单相和双相不锈钢纳米涂层的电化学腐蚀行为

用磁控溅射技术在玻璃基体上制备由两种相组成(单相和双相)的不锈钢纳米涂层,利用动电位极化､交流阻抗技术及扫描电子显微镜研究两种不锈钢纳米涂层在0.25 mol/L Na2SO4 + 0.05 mol/L H2SO4 和 0.5 mol/L NaCl + 0.05 mol/L H2SO4溶液中的电化学腐蚀行为,观察相组成对纳米不锈钢涂层耐蚀性能的影响｡结果表明,与不锈钢单相涂层相比,不锈钢双相纳米涂层具有较差的抗局部腐蚀能力,其钝化膜的载流子密度远远大于不锈钢单相钝化膜的载流子密度,使得钝化膜的离子传输能力大大增强,从而降低了钝化膜的稳定性｡     

309不锈钢纳米涂层在酸性溶液中的电化学腐蚀行为

用动电位极化、恒电位极化及交流阻抗技术研究了 309 不锈钢及其溅射纳米涂层在 0.25 mol/L Na2SO4 0.05 mol/L H2SO4 和 0.5 mol/L Nacl 0.05 mol/L H2SO4溶液中的电化学腐蚀行为.结果表明,在 0.25 mol/L Na2SO4 0.05 mol/L H2SO4 溶液中,纳米涂层和不锈钢形成的钝化膜的抗腐蚀能力差别较小;而在 0.5 mol/L NaCl 0.05mol/L H2SO4 溶液中,纳米涂层的耐点蚀性能有了很大提高,这是由于纳米化使涂层表面形成的钝化膜更加致密、更加稳定;同时,通过容抗测量研究了纳米涂层和不锈钢钝化膜的电子结构,并提出了相应的腐蚀机制.     

304不锈钢在硝酸盐及硫酸溶液中的钝化

利用电化学方法和表面分析技术研究了304不锈钢在 硝酸盐及硫酸溶液中的钝化行为.结果表明，304不锈钢经硝酸盐及硫酸溶液中钝化后在3.5%NaCl溶液中的耐蚀性大为提高.SEM分析表明，经过H2SO4+KNO3钝化后，钝化膜具有网状的结构，膜层结合紧密；而单独在H2SO4溶液中钝化后，表面为有裂纹的钝化膜，微孔较多；单独在KNO3溶液中钝化，与未处理的基本相同.     

不锈钢电化学抛光及着金黄色工艺

通过正交试验和单因素试验研究了不锈钢电化学抛光及着色工艺。结果表明,在用14 g CrO3、30 mlC3H8O3、90 ml H3PO4、60 ml H2SO4和20 ml H2O配制的抛光液中,控制温度约80℃、电流密度约15 A/dm2,对不锈钢试片电化学抛光约10 min,其光亮度可达1级;在用21 g CrO3、60 ml H2SO4和100 ml H2O配制的着色液中,控制电流密度约0.60 A/dm2、温度70℃,对不锈钢电化学着色约3 min,其金黄色着色膜美观均匀、与基体结合力强、耐磨、耐腐蚀、耐高温。此工艺具有设备简单、可控性好、效率高、重现性好等优点。     

铁基非晶涂层在NaCl和H_2SO_4溶液中的钝化行为

采用超音速火焰喷涂(HVOF)方法制备了一种Fe Cr Mo Mn WBCSi非晶态合金涂层,测试并分析了非晶涂层组织、钝化膜成分及涂层在不同浓度Na Cl和H2SO4介质中的钝化行为,并与304不锈钢和ND钢进行对比.结果表明,非晶涂层由于钝化膜中高含量的Cr,Mo及W的氧化物,钝化区间宽,抗钝化膜破裂能力强,孔隙的存在降低其均匀腐蚀抗力.304不锈钢钝化膜破裂电位较低且与Na Cl溶液浓度密切相关.304不锈钢和ND钢只有在浓H2SO4溶液中具有较稳定的钝化特征,非晶结构有助于涂层在稀H2SO4溶液中形成更加稳定的钝化膜,厚度较小的涂层(200μm)具有较高的非晶相含量,形成的钝化膜较厚,耐蚀性更加优异.     

316L不锈钢钝化膜在Cl~-介质中的耐蚀机制

研究了 316L不锈钢在以硝酸为主体的氧化性介质中经过化学钝化处理形成的钝化膜在 3.5 %NaCl溶液中的电化学行为 ,运用X射线光电子能谱 (XPS)分析了钝化膜的组成与结构 ,运用交流阻抗技术研究了钝化膜的电性能 .结果表明 ,经过化学钝化处理后的成膜试样在Cl-介质中耐点蚀性能明显提高 ;钝化膜的主要组成元素Cr、Fe、Ni在膜中分别以Cr2 O3 、FeO、NiO存在 ;钝化膜呈p型半导体特性 .     

