Influence of the surface state on the Initiation of Crevice Corrosion on stainless steels

Results from sea-water and laboratory exposure tests with multiple crevice assemblies are presented. The results from tests on austenitic and ferritic-austenitic stainless steel samples subjected to various surface treatments demonstrate that an acid treatment greatly improves the crevice corrosion resistance of previously ground surfaces. Pickling in dilute sulphuric acid and passivation in nitric acid has thereby virtually the same beneficial effect as the common nitric + hydrofluoric pickling acid. The beneficial effect of pickling and passivation is related to the removal from the surface of sulphide inclusions, being potential nucleation sites for the initiation of discrete pitting attacks preceding the onset of crevice corrosion. Potentiodynamically determined pitting potentials and results from testing in 10% FeCl₃ · 6 H₂O according to ASTM G 48–76 show poor correlation with results from sea-water exposures.     

Einfluß von Passivierungs- und Kohlenstoffschichten auf austenitischen CrNiMo-Stählen auf die Beständigkeit gegen Lochfraß und Spannungsrißkorrosion

Effects of passivation and carbon films on austenitic CrNiMo steels on their piting and stress corrosion resistance The influence of passive film and combinations of a passivation and a carbon layer on the resistance to pitting and SCC of austenitic CrNiMo steels has been investigated in physiological sodium chloride solution (Tyrode solution) at pH 6.9 to 7.4 at 37 ± 1°C. The passive film was obtained after electrolytic polishing in H₃PO₄ + H₂SO₄ + C₆H₅NHCOCH₃ + oxalic acid + corrosion inhibitor CS by treatment with 40% nitric acid the carbon film was obtained by CVD. Impurities in the steel (non-metallic inclusions) and the different metallic phases were investigated and the chemical composition of the passive film was determined by quantitative analysis. The resistance to pitting of the steel with and without passive film was determined potentiodynamically in Tyrode's solution at 37 ± 1°C. The resistance to SCC was determined in Tyrode's solution at 37 ± 1°C, in neutral glycerole and in boiling magnesium chloride solution at 154 ± 1°C and evaluated in terms of K_σ and K_τ. The corrosion damage was investigated by optical and scanning electron microscopy. The investigations have revealed that the different surface conditions considerably improve the pitting and SCC resistance of the steels in the media used in this work, so that they make possible the use of these materials as surgical implants.     

Improvement on the pitting corrosion resistance of 304 stainless steel via duplex passivation treatment

A remarkable improvement in the pitting corrosion resistance of 304 stainless steel was attempted using a novel duplex passivation treatment method. First, chemical passivation in nitric acid followed electrochemical passivation via potential polarization of step cycling in sodium nitrate electrolyte. Compared with traditional chemical passivation, breakdown potential was increased from 0.31 V_SCE to positive than 0.9 V_SCE at 70°C in a solution bearing 0.6 M [Cl^?] concentration. The critical pitting temperature was enhanced from 21.5°C to above 70°C in a solution with 6 M [Cl^?] concentration. Impedance analysis and X‐ray photoelectron spectroscopy results show that a more compact passive film with a higher ratio of chromium oxide on iron oxide was achieved by electrochemical passivation compared with chemical passivation. Morphology observation suggested that the potential polarization of step cycling slightly increased the dissolution of inclusions after being subjected to chemical passivation. The probable reason for the improvement on pitting resistance is discussed in detail based on inclusion dissolution and the protectiveness in passive film.     

高pH值完井液中钛合金管材的腐蚀行为研究

基于高温高压腐蚀速率和原位电化学测试,并结合分子动力学模拟和第一性原理计算,探讨了钛合金(TC4)管材在高pH值完井液中的腐蚀行为,以及钝化膜的热力学稳定性。结果表明:TC4钛合金在180℃的高pH值磷酸盐完井液中的腐蚀极为严重,其均匀腐蚀速率高达0.4429mm/a;在高pH值磷酸盐完井液中,TC4钛合金的腐蚀为阳极反应过程控制,随着温度的升高,其腐蚀电位、腐蚀产物膜的膜阻和极化电阻显著降低,腐蚀反应的热力学驱动力增大、动力学阻力降低,腐蚀电流密度显著升高;在碱性溶液中,TiO_2钝化膜的钛氧键发生不同程度断裂,并且随着温度升高、碱性增强,TiO_2与溶液的界面结合能逐渐增大,钝化膜的热力学稳定性明显降低;在碱性焦磷酸钾溶液中,TiO_2钝化膜均可与K_2HPO_4、K_3PO_4反应生成疏松多孔的KTiOPO_4腐蚀产物膜,但TiO_2与K_3PO_4反应的热力学倾向更大。     

