Computational modeling of cathodic limitations on localized corrosion of wetted SS 316L at room temperature

The ability of a SS 316L surface wetted with a thin electrolyte layer to serve as an effective cathode for an active localized corrosion site was studied computationally. The dependence of the total net cathodic current, I_net, supplied at the repassivation potential E_rp (of the anodic crevice) on relevant physical parameters including water layer thickness (WL), chloride concentration ([Cl⁻]) and length of cathode (Lc) were investigated using a three-level, full factorial design. The effects of kinetic parameters including the exchange current density (i_o,c) and Tafel slope (β_c) of oxygen reduction, the anodic passive current density (i_p) (on the cathodic surface), and E_rp were studied as well using three-level full factorial designs of [Cl⁻] and Lc with a fixed WL of 25 μm. The study found that all the three parameters WL, [Cl⁻] and Lc as well as the interactions of Lc × WL and Lc × [Cl⁻] had significant impact on I_net. A five-factor regression equation was obtained which fits the computation results reasonably well, but demonstrated that interactions are more complicated than can be explained with a simple linear model. Significant effects on I_net were found upon varying either i_o,c, β_c, or E_rp, whereas i_p in the studied range was found to have little impact. It was observed that I_net asymptotically approached maximum values (I_max) when Lc increased to critical minimum values. I_max can be used to determine the stability of coupled localized corrosion and the critical Lc provides important information for experimental design and corrosion protection.     

Sintered stainless steels: Fatigue crack propagation resistance under hydrogen charging conditions

Monophasic and multiphasic (two and three phases) sintered stainless steels were prepared both considering premixes of AISI 316LHC and AISI 434LHC stainless steels powders and using a prealloyed duplex stainless steel 25% Cr, 5% Ni, 2% Mo powder. Their fatigue crack propagation resistance was investigated both in air and under hydrogen charging conditions (0.5 M H₂SO₄ + 0.01 M KSCN aqueous solution; applied potential = −700 mV/SCE), considering three different stress ratios (R = 0.1; 0.5; 0.75). Fatigue crack propagation micromechanisms were investigated by means of fracture surface scanning electron microscope (SEM) analysis.For all the investigated sintered stainless, fatigue crack propagation resistance is influenced by hydrogen charging and an increase of crack growth rates dependent on the steel microstructure is obtained. Experimental results also allow to identify the sintered stainless steel obtained from the prealloyed 25% Cr, 5% Ni, 2% Mo powder as the most resistant to fatigue crack propagation in air and under hydrogen charging conditions.     

从改革中求发展 从改革中求效益

总结了解放４５年来上海钢铁工业所取得的成就，重点阐述了技术、工艺、装备方面的现状和不足以及发展目标，指出：只有实行改革开放，加快技术改造，才能提高上海钢铁工业的总体水平，提高经济效益，也才能使老企业焕发青春，步入现代化钢铁工业之林。     

耐腐蚀高压柱塞泵用新型双相不锈钢的研究

叙述了新型双相不锈钢－ＷＳＤ钢的组织及其耐蚀性能。试验结果表明，ＷＳＤ钢在氯化物介显示出优异耐蚀性能，其抗点蚀性能远超过Ｃｒ１３，１８－８Ｔｉ，３１６Ｌ等钢种，达到国外Ａｌ－６Ｘ，ＳＡＦ２２０５等钢种的水平。     

轴对称与非轴对称截面冷拔棒材表面残余应力的比较

用物理测定法测定了矩形截面冷技型钢表面的残余应力，并与圆形截面冷拔型钢表面残余应力进行比较。提出用高温近火方法来改善矩形截面冷拔型钢表面残余应力的工艺探索。     

17-4PH沉淀硬化不锈钢氮离子注入及其复合改性的研究

采用N+注入，N-C-O共渗结合N+注入的表面复合改性方法，探索强化17－4PH钢表面的有效途径，该方法赋予基体表面一定深度的改性范围与低摩擦系数，因而强化效果达到最佳。同时还探索了不同时效温度下，基体心部硬度变化的规律。     

Passivation of Fe-Cr alloys studied with ICP-AES and EQCM

The response of sputter deposited Fe-15Cr and Fe-25Cr alloys to a rapid potential increase in the passive region was studied using two in situ methods: electrochemical quartz crystal microbalance and inductive coupled plasma-atomic emission spectroscopy (ICP-AES). Both methods indicated an increase in the dissolution rate of iron following the potential change; the total amount of material dissolved being higher for the Fe-15Cr alloy. For both alloys, about 10% of the total dissolved material was Cr. This result compared well with experiments on a 430 stainless steel. ICP-AES is shown to be useful for the in situ determination of partial currents of metal dissolution using solution analysis in a flow cell.     