电化学氧化法再生不锈钢着色老化液的研究

通过循环伏安法测定了Pb及Pb-PbO2电极在1.0mol/L H2SO4介质中,Cr2(SO4)3发生电化学氧化的相关参数,选择Pb-PbO2电极为阳极,采用双室隔膜电解槽进行电化学氧化再生不锈钢着色老化液,确定了操作工艺条件如下:阴极支持液为5%的H2SO4溶液,阳极电流密度为5A/dm2。恒电流电解7.5h,三价铬转化率为25.97%,电流效率为68.45%。经过电化学氧化法再生后,老化液中的Cr6+即恢复至效用范围,用于着色不锈钢片能达到与新配制的着色液一致的效果。     

粘结剂成分对Ti(C,N)基金属陶瓷腐蚀行为的影响

研究了含38 wt% Ni或Ni–20Cr粘结剂的2种Ti(C,N)基金属陶瓷在0.2 M H2SO4和0.2 M NaOH溶液中的室温腐蚀行为。在0.2 MH2SO4溶液中,2种金属陶瓷的腐蚀行为和耐蚀性存在一些明显的差异：与以Ni作粘结剂的金属陶瓷不同,以Ni–20Cr作粘结剂的金属陶瓷浸泡过程中表面自发生成NiO、Ni(OH)x(SO4)y、Cr2O3和Cr(OH)3,致使粘结相溶解十分缓慢;动电位极化过程中不发生钝化,伪钝化后电流密度增加较快。在0.2 M NaOH溶液中,2种金属陶瓷的腐蚀行为和耐蚀性无明显差异：浸泡过程中陶瓷晶粒溶解十分缓慢,同时生成NiOOH和Cr6+化合物;动电位极化过程中不发生钝化,但发生伪钝化。     

316L不锈钢在不同pH值硼酸溶液中的电化学行为研究

采用动电位极化、电化学阻抗及Mott-Schottky技术研究了316L不锈钢在pH值分别为4,7和11的硼酸溶液中钝化膜的电化学行为,并对钝化膜成分进行了X射线光电子能谱分析。结果表明:316L不锈钢在酸性、中性和碱性硼酸溶液中均能形成稳定的钝化膜,且随p H值增加钝化电位区间减小,过钝电位显著下降。碱性硼酸溶液中316L不锈钢过钝电流显著增加。钝化膜完整性在中性硼酸溶液中最好,酸性溶液中最差。MottSchottky曲线结果表明,在酸性环境中随着电位的升高,钝化膜由n型向p型转变;在中性和碱性环境中,钝化膜半导体类型分别为n型和p型。这是由于随p H值增加,Cr的氢氧化物消失,钝化膜中Fe由Fe O(OH)转变为Fe_3O_4;在碱性环境下钝化膜中Cr_2O_3含量减少导致耐蚀性下降。     

含Ag抗菌双相不锈钢表面腐蚀产物的XPS分析

采用X射线光电子能谱技术(XPS)研究了含Ag抗菌双相不锈铸钢在有菌环境中经电化学极化后的表面腐蚀产物。结果表明:添加纯Ag颗粒制备的不锈钢经1150℃固溶处理后,其钝化膜表层中的Ag主要以Ag2+氧化物和游离态的形式存在,Cr主要以CrO2,CrO3和Cr(OH)3形式存在,而添加150～300μm Cu-Ag中间合金颗粒制备的不锈钢经1150℃固溶处理后,其钝化膜表层中的Ag主要以Ag2+,Ag+和Ag2/3+氧化物形式存在,Cr以CrO2、Cr2O3和CrO3等多价态铬氧化物形式共存,且与前者相比,添加150～300μm Cu-Ag中间合金颗粒制备的材料其钝化膜中Cr2O3、钼氧化物和MoO42-的含量更多,而α-FeOOH和Cr(OH)3等氢氧化合物以及水合物的含量更少,表明其钝化膜的稳定性优于添加纯Ag颗粒制备的材料。     

Eis and XPS study of surface modification of 316LVM stainless steel after passivation

The effects of surface finish, nitric acid passivation and ageing in air on corrosion resistance of 316LVM stainless steel in 0.5% H₂SO₄ have been investigated by EIS, potentiodynamic polarization measurements and XPS. The results indicate that a smoother surface exhibits to a higher corrosion resistance. The effectiveness of the passivation treatment strongly depends on nitric acid concentration, passivation time and temperature. The passivation treatment significantly increases the corrosion resistance due to a high Cr content in the passive film and increased film thickness. Ageing after passivation increases the corrosion resistance whereas ageing before passivation has little effect.     