复配BTA与TTA钝化纯铜工艺研究

目的为了提高纯铜表面的耐腐蚀性。方法通过苯并三氮唑(BTA)与甲基苯并三氮唑(TTA)复配,对纯铜进行钝化,并分析钝化温度、时间及pH值对纯铜钝化效果的影响。分别运用电化学法、硝酸点滴实验、中性盐雾实验、SEM等手段对不同钝化液钝化膜的微观结构与耐蚀性能进行研究,并与铬酸盐钝化结果进行对比。结果将4 g/L BTA、4 g/L TTA复配,辅以氧化剂20 m L/L H_2O_2,对纯铜以pH值为4、钝化时间3 min、钝化温度40℃、自然风干老化1 d的钝化工艺处理后,可以生成明显的钝化膜。其表面致密,耐蚀性较好,在盐雾试验中腐蚀缓慢,其平均腐蚀速率为0.76 mg/d,自腐蚀电流密度仅为1.5660μA/cm2,缓蚀率达到81.9%,接近铬酸盐钝化的抗腐蚀效果。结论在适宜的钝化工艺下,经过BTA与TTA复配钝化后,可以在基体表面生成Cu/Cu_2O/Cu(I)BTA聚合物保护膜,同时TTA的非极性甲基形成的单分子层膜的疏水性更好,两者共同作用,形成较为致密的钝化膜覆盖在铜基体表面,明显提高纯铜表面耐蚀性。     

Cu-Ni合金BTA复配体系钝化处理工艺研究

采用苯并三氮唑(BTA)复配钝化体系对B10 Cu-Ni合金进行钝化处理,以提高其在含硫化物环境介质中的耐腐蚀性能,并研究工艺参数对钝化膜耐蚀性的影响规律.利用动电位极化曲线和电化学阻抗谱研究钝化膜的耐腐蚀性能,采用X射线光电子能谱分析钝化膜的化学成分.实验结果表明,在BTA与磺基水杨酸组成的复配体系中形成的钝化膜比BTA单一体系中形成的钝化膜具有更高的耐蚀性,这是磺基水杨酸与基体合金反应形成的络合物膜与Cu(I)BTA膜协同作用的结果;钝化处理的时间和温度是影响钝化膜耐蚀性的重要工艺参数,延长钝化时间和提高钝化温度均可以提高钝化膜的耐蚀性,60℃高温条件下5 min的钝化处理即能够达到常温条件下3 h的钝化处理效果.     

Effects of nitric acid passivation on the corrosion behavior of ZG06Cr13Ni4Mo stainless steel in simulated marine atmosphere

ZG06Cr13Ni4Mo martensitic stainless steel was nitric acid-passivated to improve its corrosion performance. The effects of nitric acid passivation on the surface morphology, chemical composition, electrochemical properties, semiconductor behavior, and long-term corrosion performance of the stainless steel were investigated using various analytical techniques. An in-depth analysis of X-ray photoelectron spectroscopy (XPS) showed that the passive film formed after the acid passivation process showed high thickness and a duplex character as it consisted of a hydroxide layer and an oxide layer. The oxide layer affected the corrosion resistance and thickness of the passive film. The thickness of the passive film was calculated theoretically as well as experimentally by fitting the electrochemical impedance spectroscopy and XPS results. The electrochemical tests revealed that the dramatic increase in the corrosion resistance of the stainless steel after the passivation was due to the formation of a thick, low-disorder passive film rather than Cr enrichment. The removal of inclusions resulted in higher pitting resistance, whereas the increased roughness showed a negative effect on the corrosion behavior of the stainless steel. During the wet–dry cyclic tests, the modification of the passive film was examined. The passivated stainless steel exhibited good corrosion resistance for up to 50 days of exposure in the simulated environment.     

