强碱性介质铝阳极析氢影响因素研究

结合恒电流集气试验和表面分析手段研究了强碱性介质中影响铝阳极析氢作用的因素,分析了铝阳极的合金化、电解液浓度、工作温度和抑氢物质对材料析氢性能的影响.结果表明:4 mol/L KOH是综合性能较好的强碱性介质,并且选择稀土铝阳极,引入邻胺基苯酚抑氢剂,能够显著抑制铝阳极表面的析氢速率.     

碱性介质中Al-Ga-Sn-Mg的阳极行为研究

炼制了纯铝及含有Ga、Sn、Mg的铝合金阳极，通过极化曲线、交流阻抗、恒电流集气等电化学方法研究了其在4mol/L KOH溶液中的阳极行为，并探讨了Na2SnO3在此介质中对铝阳极性能的影响。结果表明：铝在碱性介质中的自腐蚀析氢呈现典型的正差异效应。铝合金在碱性介质中的阳极极化小，表面的析氢量低，极化电位负，表面溶解均匀，阳极性能较好。锡酸钠不仅可以有效抑制铝阳极在碱性介质中的析氢，同时活化了铝阳极。     

碱溶液中添加剂对铝阳极行为的影响

为了提高铝活化性能以及降低析氢腐蚀,用电化学方法研究了在4mol／LKOH溶液中,添加剂酒石酸钾钠（C4H4O6KNa）、邻氨基苯酚（NH2C6H4OH）以及复合添加剂对铝阳极（W（AJ）=99．999％）电化学行为的影响。结果表明：C4H4O6KNa对抑制铝的析氢腐蚀作用不大,但大幅度提高铝阳极的活性。添加NH：C6H40H,主要作用是大幅度抑制铝的析氢腐蚀,对铝活性几乎无影响。复合添加剂（C4H4O6KNa＋NH2C6H4OH＋KMnO4）能明显降低铝阳极在碱性介质中的极化,提高其活性,同时析氢腐蚀也降低,其最佳配方为：15mmol/L C4H4O6KNa＋0．4mol／LNH2C6H4OH＋0．8mmol／LK2MnO4。     

铝基牺牲阳极的溶解过程和负差异效应

用旋转环一盘电极、电子探针和形貌分析等手段研究了铝基牺牲阳极的溶解过程及其负差异效应。结果表明,铝基牺牲阳极的溶解是从第二相组织边界处引发,从而破坏表面膜而活化。阳极溶解过程中的自腐蚀(表现为析氢)是负差异效应的主要原因,它随外加电流而线性增大。铝基牺牲阳极的负差异效应系数为12.8%。     

高活性铝合金阳极的电化学行为

制备了Al-Ga-In-Bi-Pb-Mg、Al-Ga-In-Cd-Mg和Al-Ga-In-Pb-Mg等3种铝阳极合金材料.采用腐蚀质量损失法、排水法和电化学方法分别测试了合金的自腐蚀速率、析氢速率及电化学性能,并采用SEM分析了合金腐蚀后的表面形貌.结果表明,制备的3种铝阳极合金在5 mol/L的NaOH溶液中均具有较负的开路电压、低的自腐蚀速率和析氢速率,并且随着极化电位的增加,各合金均具有很高的电化学活性.     

高性能铝合金阳极碱性介质中的电化学性能

制备了Al-Ga-In-Mn-Bi-Pb、Al-Ga-In-Mn-Cd和Al-Ga-In-Mn-Pb3种铝阳极合金。分别测试了3种合金的自腐蚀速率、析氢速率、电化学性能等,并采用SEM分析了合金腐蚀后的表面形貌。结果表明:制备的3种铝阳极合金在5mol/LNaOH溶液中均具有较负的开路电位、低的自腐蚀速率和析氢速率,并且随着极化电位的增加,各合金均具有很高的电化学活性。     

冷变形对铝空气电池用阳极电化学性能的影响

通过测量不同变形量的Al-Ga-Sn-Bi阳极合金在4 mol/L KOH溶液中自腐蚀速率、析氢速率、放电曲线等,研究了冷变形对铝空气电池用铝阳极电化学性能的影响。结果表明:与铸态合金相比,冷轧变形可以提高铝阳极合金的电化学性能。变形量80%的合金具有较低的自腐蚀速率和析氢速率及较长而稳定的放电特性。对铸态合金进行80%的冷变形能够较大幅度地提高合金的电化学性能。     

