor contributing to the high rate of crack growth in pipe steel in near-neutral pH electrolyte. A further investigation of the synergistic effect of hydrogen and stress on dissolution at the crack-tip is essential to determine the mechanism of near-neutral pH stress corrosion cracking of pipelines.     

盐酸小檗碱-环糊精包合物的体外溶出度研究

目的探讨包合技术对中药制剂体外溶出度以及缓释作用的影响。方法选用饱和溶液法生成包合物 ,用DSC证明包合物的生成 ;采用分光光度法 ,考察盐酸小檗碱包合物的体外溶出度和缓释作用。结果 β CD·BH、RM β CD·BH和BH的T50 、Td分别为 5 69.8,740 .2min ;73 .7,10 7.0min和 19.6,2 5 .5min ,包合物的释药数据与t作线性回归方程为 :Y =0 .0 63 9t -0 .473 8,Y =0 .5 5 64t+5 .65 8。结论RM β CD·BH和 β CD·BH的溶出速率明显慢于BH ,具有一定的缓释作用 ,同时RM β CD·BH较β CD·BH具有更好的生物利用度 ;β CD·BH和β CD·BH的体外溶出度与t为一相关性良好的线性方程 ,符合零级释药方程。     

An electrochemical study of the dissolution of gold in thiosulfate solutions. Part II. Effect of Copper

Thiosulfate has been considered as one of the most promising of the non-toxic alternatives to cyanide for the leaching of gold and much work has been carried out with the aim of understanding and improving the ammoniacal thiosulfate leaching process. In particular the behaviour of gold in thiosulfate solutions containing copper in the absence of ammonia has received little attention. It has been shown in this study involving electrochemical and leaching tests that copper ions catalyze not only the oxidation of thiosulfate but also the dissolution of gold in alkaline thiosulfate solutions. Electrochemical studies have shown that copper has a positive effect on the anodic dissolution of gold with increasing concentrations of copper resulting in higher dissolution rates of gold at a potential of 0.3V. Studies on the dissolution of gold powder in alkaline oxygenated thiosulfate solutions containing low concentrations of copper have shown that the role of copper in enhancing the dissolution rate of gold is possibly associated with the formation of a copper–thiosulfate–oxygen intermediate which is more reactive in terms of cathodic reduction than dissolved oxygen. The electrochemical experiments have been complemented by a leaching study which has shown that milling of gold powder in the presence of copper (added as ions, metal, or oxide) assists with the dissolution of gold in thiosulfate solutions.     

Anodic dissolution of spongy titanium in ethanol solution for preparation of nano-sized TiO2 powder

Nano-sized TiO₂ powder was prepared by electrochemical dissolution of spongy titanium in an ethanol solution following direct hydrolysis of the electrolyte solution. Characterization of the electrochemical product revealed that Ti(OEt)₄ was formed by anodic dissolution of spongy titanium in ethanol solution. X-ray diffraction and transmission electron microscope were, respectively, used to investigate the structure of TiO₂. This study showed that nano-sized TiO₂ prepared by this method has a structural and thermal stability with a narrow size distribution of 5-10 nm. The optimum electrochemical operating conditions established were a temperature of 333-343 K, current density of 400 A m⁻² and faradaic efficiency of 86%. Experiments showed that this process might be recommended as a promising technique for synthesis of nano-sized powder.