热镀锌板表面无机组分与有机硅烷复合钝化膜

以硅烷偶联剂KH560和KH602复配出有机硅烷钝化组分,再加入双氧水改性的TiOSO4和Na3VO4无机组分,配制出无机组分-有机硅烷复合钝化液。通过电化学Tafel极化曲线、交流阻抗谱(EIS)和中性盐雾试验,对比了未钝化镀锌板、添加和未添加无机组分钝化的镀锌板的耐蚀性;通过附着力测试,评价了两种钝化膜层的附着性能;通过扫描电子显微镜,对比了三种试样表面的微观形貌。结果表明:加入无机组分能有效改善钝化膜的耐蚀性,提高膜层表面结构的致密性,从而形成耐蚀性好、附着力强、表面均匀、结构致密的复合钝化膜。     

不锈钢电化学着黑色工艺与成膜机理研究

采用电化学着色法对不锈钢着黑色进行了研究,讨论了钝化处理、着色液组成等因素对着色的影响,测定了着色膜的耐磨性和耐蚀性,并根据着色膜的组成、微观结构分析了成膜机理.结果表明:钝化和封闭处理能明显提高着色膜的耐磨性和抗色变性;电化学分析表明在1 mol/L H2SO4溶液、3.5%NaC l溶液和10%NaOH溶液中,着色膜腐蚀电位比不锈钢基体分别正移1130、565和790 mV,且腐蚀电流密度都比相应介质中的小;扫描电镜和能谱结果显示膜层为封闭块状结构,着色膜主要成分是Fe、Cr、Mn等元素,封闭处理能明显减少其裂纹数目.该成膜反应机理为:1)不锈钢基体的溶解形成大量的M e2+;2)金属/溶液界面上的M e2+与Cr3+水解形成合金氧化膜沉积在基体表面上;3)电化学致密过程中4H2MoO4+2SO42-+4H+2(MoO)2SO4+6H2O+6[O]和M e+[O]=M eO反应是着色膜致密的主要原因.     

Enhancing General Corrosion Resistance of Biomedical High Nitrogen Nickel-Free Stainless Steel by Nitric Acid Passivation

A systematic study of nitric acid passivation was investigated to enhance the general corrosion resistance of biomedical high-nitrogen nickel-free stainless steels(HNSs).After passivation,the corrosion rate of HNS could dramatically reduce to 1/20 of the untreated in 37℃0.9 wt% NaCl solutions.Then,the passive film on HNS was analyzed by X-ray photoelectron spectroscopy.It was found that chromium enrichment in the passive film and nitrogen enrichment in the film/metal interface contributed to the improvement in general corrosion resistance of HNS.     

硅烷-钼复合无铬钝化膜的耐蚀性及标准曲线构建

为更好地指导新型硅烷-钼复合无铬钝化膜的工业化生产,研究钝化膜的耐蚀性能,构建皮膜量标准曲线。分别使用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)分析钝化膜的物相组成和表面元素价态。利用中性盐雾试验和电化学测试,探讨钝化膜的耐蚀性能。采用X射线荧光光谱法(XRF),绘制和构建皮膜量标准曲线。结果表明:硅烷-钼复合无铬钝化膜层中Si、Mo元素能分别与Zn形成化学键,膜层结合性较好。膜层耐蚀性在一定范围内随着膜层皮膜量升高而升高,当皮膜量高于800 mg/m2时,耐蚀性趋于稳定,其耐蚀性与稳定性接近Cr6+。此外,皮膜量与XRF射线强度呈线性关系,斜率为3.413。     

热镀锌板三价铬钝化剂的制备及其钝化膜耐蚀性能

目的制备钝化膜耐蚀性良好的热镀锌板三价铬钝化剂。方法以铬酸酐、酒石酸盐、无机混酸、纳米硅溶胶为原料,制备三价铬钝化剂。采用该钝化剂对热镀锌板进行钝化处理,通过中性盐雾试验、Tafel极化曲线和交流阻抗谱分析钝化膜的耐蚀性能,并表征钝化膜的表面形貌和元素组成。结果钝化镀锌板经120 h中性盐雾试验后,腐蚀面积仅为5%。与未钝化镀锌板相比,钝化试样的自腐蚀电位有所正移,自腐蚀电流密度降低了约2个数量级。钝化膜表面较为平整,有少量白色颗粒沉积,膜中主要含有C,O,Si,Cr,Zn等元素,且Cr主要以三价和六价存在,Zn以二价存在。结论该三价铬钝化剂可提高镀锌板的耐蚀性能,具有较好的工业使用推广价值。     

