铜镍合金在NaCl溶液中点蚀行为的研究

对铜镍合金BFe30-1-1在NaCl溶液中出现的点腐蚀行为进行了研究.首先测试其在不同pH值的0.5 mol/L Nacl溶液中的阳极极化曲线以确定点蚀电位,并在点蚀电位之上进行恒电位腐蚀.通过原子吸收光谱测定腐蚀后溶液中的Cu2 和Ni2 含量,采用扫描电镜进行形貌观察以及分析试样断面的微区成分,并对点蚀坑内的腐蚀产物进行X射线衍射分析,以了解不同条件下铜镍合金的点腐蚀行为.结果表明,BFe30-1-1合金在酸性和弱碱性的0.5 mol/L NaCl溶液中的腐蚀规律基本相似;在强碱性溶液中的低电位下,合金表面可以形成较稳定的钝化膜,因而耐腐蚀性能较好;铜镍合金BFe30-1-1的点蚀坑内发生了脱镍腐蚀.     

钢铁点蚀坑内腐蚀产物对点蚀扩展的影响

为了探讨钢铁点蚀坑内部生成的腐蚀产物对点蚀生长的影响,使用自制的2种铁微电极,通过电化学三电极体系,使之在阳极极化条件下发生溶解,一定程度上模拟点蚀生长的特征。结果表明:采用微型注射器可以将2种铁微电极表面黑色腐蚀产物沉积层冲洗到模拟点蚀坑外部,消除其对点蚀扩展的影响;通过对比冲洗前后的阳极溶解电流随时间的变化趋势,可以计算该腐蚀产物对模拟点蚀生长速率的影响;借助2种铁微电极的特殊性,提出了对其点蚀内部腐蚀产物影响进行量化的方法,将其用于修正点蚀内部金属离子的扩散系数,在一定程度上可完善点蚀的生长和预测模型。     

铝电解电容器高压电子箔点蚀机理的研究

采用极化曲线和场发射扫描电镜等方法,研究了铝电解电容器高压电子箔在高温强酸性溶液中的点蚀机理。结果表明:在开路状态下铝光箔在硫酸盐酸发孔溶液中可以产生点蚀,测到自腐蚀电位就是点蚀电位;形成隧道孔后,阳极极化曲线出现点蚀电位,且点蚀过电位与隧道孔长度之间存在线性关系。根据点蚀的微电池模型及其在阳极极化下微电池的腐蚀极化图,提出产生上述现象的原因是阳极极化时带孔铝箔的表面由阴极向阳极转变,其转变的临界点即所测到的点蚀电位。     

2种不同形态的Mg-0.12Ca-0.08Ba镁合金的腐蚀行为研究

镁合金的应用受到其变形能力差、耐腐蚀性差的制约。为推广镁合金应用，采用低合金化设计并制备了新型Mg-0.12Ca-0.08Ba合金，通过NaCl溶液浸泡试验、SEM、EDS分析和电化学测试等手段考察了其在3.5%NaCl溶液中的腐蚀行为。实验结果表明：随着腐蚀时间的延长，挤压态及挤压退火态Mg-0.12Ca-0.08Ba合金表面由局部点蚀变为大范围面腐蚀，腐蚀产物逐渐增多，腐蚀产物主要为MgO、Mg(OH)₂,合金表面的线粗糙度、面粗糙度明显增大，析氢速率逐渐减小。与挤压态镁合金相比，退火态合金析氢速率较慢，开路电位更高，腐蚀电流更小，表明退火态合金耐腐蚀性能较好。     

镁合金阳极的析氢、效率与电偶腐蚀放大效应

为了解决镁工程应用公认的主要障碍——电偶腐蚀,探明镁合金固有的负差数效应导致的阳极溶解异常放大和阳极析氢现象,本文通过阳极化镁的析氢速率、镁丝阵列电极、材料表面微观技术的测量,以及部分膜单价镁离子机制的理论推导和分析,发现阳极析氢对镁的"负差数效应"和电偶腐蚀有极强的加速作用;电极表面的微电偶并非强阳极极化条件下镁阳极效率低的根本原因;锌离子的"次生效应"对镁阳极过程有一定的抑制作用;镁表面膜的保护性是决定阳极析氢、电流效率、电偶腐蚀放大效应的关键因素.     

