微液滴现象与大气腐蚀——Ⅱ.微液滴现象的电化学表征

用扫描Kelyin探头和电化学极化等手段,研究了微液滴现象与大气腐蚀的电化学过程之间的相关性.扫描Kelvin探头测定主液滴周围的电位分布显示,微液滴只在表面的正电性区域出现;当有微液滴形成时,火山形电位分布的峰高且宽、谷深且窄;同时,峰变宽的速率与微液滴的扩展速率近似相等.电化学极化结果显示,微液滴的成核速率随极化电流的增加而线性加速,促使大气腐蚀过程发生的电位差和相应的腐蚀电流是微液滴形成和发展的推动力.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

Breakdown of passive film on nickel in borate solutions containing halide anions

The effect of Cl⁻, Br⁻ and I⁻ anions as aggressive agents on the anodic behaviour of nickel electrode in deaerated Na₂B₄O₇ solutions have been investigated by galvanostatic polarization technique. Lower concentrations of the halide anions have no effect on the mechanism of nickel passivation. An increase in the halide anions concentration causes oscillation of the potential in the oxygen evolution region. This could be attributed to the destruction of the passivity by halide anions and repassivation of the film by anodic current and/or OH⁻ anions. Higher aggressive anion concentrations cause breakdown of the passive film and initiated pitting corrosion. As the temperature increases, the breakdown potential is shifted towards the more negative direction. On the other hand, as the pH of the solution increases, the breakdown potential is shifted toward more positive direction, indicating increased protection of the passive film. The activation energy, , of the oxide film formation in the presence of Cl⁻ anions was calculated and was found to be 21 kJ/mol.     

321不锈钢点蚀电位影响因素的研究

通过正交设计和对比实验研究了温度、pH值以及Cl-和SO2-4含量对321不锈钢点蚀电位的影响.正交设计表明,温度和Cl-(Cl-≥0.014mol/L)含量对点蚀电位Eb的影响显著,但pH值(6～9)则没有影响.对比实验表明,当Cl-≤0.014 mol/L时,Cl-对Eb没有影响,当Cl-＞0.014 mol/L,则Eb随Cl-浓度对数升高而线性下降.点蚀电位随温度升高而下降.如不含Cl-,则SO2-4对Eb没有影响,当Cl-=0.028 mol/L时,Eb随SO2-4浓度升高而升高,并趋于稳定值.     

外场作用下由工业TiOSO4液合成介孔二氧化钛

以工业硫酸氧钛为钛源,采用复合模板合成路线,分别于超声,微波和水热外场作用下合成了介孔二氧化钛前驱体.通过调节反应体系的pH值来控制TiOSO4液的水解和缩聚速率.煅烧脱除模板后得到锐钛型的介孔二氧化钛.产物采用XRD,氮等温吸附脱附,粒度分布,SEM,TEM,SAD和X射线能谱分析(XPS)等技术进行了表征.结果表明具有强极化作用和温和水热环境的外场利于制备结构更佳的介孔二氧化钛;超声振动利于介观结构的形成.在微波辐照下,所制得介孔二氧化钛的比表面积为146.6 m2/g,平均孔径2.57 nm,晶粒尺寸13.65 nm.超声、微波和水热较常规合成方法更利于形成和稳定介孔结构.     

过冷及非晶态Cu扩散性质的分子动力学模拟

采用分子动力学方法，模拟了液态Cu在快速凝固过程中处于过冷态和非晶态时原子的扩散行为，原子间相互作用势采用镶嵌原子(EAM)势，扩散性质由平均方差(MSD)时间关联函数描述，结构分析使用偶关联函数和对分析技术．计算结果表明扩散运动对于晶体的产生起着重要的作用．给出了不同弛豫时刻的微观结构信息．     

波型与电位对A537钢疲劳裂纹扩展的影响

研究了A537钢在3.5%NaCl水溶液中阴极极化与阳极极化条件下加载波型对疲劳裂纹扩展速率的影响并研究了相应电位条件下应变电极的电化学响应规律,结果表明,在外加电位为-800mV(SCE)以上时阳极溶解机制起主导作用,在-800mV以下时氢脆机制起主导作用,在阳极极化条件下,持续应变型加载波型的影响主要体现于低△K范围,而在阴极极化条件下,其影响体现于高△K范围,持续应变导致了自腐蚀电位的下降与阳极溶解电流密度的大幅度提高     

循环冷却水中微生物对黄铜管的腐蚀影响

采用交流阻抗(EIS)测试技术，研究了电厂循环冷却水中微生物对黄铜腐蚀行为影响。结果表明黄铜电极在有菌培养基溶液中浸泡初期，电极表面形成的生物膜抑制了黄铜的腐蚀，随着浸泡时间的延长，生物膜内微生物的代谢活动和代谢产物促进了黄铜的腐蚀。提出了在无菌和有菌培养基溶液中所测得的EIS的等效电路，并计算了相应的等效电路参数。     

Impact of transient chemistry on the corrosion potential of a steam turbine disc steel

The adoption of two-shifting in coal-fired power generation (switching from on-load to off-load conditions on a daily basis and off-load for the weekend) results in regular cycling of the solution chemistry of the condensed steam on the turbine discs. A first stage investigation has been made of the effect of such chemistry cycling on the corrosion potential of the disc steel. The corrosion potential is typically about +0.05 V (SCE) in off-load chemistry (aerated pure water) and below −0.6 V (SCE) in on-load chemistry (deaerated solution containing chloride or chloride and sulphate anions). The critical observation was the sluggish response of the corrosion potential upon restoration of deaerated on-load conditions with the implication of a likely increase in pit and stress corrosion crack development.     

Corrosion behaviour of brazed multilayer material AA4343/AA3003/AA4343: Influence of coolant parameters

This paper is the second part of a work devoted to corrosion in brazed AA4343/AA3003/AA4343 materials on the water side of automotive heater cores. In the first part of the study [S. Tierce, N. Pébère, C. Blanc, C. Casenave, G. Mankowski, H. Robidou, Electrochim. Acta 52 (2006) 1092], corrosion initiation in the surface layer (i.e. the residual cladding) has been investigated. It has been associated to defective sites in the passive film covering the alloy. The defective sites are linked to α-Al(Mn,Fe)Si particles built up during brazing process. Interactions between α-Al(Mn,Fe)Si particles and the matrix are responsible for the observed behaviour. The present study focuses on the propagation of corrosion through the material in neutral water–ethylene glycol mixtures with and without chlorides. Comparison of the electrochemical behaviour of the three layers of the brazed material (i.e. the residual cladding, the “band of dense precipitates (BDP)” and the core material) revealed that the residual cladding was nobler than the BDP and the core material and thus that the corrosion should propagate through the inner layers due to galvanic coupling: the inner layers constitute the anode and the residual cladding the cathode. Increasing the ethylene glycol content in the water–ethylene glycol mixture decreased the rate of consumption of the materials whereas addition of chloride ions increased it. Mass variation measurements of brazed material in different solutions containing the degradation products of ethylene glycol showed that only glycolate ions had a slight detrimental effect. Corrosion tests performed in heater core tubes allowed the propagation mechanisms to be confirmed.