室温轧制及固溶处理对Al-Ga-Mg-Mn-Bi阳极合金电化学性能的影响

对Al-Ga-Mg-Mn-Bi阳极合金固溶处理和常温轧制变形,测量不同处理状态下的电化学阻抗谱、极化曲线、自腐蚀速率等,研究固溶和轧制处理对该合金的组织及电化学性能的影响。结果表明:与铸态试样相比,固溶处理减少了铝阳极组织中第二相的数量,较大程度地降低铝阳极的自腐蚀和析氢速率,改善了合金的腐蚀形貌,使恒流放电的电位负移;轧制处理使恒流放电的电位负移,能够明显改善铝阳极的腐蚀形貌。     

用旋转圆柱电极研究碱性溶液中添加剂对铝阳极电化学行为的影响

为了提高铝阳极活化性能以及降低腐蚀,用旋转圆柱电极和电化学方法研究了在4 mol/L NaOH溶液中传统添加剂Na2SnO3、含氟阴离子表面活性添加剂F1以及两者的复合添加剂在静态和动态情况下对铝合金阳极电化学行为的影响.结果表明:Na2SnO3在静态下对提高铝阳极活化及抑制铝阳极腐蚀均作用明显,但在动态下作用减弱;F1在动、静态条件下对抑制析氢效果明显;复合添加剂在动态条件下能够有效抑制铝阳极的腐蚀和提高其活化性能.     

氯离子浓度对AZ63镁合金初始腐蚀的影响

采用腐蚀电位、线极化、电化学阻抗谱和极化测量等方法研究AZ63镁合金在1％、3％、5％和7％NaCl(质量分数)腐蚀介质中的初始腐蚀行为.结果表明,随着氯离子浓度的增加,腐蚀速率加快.基于得到的动力学参数,讨论了阳极溶解和析氢反应的机理,并建立了动力学模型.结果显示,阳极溶解是发生在Temkin条件下,析氢反应取决于M...     

混合稀土对碱性介质中铝阳极性能的影响

采用交流阻抗、恒电流集气等电化学方法对比了含与不含混合稀土铝合金在4 mol/L KOH溶液中的阳极行为，并结合金相显微镜、电子探针等表面分析技术探讨了混合稀土元素对铝阳极性能的影响.结果表明:稀土使铝阳极的晶粒细化，阴极相减少，溶解均匀性增强，自腐蚀析氢量减少，性能得到优化.     

The negative difference effect of magnesium and of the AZ91 alloy in chloride and stannate-containing solutions

The negative difference effect of pure magnesium and of the alloy AZ91 was investigated by volumetric tests in NaCl with and without addition of Na₂SnO₃. Hydrogen comes from two sources: H₂ which accompanies localized magnesium dissolution inside the pits and H₂ from H₂O reduction at the passive surface outside the pits. By separating the two parts it could be shown that the rate of hydrogen evolution inside the pits is quantitatively consistent with a two-step EC-mechanism of magnesium dissolution with hydrogen evolution coupled to the second dissolution step. Addition of Na₂SnO₃ does not influence the second step.     

氢在钢的硫化物应力腐蚀破裂中的作用

本文研究了12MnMoVNbTi低合金钢在饱和H_3S溶液中的极化和应力腐蚀行为,并与电解充氢条件下的应力破裂行为进行了对比。证明钢中Mo、Nb含量的变化与热处理条件的不同对其一般腐蚀行为影响很小,但能显著改变其抗应力腐蚀性能,12MnMoVNbTi钢在H_2S介质中的应力腐蚀破裂行为与它们在充氢条件下的应力破裂行为非常类似,显示其应力腐蚀破裂的实质是氢脆。充氢条件下应力弛豫和恒载荷拉伸试验结果表明,氢有引起钢的软化和硬化的双重作用。由于氢的进入所产生的软化作用使钢在屈服强度以下发生塑性变形,但随后的硬化过程又使变形速度逐步减慢。这种由氢的作用引起的在较低应力下发生的塑性变形过程并不直接导致断裂,但塑性变形行为和氢应力破裂行为之间的关系表明,这种变形过程中的位错运动能够帮助氢的移动和向塑变区及裂纹尖端集中,促进氢脆断裂。     

A new theory for the negative difference effect in magnesium corrosion

An unusual feature known as the negative difference effect (NDE) can be observed in magnesium when recording corrosion current density–potential curves. More hydrogen is evolved at a more positive potential which does not occur in conventional metals. Several models have been proposed in the literature in order to explain the phenomenon of NDE. They succeed in explaining some effects, and fail to deal with others. A new model, which explains the NDE by two electron consuming processes, is presented in this paper. By potentiostatic investigations of magnesium in a chloride electrolyte, measurements of hydrogen evolution and chemical analysis of the electrolyte the new model was experimentally verified.     