铜镍合金点蚀行为的研究

国产铜镍合金冷凝管时常因点蚀导致泄漏。本文通过在天然海水中的腐蚀试验,揭示了国产铜镍合金在静止天然海水中具有显著的点蚀敏感性。流动海水可抑制点蚀的发生,缝隙使点蚀转移到缝隙内部与电正性金属接触促进点蚀的发生和长大。点蚀起源于暗红色斑点。暗红色斑点为易剥离的膜,时间长时变为有突起感的扁丘,膜下有时中空含水,形成膜下闭塞腐蚀条件,从而导致点蚀。     

镁合金负差数效应的研究进展

随着我国工业水平的不断进步，工程应用领域对轻量化的需求愈加迫切，极大推动了镁合金的快速发展。然而，镁合金的耐蚀性较差，严重阻碍了其实际工程应用。为了有效解决镁合金耐蚀性差的问题，亟需深入研究其腐蚀机理。镁合金电化学腐蚀过程中存在典型的负差数效应(Negative difference effect,NDE)，即在阳极极化下镁合金的析氢速度随电位升高而增加，与传统的电化学动力学理论相异。近年来，国内外学者对镁合金的负差数效应开展了大量研究，先后建立了局部保护膜模型、单价镁离子模型、溶解脱落模型、氢化镁促溶理论、综合理论、部分电子外电路消耗机理、析氢交换电流密度i0增大机理和电催化机理八种理论模型。基于上述模型，人们深化了对镁合金析氢过程的认识，提升了镁合金腐蚀机理的研究深度。本文综述了镁合金电化学腐蚀过程中负差数效应的基本原理及研究现状，归纳出八种负差数效应的理论模型，总结了各模型的发展历程，指出了它们各自存在的不足之处，展望了镁合金腐蚀负差数效应的研究方向。     

SiCp/Al复合材料在Cl-环境中的点蚀行为

通过浸泡模拟实验方法,研究了SiCp/Al复合材料在Cl-环境中的点蚀行为。结果表明,SiCp/Al复合材料点蚀主要出现在SiC颗粒附近,SiC与Al基体界面结合处为点蚀的优先发生位置。Cl-和界面反应物对点蚀的形成和发展起主要促进作用。Nyquist曲线在0~3 d时由容抗弧组成,Bode曲线在0.1~10 000 Hz出现高频相角峰,点蚀腐蚀过程机制表现为单纯电荷传递过程机制。3 d后Nyquist曲线出现一个高频区的容抗弧和低频区的一条与实轴成45°的直线(经典Warburg阻抗),Bode曲线在0.1~10000 Hz出现高频相角峰并在0.001~0.1 Hz出现一个不太明显的低频相角峰,点蚀腐蚀过程机制表现为电荷传递过程与腐蚀产物扩散共同作用的混合机制。     

AZ31镁合金阳极氧化膜在3.5%NaCl溶液中不同浸泡时间的腐蚀机制

为了进一步弄清AZ31镁合金阳极氧化膜在NaCl溶液中的腐蚀机制,采用极化曲线、电容测量技术,基于半导体电化学方法研究了其在3.5%NaCl溶液中耐蚀性能与其半导体特性的关系,得到不同浸泡时间下的载流子浓度以及平带电位。结果表明:镁合金阳极氧化膜为N型半导体,随浸泡时间的增加,载流子浓度呈上升趋势,由浸泡10 min时的1.83×1018cm-3增大到96 h时8.60×1020cm-3,平带电位为-1.69～-1.52V,低于镁合金(-1.44～-1.57 V),在浸泡时间为1 h时膜的平带电位最负,耐蚀性最好;镁合金阳极氧化膜的腐蚀失效过程会经过自我修复期-点蚀诱导期-点蚀期-快速腐蚀期4个阶段。     

