不锈钢的腐蚀破坏与防蚀技术（二）缝隙腐蚀

缝隙腐蚀是在电解质溶液(特别是含有卤素离子的介质)中,在金属与金属或金属与非金属表面之间狭窄的缝隙内,由于溶液的移动受到阻滞,在缝隙内溶液中的氧耗竭后,氯离子即从缝隙外向缝隙内迁移,又由于金属氯化物的水解酸化过程,导致钝化膜的破裂而产生与自催化点腐蚀相类似的局部腐蚀。这种腐蚀可能破坏机械连接的整体性和设备的     

Ti—75合金的耐蚀性

用重量法研究了Ti-75合金在60℃。3.5%NaCl溶液中的均匀腐蚀、缝隙腐蚀及对B30合金的接触腐蚀,并与TA5合金进行了对比。结果表明:该合金在上述介质中无论是均匀腐蚀、缝隙腐蚀敏感性,或是接触作用都略好于TA5合金,是较为理想的中强耐蚀结构材料。     

耐蚀合金在中性含氯离子环境中缝隙腐蚀预测方法的探讨

作者提出以合金均成的缝隙中溶液所能达到的稳定pH值与合金钝态受到破坏的去钝化pH值比较为判据,来判断合金在含氯离子的环境中会不会发生缝隙腐蚀,也即当pH稳定>pH去钝化,可判定该合金在应用中将是安全的,反之,当pH稳定≤pH去钝化,则该合金在恶劣条件下将发生缝隙腐蚀。设据此计了人工缝隙装置及酸化处理以获得缝隙中溶液的稳定pH值,并据此在模拟溶液中测定阳极极化曲线以确定是否出现活化峰,用这样的方法对已经公开发表的、有缝隙腐蚀挂片试验结果的六种合金进行了验证,其结果与Wilde海水挂片四年另三个月及上海钢铁研究所在广东湛江港口挂片一年的结果完全一致。用本方法对十种合金所作的预测也与它们在山东胜利油田含氯离子流动污水中挂片八个月的结果一致。     

不锈钢缝隙腐蚀的微区电化学行为及缝内钝化膜厚度的变化

利用微电极和椭圆偏振仪研究了2Cr13不锈钢在3.5%NaCl 溶液中的缝隙腐蚀历程。实验结果表明,不锈钢的缝隙腐蚀经历了三个阶段一孕育期,发展期和稳定期。缝内 pH 值下降和 Cl~-浓度增加均促进了钝化膜的溶解和加速了缝隙腐蚀。从孕育期向发展期的过渡中,存在着使合金钝化膜破裂的临界缝隙溶液(CCS)。在本试验条件下,其组成大约为 pH=3.5,[Cl~-]:1.2N。在孕育期,缝内钝化膜厚度随时间逐渐减薄,直到钝化膜肢裂,此时,缝隙腐蚀即进入发展期。微电极测试技术和椭圆偏振法可应用于不锈钢缝隙腐蚀过程的原位测试。     

低合金钢和碳钢在90℃地下水模拟溶液中的缝隙腐蚀

利用浸泡实验与电化学实验研究了低合金耐候钢CortenA和碳钢Q235在90℃地下水模拟溶液中的缝隙腐蚀行为.采用SEM,EDS和Raman光谱分析了缝内腐蚀产物膜的形貌和成分.结果表明,2种钢均发生了缝隙腐蚀,且随着腐蚀时间的延长缝隙腐蚀越严重;CortenA的缝隙腐蚀比Q235严重;在中性或偏酸性的溶液中,耐候钢的耐腐蚀性能优于碳钢,而在pH值为1的溶液中,耐蚀性则相反;合金元素Cr,Cu和Si对CortenA在溶液中的耐缝隙腐蚀性能不利.     

FeCrNiCo(Cu/Mn)高熵合金组织及腐蚀性能

采用电弧熔炼方法制备了FeCrNiCoCu及FeCrNiCoMn两种高熵合金,借助第一性原理模拟计算及腐蚀电化学测试技术,研究Cu、Mn元素对制备高熵合金在3.5%NaCl、5%NaOH和0.5 mol/L H2SO4溶液中的电化学腐蚀行为的影响规律。结果表明:FeCrNiCoCu及FeCrNiCoMn高熵合金均为单一的FCC结构,其中FeCrNiCoMn态密度达到最大值时对应的能量较低,结构更趋于稳定,耐蚀倾向性好。FeCrNiCoMn高熵合金在三种溶液中的耐蚀性均高于FeCrNiCoCu的,这是由于Cu元素的存在会引起元素偏聚,降低了合金的耐蚀性。而Mn元素以金属间化合物的形式存在,降低了合金中耐蚀性差的元素含量,提高了合金的耐蚀性。     