Hydrogen evolution reaction on spheroidal graphite cast iron with different pearlite areas in sulphuric acid solutions

The rate equation of hydrogen evolution reaction of spheroidal graphite cast iron with different pearlite area has been studied in sulphuric acid solutions at 298 K. The cathodic Tafel slope of ?0·130 V/decade and the reaction order with respect to the activity of hydrogen ion of 1 are obtained by linear potential sweep technique. The rate equation of hydrogen evolution reaction does not depend on the area of pearlite. There is no difference in hydrogen evolution reaction mechanisms between pure iron and spheroidal graphite cast iron.     

INFLUENCE OF B ON H_2S CORROSION-RESISTANTBEHAVIOR OF Fe-BASED AMORPHOUS

Substituting boron for carbon can improve the corrosion behavior of Fe-based amorphoussignificantly especially in acid solution with saturated H_2S. XPS analysis proves that boronenriches in the surface layer of amorphous and reacts with hydrogen to form B_(10)H_(14) . Itefficiently prevents the intrusion of hydrogen to the sample, thus the destructive effect ofhydrogen can be decreased greatly.     

Synthesis of imidazoline‐based dissymmetric bis‐quaternary ammonium gemini surfactant and its inhibition mechanism on Q235 steel in hydrochloric acid medium

An imidazoline‐based dissymmetric bis‐quaternary ammonium gemini surfactant has been synthesized. Its surface active properties at equilibrium in water at 25 °C were determined. The inhibitive effect of the compound on Q235 steel in 1 M hydrochloric solution was investigated by the weight‐loss method, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) analysis, and quantum chemical calculations. The results indicate that the compound has high surface properties and the inhibition efficiency (IE) increases with the increase in inhibitor concentration, which attain the maximum value around the CMC value. The imidazoline‐based dissymmetric bis‐quaternary ammonium acts as a mixed type inhibitor mainly inhibiting the cathodic processes and does not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The best IE is obtained at the immersion time of 144 h. The adsorption of the studied inhibitor on Q235 steel can be fitted to a Langmuir isotherm and the adsorption process is a spontaneous chemical adsorption. Quantum chemistry calculation results show that the imidazoline ring and heteroatoms of N, O, are the active sites of the inhibitors.     

Effects of turbulent flow on the corrosion inhibition properties of 2‐mercaptobenzimidazole

The electrochemical techniques, that is, polarization resistance (R_p) and potentiodynamic polarization curves, were used in order to determine the effect of turbulent flow on the corrosion inhibiting effect of 2‐mercaptobenzimidazole (2‐MBI) on API 5L X52 grade steel samples immersed in a 3% NaCl aqueous solution saturated with CO₂ at 60 °C. Turbulent flow conditions were controlled using a rotating cylinder electrode (RCE). An inhibition efficiency of 98% was measured at a concentration of 10 ppm of 2‐MBI at a rotation rate of 5000 rpm. This efficiency value is similar to those efficiency values measured at 25 and 40 ppm 2‐MBI and at the same rotation rate. These observations suggest that as the turbulent flow conditions increase the corrosion inhibiting effect of 2‐MBI is enhanced. 2‐MBI follows a Langmuir adsorption isotherm. The calculated values of adsorption equilibrium constant (K_ads) and adsorption free energy ($\Delta G_{{\rm ads}}^{{\rm o}} $ ) suggest that the adsorption process taking place is chemical. The polarization curves indicate that the 2‐MBI does not modify the electrochemical mechanism of the anodic (Fe dissolution) and cathodic (hydrogen evolution) reactions. It is suggested that 2‐MBI decreases the rate at which these reactions occur, blocking the active sites on the steel surface.