溶解氧对碳锰钢点蚀电位测定的影响

选择常用的碳素船体钢和锰系船体钢各一种,在除氧及不除氧的3%NaC l溶液中进行了极化试验,测定了钢的点蚀电位,并利用电子探针分析了腐蚀形貌。结果表明,钢样在除氧溶液中的阳极极化是典型的钝化-点蚀过程;在相同的电位区间,钢样在不除氧的溶液中的表观极化行为与前者截然不同,但是钢样自身的极化过程仍是钝化-点蚀过程,点蚀仍是由钢中的夹杂物诱发,所测点蚀电位值比溶液除氧条件下的结果更正;在有溶解氧条件下测得的点蚀电位同样可以比较不同钢之间的点蚀诱发敏感性,其结果更方便、准确。     

Pitting corrosion of a Rare Earth Mg alloy GW93

Pitting corrosion of magnesium(Mg) alloys is greatly associated with their microstructure, especially second phases. The second phases in traditional Mg alloys such as AZ91 are electrochemically nobler than Mg matrix, while the second phases in Rare earth(RE) Mg alloy GW93 are more active than Mg matrix. As a result, the pitting corrosion mechanism of Mg alloy GW93 is different from the traditional ones. This paper aims to clarify the pitting corrosion mechanism of Mg alloy GW93 through the studies of Volta potential by Scanning Kelvin Probe Force Microscopy(SKPFM), corrosion morphology by Scanning Electron Microscope(SEM), and corrosion resistance by electrochemical tests. Results reveal that the pitting corrosion of GW93 includes three stages, first, dissolution of the second phases, followed by corrosion of Mg matrix adjacent to the dissolved second phases, and finally, propagation of corrosion pits along the depth direction of the dissolved second phases. Anodic second phases and enrichment of Clin the thick corrosion product films dominate the propagation of pitting corrosion.     

Evaluating the improvement of corrosion residual strength by adding 1.0 wt.% yttrium into an AZ91D magnesium alloy

The influence of yttrium on the corrosion residual strength of an AZ91D magnesium alloy was investigated detailedly. Scanning electron microscope was employed to analyze the microstructure and the fractography of the studied alloys. The microstructure of AZ91D magnesium alloy is remarkably refined due to the addition of yttrium. The electrochemical potentiodynamic polarization curve of the studied alloy was performed with a CHI 660b electrochemical station in the three-electrode system. The result reveals that yttrium significantly promotes the overall corrosion resistance of AZ91D magnesium alloy by suppressing the cathodic reaction in corrosion process. However, the nucleation and propagation of corrosion pits on the surface of the 1.0 wt.% Y modified AZ91D magnesium alloy indicate that pitting corrosion still emerges after the addition of yttrium. Furthermore, stress concentration caused by corrosion pits should be responsible for the drop of corrosion residual strength although the addition of yttrium remarkably weakens the effect of stress concentration at the tip of corrosion pits in loading process.     

Pitting Corrosion Behaviour of Monel-400 Alloy in Chloride Solutions

1-IntroductionPittingcorrosionisthemostdestructiveformamongthedifferentformsoflocalizedcorrosionofmetals.Thebreakdownofthepassivefilmbyag-gressiveionssuchaschlorideionscanleadtohighpenetrationrates.Copper-nickelalloysarewidelyusedascorrosionresistantmaterialsinmarineengineering.Theircor-rosionratesdecreasesharplywithincresingNicon-tent.AseriesofCu-Nialloyshavebeenwidely.tudi.d[1~12]innaturalseawaterandinNaClsolu-tionsusingdifferentelectrochemicalmethods.Con-tradictoryresultshavebeenobtained…     