Formation of the Fe(II)-Fe(III) hydroxysulphate green rust during marine corrosion of steel

Rust layers formed on steel sheet piles immersed 1 m above the mud line for 25 years were analysed by Raman spectroscopy, scanning electron microscopy and elemental X-ray mappings (Fe, S, O). They consist of three main strata, the inner one mainly composed of magnetite, the intermediate one of iron(III) oxyhydroxides and the outer one of hydroxysulphate green rust GR(SO₄²⁻). Simulations of GRs formation in solutions having large [Cl⁻]/[SO₄²⁻] ratios revealed that the hydroxysulphate GR(SO₄²⁻) was obtained instead of the hydroxychloride GR(Cl⁻), as demonstrated by X-ray diffraction and transmission Mössbauer spectroscopy analyses. Measurements of the [S], [Fe] and [Cl] concentrations allowed us to establish that GR(SO₄²⁻) formed along with a drastic impoverishment of the solution in sulphate ions; the [Cl⁻]/[SO₄²⁻] ratio increased from 12 to 240. The GR, acting like a “sulphate pump”, may favour the colonisation of the rust layers by sulphate reducing bacteria.     

Enhanced oxidation of the 9%Cr steel P91 in water vapour containing environments

The short term (∼100 h) oxidation behaviour of the 9%Cr steel P91 was studied at 650 °C in N₂-O₂-H₂O gas mixtures containing a relatively low oxygen level of 1%. The oxidation kinetics were measured thermogravimetrically and the oxide scale growth mechanisms were studied using H₂¹⁸O-tracer with subsequent analyses of oxide scale composition and tracer distribution by MCs⁺-SIMS depth profiling. The corrosion products were additionally characterised by light optical microscopy, SEM-EDX and XRD. It was found that the transition from protective, Cr-rich oxide formation into non-protective mixed oxide scales is governed by the ratio H₂O^(g)/O₂ ratio rather than the absolute level of H₂O^(g). The results of the tracer studies in combination with the data obtained from experiments involving in situ gas changes clearly illustrated that under the prevailing conditions the penetration of water vapour molecules triggers the enhanced oxidation and sustains the high growth rates of the poorly protective Fe-rich oxide scale formed in atmospheres with high H₂O^(g)/O₂ ratios. The experimental observations can be explained if one assumes the scale growth to be governed by a competitive adsorption of oxygen and water vapour molecules on external and internal surfaces of the oxide scales in combination with the formation of a volatile Fe-hydroxide during transient oxidation. The formation of the non-protective Fe-rich oxide scales is suppressed in atmospheres with low H₂O^(g)/O₂ -ratios, and the healing of any such scale is promoted.     

Synergistic inhibition between o-phenanthroline and chloride ion for steel corrosion in sulphuric acid

The corrosion inhibition of cold rolled steel in 0.5 M sulphuric acid in the presence of o-phenanthroline and sodium chloride (NaCl) has been investigated by using weight loss and electrochemical techniques. The experimental data suggest that the inhibition efficiency increases with increasing NaCl concentration in the presence of 0.0002 M o-phenanthroline, but decreases with increasing temperature. A synergistic effect is observed when o-phenanthroline and chloride ions are used together to prevent cold rolled steel corrosion in 0.5 M sulphuric acid. The polarization curves showed that the complex of o-phenanthroline and NaCl acts as a mixed type inhibitor. The experimental results suggested that the presence of chloride ions in the solution stabilized the adsorption of o-phenanthroline molecules on the metal surface and improved the inhibition efficiency of o-phenanthroline. The adsorption of the complex accords with the Langmuir adsorption isotherm. Some thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy have been calculated by employing thermodynamic equations. Kinetic parameters such as apparent activation energy and pre-exponential factor have been calculated and discussed.