Passivity of stainless steel in sulphuric acid under chemical oxidation

The main purpose of the present work was to study the passivity of stainless steel in sulphuric acid under chemical oxidation with H₂O₂ solution. Potentiodynamic polarisation and open circuit potential (OCP) measurements indicated that H₂O₂ facilitates the increase of OCP of stainless steel which shifts from active region into passive region. The X-ray photoelectron spectroscopy results suggested that a passive film, composed of oxyhydroxides, Cr₂O₃, Cr(VI) species, NiO, and sulphate (FeSO₄, Cr₂(SO₄)₃·xH₂O), is achieved after H₂SO₄–H₂O₂ passivation. The passive mechanism under H₂O₂ oxidation was discussed and the corrosion resistance of passive film was compared with that of the passive films produced by HNO₃ passivity and H₂SO₄ potentiostatic passivity. The results of electrochemical impedance spectroscopy, cyclic voltammetry, and anodic polarisation experiments confirmed that the chemical oxidation with H₂O₂ solution is capable of improving the corrosion resistance of stainless steel significantly and the passive film is more stable than those produced by other passivating methods.     

The preparation, characterization and corrosion behaviour of ion-implanted and ceramic-coated AISI 321 steel samples

Ion Beam Techniques were used to modify near-surface layers of austenitic stainless steel AISI 321 samples in order to improve their corrosion resistance. Mg-, Y- (implantation energy: 40 keV) and Al-implantation (implantation energy: 40, 60, 80 and 200 keV), as well as Dynamic Ion Mixing (DIM) (SiC deposition and mixing with 160 keV Xe ⁺ ions) and Sputtering (Si₃N₄ deposition with 15 keV Ar⁺ ions) were applied for this purpose. The characterization of the samples was performed using Nuclear Reaction Analysis (NRA) and ⁴He-Rutherford Backscattering Spectroscopy (RBS). The corrosion behaviour was investigated in 1N H₂SO₄ using cyclovoltammetry and potentiodynamic polarization. The values of the critical and passivation current density as well as of the corrosion, passivation and repassivation potentials, showed an increase of the corrosion resistance of the treated steel samples. This improvement is connected with the properties of the modified region (thickness, adhesion, formation of oxide films). The surface morphology and microstructure of the specimens before and after the corrosion experiments were investigated by Scanning Electron Microscopy (SEM).     

Role of nitrogen on the corrosion behavior of austenitic stainless steels

The role of nitrogen in the mechanisms of localized corrosion resistance and repassivation were electrochemically investigated using a nitrogen-bearing austenitic stainless (SUS316L) steel in 0.1 and 0.5 M Na₂SO₄ solutions and a 3.5% NaCl solution. Almost 100% of the nitrogen compounds dissolved into the bulk solution after crevice corrosion were transformed into NH₃. That is, the mole amount of ammonia in the solution was approximately equivalent to the mole amount of nitrogen dissolved in the steel. This suggests that NH₄⁺ consuming H⁺ in the pit controlled the local decrease of pH and promoted the repassivation. NO₃-N and NO₂-N were not detected by chemical analyses in the high potential and thermodynamically stable zone as NO₃⁻ in the potential-pH diagram. The repassivation in nitrogen-bearing SUS316L steel in a 0.1 M Na₂SO₄ solution was studied using the scratching electrode technique, which measured the partially destroyed passivation films on the steel. This technique showed that nitrogen dissolved in the steel has a strong repassivation capacity.     

不锈钢表面Cr-Pd合金电沉积及镀层在强还原性介质中的耐蚀性

通过选择络合剂、缓冲剂及采用方波脉冲电流和优化电镀工艺, 在酸性镀液中实现了Cr-Pd共镀, 并在不锈钢表面制备出均匀致密且与基体结合良好的Cr-Pd合金镀层. 通过改变镀液中铬盐和钯盐的相对含量, 可以大范围改变镀层成分. Cr-Pd合金镀层可显著提高不锈钢在高温还原性腐蚀介质中的耐蚀性, 在沸腾的20%(质量分数)H₂SO₄溶液中, Cr-Pd合金镀层使316L不锈钢的腐蚀速率降低了4个数量级以上. 镀层中的Cr和Pd对致钝具有协同促进作用, 当镀层中含有2.5%Pd(质量分数)时即具有明显的促进钝化效果, 含33.3%Pd镀层对不锈钢的保护效果与纯Pd镀层相当.     