Pitting Corrosion of Cu-Zn-Al Shape Memory Alloy in Simulated Uterine Fluid

Electrochemical test technology and surface analysis method were employed to investigate the pitting corrosion of Cu-Zn-AI shape memory alloy in simulated uterine fluid. The results showed that the breakage of the breaking-renovating equilibrium of surface layers resulted in the pitting corrosion of Cu-Zn-AI shape memory alloy in simulated uterine fluid. The development of pitting corrosion was controlled by dissolution of surface layers. The critical pitting corrosion potential was 1.70 VSCE. The kinetics equation for the development of pitting corrosion for Cu-Zn-AI shape memory alloy in simulated uterine fluid was io=465.68 t-0.5+1.5. Pitting appearances of pits could be two types: tortoise-shell, and anomaly abscess. Cl- ion facilitated the pitting corrosion of Cu-Zn-AI shape memory alloy by competing adsorption and concentrating on alloy surface at high positive potential.     

EIS Study on Pitting Corrosion of AA5083-H321 Aluminum-Magnesium Alloy in Stagnant 3.5% NaCl Solution

In this research, EIS （electrochemical impedance spectroscopy） technique was utilized to study the pitting corrosion behaviour of AA5083-H321 aluminum-magnesium alloy in 3.5% NaCl solution. Impedance spectra were obtained during 240 h of exposure of the sample to the test solution. The surface and cross-section of the samples were studied by scanning electron microscopy （SEM） and EDAX （energy dispersive analysis of X-ray） analysis. The results indicated that as the resistance of the passive layer on intermetallic particles is very small, this parameter on the sample surface layers is controlled by that of pure passive layer. However, the capacitors in the proposed equivalent circuit are replaced with the constant phase elements （CPE）, due to non-uniformity and occurrence of pitting corrosion on the surface. The outward diffusion of Al^＋3 ions through the passive layer and the thickening of this layer cause the impedance decrease in the first 24 h and increase afterwards. The detachment of intermetallic particles from some of pits and the accumulation of the corrosion products inside some others are factors that prevents the continuation of cathodic reactions on the top of the intermetallic particles.     

T6处理对AZ63镁合金在模拟海水中耐蚀性的影响

为研究热处理工艺对合金耐腐蚀性的影响,采用X射线衍射仪(XRD)、扫描电镜(SEM)、析氢失重以及多种电化学测试等方法研究了经T6处理(固溶处理+人工时效)的AZ63镁合金在模拟海水中的腐蚀行为。结果表明:T6处理(固溶处理+人工时效)镁合金第二相沿晶界呈网状分布,与铸态镁合金相比氢气析出多、腐蚀速度快,并有点蚀产生;T6处理(固溶处理+人工时效)改变了镁合金的组织结构以及分布,增大了稳定相第二相与基体相的接触,降低了合金的耐蚀性。     

New insights into the effect of Tris-HCl and Tris on corrosion of magnesium alloy in presence of bicarbonate,sulfate,hydrogen phosphate and dihydrogen phosphate ions

In vitro degradation is an important approach to screening appropriate biomedical magnesium(Mg) alloys at low cost. However, corrosion products deposited on Mg alloys exert a critical impact on corrosion resistance. There are no acceptable criteria on the evaluation on degradation rate of Mg alloys. Understanding the degradation behavior of Mg alloys in presence of Tris buffer is necessary. An investigation was made to compare the influence of Tris-HCl and Tris on the corrosion behavior of Mg alloy AZ31 in the presence of various anions of simulated body fluids via hydrogen evolution, p H value and electrochemical tests.The results demonstrated that the Tris-HCl buffer resulted in general corrosion due to the inhibition of the formation of corrosion products and thus increased the corrosion rate of the AZ31 alloy. Whereas Tris gave rise to pitting corrosion or general corrosion due to the fact that the hydrolysis of the amino-group of Tris led to an increase in solution p H value, and promoted the formation of corrosion products and thus a significant reduction in corrosion rate. In addition, the corrosion mechanisms in the presence of Tris-HCl and Tris were proposed. Tris-HCl as a buffer prevented the formation of precipitates of HCO_3~-, SO_4~(2-),HPO_4~(2-) and H_2PO_4~- ions during the corrosion of the AZ31 alloy due to its lower buffering p H value(x.x).Thus, both the hydrogen evolution rate and corrosion current density of the alloy were approximately one order of magnitude higher in presence of Tris-HCl than Tris and Tris-free saline solutions.     