Effect of temperature on copper corrosion in high-level nuclear waste environment

The effect of temperature on the corrosion behavior of copper in simulated high-level nuclear waste environment was systematically studied. Electrochemical methods, including electrochemical impendence spectra, Mott–Schottky technology, cyclic polarization, and potentiostatic polarization, were employed to characterize the corrosion behavior of copper at different temperatures. Stereoscopic microscopy and scanning electron microscopy were used to examine the surface morphology, and X-ray photoelectron spectroscopy analysis was used to identify the composition of the passive film. The experimental results show that corrosion resistance of the passive film does not blindly decrease with the increase of temperature but increases at 60 °C owing to a compact outer layer; there is a potential for pitting corrosion, which decreases as the temperature increases. The main product of copper in an anaerobic aqueous sulfide solution is Cu₂S but the content of CuS increases at higher temperatures. The whole passivation range shows p-type semiconductor characteristics and the magnitude of the acceptor density is 10²³ cm^?3, which increases with increasing temperature.     

Cerium chemical conversion coatings for corrosion protection of stainless steels in hot seawater environments

In order to replace the hazardous chromate‐based surface treatment, a new cerium chemical conversion coating was developed on 316L stainless steel through a mixed solution of hydrated cerium nitrate, citric acid, and hydrogen peroxide. The chemical composition was characterized by energy‐dispersive spectroscopy, X‐ray photoelectron spectroscopy and atomic force microscope. The dense conversion coating is composed of CeO₂ with a small amount of Ce₂O₃ and has small grain size lower than 50 nm. Its thickness is about 47.4 nm as determined by spectroscopic ellipsometry analysis. Potentiodynamic polarization was used to study the corrosion behavior of the coatings in the concentrated artificial seawater at 72 °C. In comparison with the conventional nitric acid‐chromate passivated specimens, the cerium conversion coatings show much higher pitting potentials. It is suggested that the cerium conversion treatment is more effective than the nitric acid‐chromate passivation to improve the pitting resistance of 316L stainless steel used in the hot seawater environments.     

Ni/Cu定向结构涂层在不同浓度H2SO4中的耐蚀性能

为了研究Cu元素对Ni基合金定向结构涂层耐腐蚀性能的影响,向Ni60合金粉末中添加了5%Cu(质量分数,下同),制备了定向结构Ni60/Cu复合涂层。采用电化学试验和浸泡试验,评估了涂层在不同浓度H₂SO₄溶液中的电化学腐蚀特性和浸泡腐蚀性能,探讨了涂层在不同浓度H₂SO₄溶液中的腐蚀行为。结果表明,涂层在不同浓度H₂SO₄溶液中的腐蚀均表现为活化-钝化-过钝化的过程,电化学阻抗谱在整个时间常数内具有典型的容抗特征,H₂SO₄溶液浓度从5%增至80%时,电荷转移电阻先减小后增大,涂层的耐腐蚀性呈现先降低后升高的趋势。随着H₂SO₄溶液浓度的增加,涂层表面的腐蚀程度先加剧后逐渐减缓,且在H₂SO₄溶液浓度为40%时,腐蚀电位移至最负,腐蚀电流密度增至最大。但在H₂SO₄溶液浓度达到80...     

Corrosion behavior and surface film characterization of TaNbHfZrTi high entropy alloy in aggressive nitric acid medium

Corrosion behavior of TaNbHfZrTi high-entropy alloy (HEA) was investigated in nitric and fluorinated nitric acid at ambient (27 °C) and boiling (120 °C) conditions. The alloy passivated spontaneously during potentiodynamic polarization in 11.5 M HNO₃ at ambient condition. The corrosion rate was negligible in boiling 11.5 M HNO₃, exposed for 240 h. Scanning electron microscopic (SEM) studies did not show any significant corrosion attack. The high corrosion resistance of TaNbHfZrTi HEA was attributed to its single phase bcc structure. X-ray photoelectron spectroscopic (XPS) analysis revealed that the protective passive film formed in boiling nitric acid was predominantly composed of Ta₂O₅, in contrast to the presence of ZrO₂ and HfO₂ in air-formed native film. Potentiodynamic polarization studies indicated a pseudo-passivation behavior of the HEA in 11.5 M HNO₃ + 0.05 M NaF at ambient condition. In boiling fluorinated nitric acid, SEM images of TaNbHfZrTi HEA displayed a severely corroded morphology indicating the instability of the metal-oxides of the alloying elements. XPS investigations confirmed the presence of ZrF₄, ZrOF₂ and HfF₄ along with un-protective oxides of Ta, Nb and Ti on the film, resulting in decreased corrosion resistance of TaNbHfZrTi HEA in fluorinated nitric acid.     