不同类型接触面对316L不锈钢缝隙腐蚀的影响

分别设计了金属-金属、金属-四氟乙烯、金属-橡胶、金属-塑料薄膜4种接触类型,探究不同类型接触面对不锈钢缝隙腐蚀的影响。对316L奥氏体不锈钢的缝隙构型进行FeCl3浸泡实验和电化学实验,研究了其对缝隙腐蚀行为的影响,通过激光共聚焦显微镜对缝隙腐蚀后样品的宏观形貌进行了研究。结果表明,金属-金属接触面条件下腐蚀形貌宽度最大,深度最浅,蚀坑横向发展,蚀坑达到一定深度后,腐蚀溶液横向扩散更容易。金属-橡胶接触面下腐蚀形貌宽度最小,深度最大,蚀坑纵向发展,这与橡胶所受应力有关,始终紧贴样品表面,腐蚀溶液不易发生横向扩散。电化学测试表明,不同类型接触面缝隙试样的破钝化电位相对于无缝隙试样均有明显降低。     

铝锌合金热镀层的缝隙腐蚀行为

通过设计缝隙腐蚀装置,应用电化学技术研究了55%Al-Zn-1.6%Si合金镀层在pH=5.5%NaCl溶液中的缝隙腐蚀行为.试验表明镀层的缝隙腐蚀符合自催化酸化闭塞电池机理;经钝化处理的合金镀层具有较好的耐缝隙腐蚀性能,缝隙腐蚀孕育期较未钝化镀层延长,腐蚀电流减小.     

库尔勒模拟溶液中HCO-3对X70钢缝隙腐蚀的影响

在含有不同浓度HCO-3的库尔勒模拟溶液中对X70钢楔形缝隙模拟构型进行缝隙腐蚀实验.实验结果表明,缝隙腐蚀理论不仅仅适用于单离子的溶液体系,也同样适用于含有多离子的溶液.实验过程中,当缝隙腐蚀发生时,从缝隙开口处到缝隙深处腐蚀电位越来越低,CI-向缝隙内富集,pH值降低.HCO-3的加入对缝隙电位、Cl-浓度、pH值都有较大的影响.     

TA19合金的耐蚀性能

研究了TA19合金在酸溶液中的均匀腐蚀和沸腾高浓度氯化物中的缝隙腐蚀.借助金相显微镜、X射线衍射和扫描电镜等进行试样分析.结果表明,TA19合金在室温、低浓度盐酸和硫酸中耐蚀性能良好,但在高温盐酸和硫酸中发生点蚀;在硝酸中耐蚀性能良好,表面生成锐钛矿TiO2;在沸腾高浓度氯化物中腐蚀速率极低,但发生缝隙腐蚀,腐蚀产物为氧化钛和氢化钛.     

Cu—Zn—Al形状记忆合金的缝隙腐蚀

采有利民化学方法研究了Cu-Zn-Al形状记忆合金及其BTA钝化处理试样在Hank′s人工体液中的缝隙腐蚀行为。结果表明：在人工体液中,Cu-Zn-Al形状记忆合金的耐缝隙腐蚀性能优于未进行热处理的Cu-Zn-Al合金,其作用机理是单相马氏体组织改善了合金的电化学行为,抑制了活性溶解,缝隙腐蚀的发生是由于形成了金属离子浓差电池。经BTA钝化后,Cu-Zn-Al形状记忆合金的耐缝隙腐蚀性能得到改善。     

藤壶附着对海水中金属腐蚀的影响

以室内试验为基础，观察了藤壶从附着到死亡全过程对四种海洋工程用金属材料腐蚀影响，并以海上试验结果作为对照，讨论了藤壶附着影响金属腐蚀的规律及机理。     

高温合金零件电刷镀时的腐蚀问题

分析了高温合金零件电刷镀时可能出现的腐蚀原因.通过工艺试验模拟了各种可能出现零件表面腐蚀的情况.结果表明,零件与夹具之间的导电性问题是腐蚀的主要原因,零件与夹具间形成的缝隙中有无镀液会改变腐蚀类型,只要保证导电性良好,在操作时间内零件不会发生明显的缝隙腐蚀.     

High Temperature Aqueous Corrosion Research at the National Physical Laboratory

Abstract

The susceptibility of stainless steels and high nickel alloys to crevice corrosion severely restricts their use for marine engineering applications. The development of crevice corrosion test procedures for alloy evaluation and development purposes is reviewed. As susceptibility to crevice corrosion is an inherent weakness of this type of alloy, it is suggested that it might in future be more rewarding to determine the design parameters required for the prevention of crevice corrosion by galvanic protection, rather than to pursue the continuing present investment in the quest for the development of an immune alloy.     

A clearer view of how crevice corrosion occurs

Crevice corrosion is a poorly understood and very damaging form of corrosion. This paper presents the essential characteristics of crevice corrosion established during the last four decades as well as some recent results that provide a fresh approach to understanding the process. A simple criterion has been developed that involves two factors. First is the current and resistance between the anodic reaction in the crevice and the cathodic reaction at the outer surface; second is the polarization curve. Practices for preventing crevice corrosion are also discussed. The size of the active peak in the polarization curve and, in particular, whether it increases or decreases can be used to determine whether or not a change in a system parameter (e.g., a solute addition to the alloy) will promote or inhibit crevice corrosion. A second indicator is whether the solution resistivity increases or decreases.     