铸造镁合金Mg-Zn-Y-Zr-Ca在模拟体液中的腐蚀行为

采用光学显微镜和扫描电子显微镜研究了铸态Mg-3Zn-0.6Y-0.5Zr-0.3Ca(质量分数/%)合金的显微组织,采用失重法测试了合金在模拟体液中浸泡不同时间的生物腐蚀性能,并对合金的腐蚀行为进行分析。结果表明,Mg-3Zn-0.6Y-0.5Zr-0.3Ca合金中沿晶界连续分布的Mg3YZn6相对合金的腐蚀具有作为微阴极加速基体腐蚀或抑制腐蚀扩展的双重作用。Mg-3Zn-0.6Y-0.5Zr-0.3Ca合金的腐蚀过程分为3个阶段:晶界附近溶质原子贫化区形成几微米宽的腐蚀凹槽,在富Zr-贫Zr区形成大量腐蚀斑点,腐蚀凹槽和腐蚀斑点相互扩展破坏基体。     

Dealloying corrosion of anodic and nanometric Mg41Nd5 in solid solution-treated Mg-3Nd-1Li-0.2Zn alloy

The microstructure and chemical compositions of the solid solution-treated Mg-3Nd-1Li-0.2Zn alloy were characterized using optical microscope,scanning electron microscope(SEM),transmission electron microscope(TEM),electron probe micro-analyzer(EPMA)and X-ray photoelectron spectroscopy(XPS).The corrosion behaviour of the alloy was investigated via electrochemical polarization,electrochemical impedance spectroscopy(EIS),hydrogen evolution test and scanning Kelvin probe(SKP).The results showed that the microstructure of the as-extruded Mg-3Nd-1Li-0.2Zn alloy contained α-Mg matrix and nanometric second phase Mg41 Nd5.The grain size of the alloy increased significantly with the increase in the heat-treatment duration,whereas the volume fraction of the second phase decreased after the solid solution treatment.The surface film was composed of oxides(Nd2O3,MgO,Li2O and ZnO)and carbonates(MgCO3 and Li2CO3),in addition to Nd.The as-extruded alloy exhibited the best corrosion resistance after an initial soaking of 10 min,whereas the alloy with 4h-solution-treatment possessed the lowest corrosion rate after a longer immersion(1 h).This can be attributed to the formation of Nd-containing oxide film on the alloys and a dense corrosion product layer.The dealloying corrosion of the second phase was related to the anodic Mg41Nd5 with a more negative Volta potential relative to α-Mg phase.The preferential corrosion of Mg41Nd5 is proven by in-situ observation and SEM.The solid solution treatment of Mg-3Nd-1Li-0.2Zn alloy led to a shift in corrosion type from pitting corrosion to uniform corrosion under long-term exposure.     

铁氧化菌作用下316L不锈钢点蚀电化学特性的研究

采用电化学测量、交流阻抗技术、扫描电镜观察和能谱分析等实验方法,研究了316L不锈钢在铁氧化菌(IOB)溶液中的腐蚀电化学行为,分析了炼油厂冷却水系统微生物腐蚀的特征及机制,结果表明,在含有IOB溶液中的自腐蚀电位(Ecorr)、点蚀电位(Epit)和极化电阻(Rp)均随浸泡时间的增加呈现出降-升-降的变化趋势;在含有IOB溶液中的腐蚀速率均大于在无菌溶液中;IOB的生长代谢活动及其生物膜的完整性和致密性影响了316L不锈钢表面的腐蚀过程,使不锈钢表面的钝化膜层腐蚀破坏程度增加,加速了316L不锈钢的点蚀.