Corrosion characterization of new tin-silver binary alloys in nitric acid solutions

Electrochemical techniques were used to characterize the corrosion behavior of four new binary alloys xSn-Ag (x = 26, 50, 70 and 96.5 wt%) alloys and their individual metal components in nitric acid solutions. The experimental data were collected by using open-circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Over the concentration range studied (0.075-4.5 M), each of the two corrosion parameters (E_corr and i_corr) shows a regular dependency on both the alloy composition and the solution concentration. In general, for all studied samples, especially pure Ag and those with lower Sn contents (26 and 50 wt%), increasing the acid concentration increases i_corr, meanwhile causes a shift of the corresponding E_corr towards more positive values. This is probably due to the increase in the effect of cathodic depolarizer as the nitric acid concentration is increased. EIS results at the free corrosion potential confirmed well this behavior, where at concentrations ?1.5 M the thickness of the surface film increases while its resistance decreases with increasing tin wt%, indicating formation of less protective thicker film. However, at higher concentrations all samples exhibit identical behavior.     

钝化处理对Al-B4C复合材料腐蚀行为的影响

采用三乙醇胺溶液对Al-B4C复合材料进行了表面钝化处理,通过电化学试验和浸泡腐蚀试验研究了钝化处理对Al-B4C复合材料腐蚀行为的影响。结果表明:钝化处理使Al-B4C复合材料表面生成双层结构的氧化膜,非晶内层氧化膜厚度约为2.5μm,外层氧化膜由三斜相和单斜相的Al(OH)3构成,厚度小于1μm;钝化处理后的AlB4C复合材料具有较大的极化电阻,表现出较好的耐腐蚀性能;经40℃硼酸溶液浸泡腐蚀1000h后,钝化Al-B4C复合材料的腐蚀质量增加和金属离子溶出显著低于未钝化Al-B4C复合材料的,说明钝化处理形成的氧化膜,能有效地提高Al-B4C复合材料的耐腐蚀性能。     

纳米 SiO2的改性及其对水性聚氨酯树脂复合涂层性能的影响

在乙醇水溶液中,用硅烷偶联剂KH560对纳米SiO2进行表面改性处理,通过测定粒径,探讨了纳米SiO2含量、乙醇水溶液配比以及改性剂含量对分散性的影响。将改性后的纳米SiO2分散液、水性聚氨酯树脂及无机组分等复配成无铬钝化液,在热镀锌板上制备钝化膜,通过电化学Tafel极化曲线、交流阻抗以及中性盐雾试验对比纳米SiO2改性聚氨酯复合钝化膜和未改性聚氨酯复合钝化膜的耐蚀性,结果表明,与后者相比,前者的耐腐蚀性能有了较大的提升。     

Cerium-tannic acid passivation treatment on galvanized steel

A novel cerium-tannic acid passivation treatment was performed on galvanized steel. The corrosion resistance of cerium-tannic passivated samples was tested by dropping test with 0.5 wt.% CuSO₄ aqueous solution. The mass loss per unit area of passivated samples was measured after the corrosion in 0.5 mol/L NaCl + 0.005 mol/L H₂SO₄ at room temperature for 96 h. The electrochemical behaviors of cerium, tannic acid, and cerium-tannic acid passivated samples on galvanized steel in 0.5 mol/L NaCl solution were investigated by polarization curves and electrochemical impendence spectra. The corrosion equivalent circuit was established according to the impedance characteristics. The results show that cerium-tannic acid treated samples exhibit better corrosion resistance than the sole cerium or tannic acid treated samples under the same condition. The mechanism of synergistic effect for cerium-tannic acid passivation on galvanized steel was discussed.