Corrosion mechanism of aluminum alloy by ethylene glycol‐based solution

Corrosion and failure mechanisms on an aluminum (Al) alloy by ethylene glycol base solution have been studied. Extensive crevice corrosion damage and localized scale deposition are clearly observed between the failed Al alloy surface and the rubber hose, in which the leakage of ethylene glycol‐based solution occurred under an actual operating. In addition, many micro‐cracks are found at the rubber hose which is clamped with the Al alloy. The scales on the Al surface appear to be due to the occurrence of Al corrosion, followed by the precipitation of additives of ethylene glycol‐based solution in the crevice between Al alloy and rubber hose. The mechanisms that can account for the crevice corrosion and solution leakage on the Al alloy surface are discussed.     

三效连续蒸发结晶装置中TA10换热器的失效分析

目的 针对国内某化工厂氯化铝生产线上三效连续蒸发装置中换热器发生的换热管束泄漏事故,进行相应的失效分析,找出其原因,以避免相似的腐蚀失效事故再次发生.方法 采用宏观检测方法确定发生腐蚀的位置及腐蚀的宏观形貌,由全浸试验确定TA10合金在管、壳程工况下的耐蚀性,通过电镜扫描观察表面腐蚀的微观形貌,最后借助能谱分析和X射线衍射的方法确定腐蚀产物的成分.结果 换热器中挡流板被腐蚀,其表面金属发生大面积不规则剥落,换热管束外侧发生严重腐蚀,金属大面积剥落,管程出口处只有焊缝处发生明显腐蚀.TA10合金在管程工况下不会发生腐蚀,而在壳程工况下,会发生较为严重的腐蚀,腐蚀表面呈现出多层状结构,且表面形状无规则,生成的腐蚀产物为TiH2.结论 TA10合金在壳程工况下,并不能达到良好的耐蚀效果,现有工艺条件下,露点的产生使换热管外侧有高浓度盐酸产生,其会和TA10合金发生严重的吸氢反应,从而导致氢致开裂以及吸氢脆化,伴随气体的冲刷,便出现了金属大面积剥落现象,换热管与管板在连接处发生缝隙腐蚀,缝隙内钛作为阳极发生溶解.最后针对性地提出了防腐蚀建议.     

Electrochemical behavior of YAG laser-welded NiTi shape memory alloy

Electrochemical behaviors of laser-welded Ti-50.6%Ni（mole fraction） shape memory alloy and the base metal in 0.9% NaCl solution were investigated by electrochemical techniques as corrosion potential measurement, linear and potentiodynamic polarization. The results indicate that the laser-welded NiTi alloy is less susceptible to pitting and crevice corrosion than the base metal, which is demonstrated by the increase in polarization resistance（Rp） and pitting potential（φpit） and decrease in corrosion current density（Jcorr） and mean difference between φpit and φprot values. It is confirmed by scanning electron microscope micrographs that pits could be observed on the surface of base metal but not on the surface of laser-welded alloy after potentiodynamic tests. An improvement of corrosion resistance of laser-welded NiTi alloy could be attributed to almost complete dissolution of inclusions upon laser welding.     

SiCp/2024Al基复合材料的点蚀行为

采用动电位阳极极化法对17%SiCp/2024Al基复合材料及其基体合金在3.5%NaCl水溶液中的耐蚀性进行了研究.结果表明:SiC颗粒的加入并不影响SiCp/2024Al基复合材料的点蚀敏感性,但与基体相比,其耐蚀性有所下降.对极化后和长期浸泡试样的腐蚀形貌观察发现:与基体相比,SiCp/2024Al基复合材料表面上的蚀孔数量相对较多,蚀孔尺寸稍小,大小分布不均匀;最大蚀孔较深,并有严重的裂缝腐蚀;裂缝腐蚀的存在会使SiCp/2024Al基复合材料的点蚀抗力明显降低.能谱分析表明:SiCp/2024Al基复合材料的腐蚀机制为富Cu阴极相与贫Cu阳极相间的电偶腐蚀,另外,SiC与Al间也存在电偶腐蚀倾向.     

Numerical simulations study of the localized corrosion resistance of AISI 316L stainless steel and pure titanium in a simulated body fluid environment

The resistance of both AISI 316L stainless steel (AISI 316L SS) and commercially pure titanium (cpTi) to localized corrosion in a simulated body fluid solution was investigated using numerical simulations. The resulting model, based on transport equations in dilute solutions, is designed to predict the susceptibility of these two biomaterials to crevice corrosion initiation. The results show that cpTi and AISI 316L SS alloy are very resistant to the initiation of crevice corrosion in 0.9% NaCl solution and AISI 316L SS alloy is more susceptible to corrosion initiation over the long term than cpTi.