The enhanced passivation of 316L stainless steel in a simulated fuel cell environment by surface plating with palladium

A thin layer of Pd deposition on the surface significantly improves the corrosion resistance of 316L stainless steel in 0.5 mol L⁻¹ H₂SO₄ + 2 ppm F⁻ solution at 80 °C. Compared with the air-formed passive film, the passive film formed in the stainless steel/Pd couple contains more Cr, Cr(OH)₃ and Fe₃O₄ and less point defects, which provides better protection to the stainless steel substrate. The interfacial contact resistance of the stainless steel surface is also decreased. The Pd plated stainless steel is a potential material for bipolar plates in proton exchange membrane (PEM) fuel cells.     

Anodic behaviour of stainless steel S43000 in concentrated solutions of sulphuric acid

Electrochemical, AES and XPS techniques were employed to characterize the anodic behaviour of S43000 stainless steel in concentrated sulphuric acid (90.0-96.4 wt.%). Electrochemical experiments showed that passivity is not spontaneous and requires anodic polarization in the acids studied. Rotating cylindrical electrode experiments showed that the corrosion rate is controlled by the mass transfer rate of FeSO₄ from a saturated surface salt. AES and XPS analyses provided evidence that passivity involves the formation of a chromium-rich oxide-hydroxide film. The passivation mechanism and passive state stability are considered to relate to the manner in which undissociated H₂SO₄ molecules participate in the corrosion process. The findings have meaningful implications regarding the development of more corrosion resistant stainless steels for acid service.     

在Q235钢表面原位生长的氧化铁膜对其在含Cl-溶液中腐蚀行为的影响Ⅰ-原位生长的γ-FeOOH膜的防护性能

    利用动电位极化曲线和交流阻抗谱等电化学测量技术,研究了Q235钢表面原位生长的γ- FeOOH膜在0.25 mol/L Na₂SO₄+10^-4mol/L NaCl、0.25 mol/L Na₂SO₄+10-3mol/L NaCl、0.25 mol/L Na₂SO₄+10^-2 mol/L NaCl水溶液中的电化学行为及在不同浓度的Cl^-水溶液中γ-FeOOH膜对Q235钢的保护作用.结果表明,Cl^-含量较低时,γ-FeOOH膜的存在明显地促进了Q235钢的阴极反应,该膜对基材无保护作用;随Cl-浓度的增加,阴极电流密度大幅减小,当Cl^-浓度达到10^-2 mol/L时,γ-FeOOH 膜能在一定程度上抑制基材的腐蚀,此时γ-FeOOH膜表现出对基材有保护作用.     

酸性介质中HR-2不锈钢表面活性的SECM三维图像表征研究

采用扫描电化学显微镜（SECM）,面扫描与线性扫描技术相结合,研究了HR-2不锈钢在0.5 mol/L H₂SO₄+0.1 mol/L NaCl溶液中的腐蚀行为。结果表明：HR-2不锈钢在该溶液中的开路电位、活化电位及钝化区电位分别为：-0.4 V、-0.23 V、0.0 V ~ 0.8 V,基底保持开路电位和活化电位时,探头最大电流为9.5 nA和35.2 nA,基底形成钝化膜后探头电流明显减小;当探头电位为-0.2 V时能有效氧化基底产生的H₂,0.6 V时能有效氧化基底反应产生的Fe₂₊,探头-基底间距为20 μm时,可较好地表征基底活性;当溶液中硫脲浓度为0.75 mmol/L时,有最佳的缓蚀作用。     

Comparative corrosion resistance of plasma-based low-energy nitrogen ion implanted austenitic stainless steel

A high nitrogen face-centered-cubic phase (γ_N) was obtained on the nitrided surface of 1Cr18Ni9Ti austenitic stainless steel by plasma-based low-energy nitrogen ion implantation. No pitting corrosion for the γ_N phase was confirmed by electrochemical polarization measurement in 3% NaCl solution. The protective passive film with a duplex character, iron hydroxide/oxides in the outer region and chromium hydroxide/oxides and iron oxides accompanying chromium and iron nitrides in the inner region, was by 2-3 times thicker than that of original stainless steel. The thick iron hydroxide/oxides region formed on the chromium hydroxide/oxides region due to the increase of alkalinity in the solution, leading to barrier against penetration of localized attack of the aggressive ions. The equivalent general corrosion resistance for the γ_N phase was observed in 0.5 mol/l H₂SO₄ solution relative to the original stainless steel. The passive film formed on the γ_N phase in 0.5 mol/l H₂SO₄ solution was similar to that of original stainless steel. The different role of nitrogen was proposed in pitting corrosion resistance and general corrosion resistance of austenitic stainless steel.