铬铝复合钝化膜的XPS研究

对Fe-Cr、Fe-Al、Fe-Cr-Al和Fe-Mn-Al-Cr合金的钝化膜进行了XPS分析研究,并在0.5mol/L H_2SO_4中测定了它们的阳极极化曲线。结果表明:在上述合金的钝化膜中,均出现Cr、Al的富集,但在Fe-Cr-Al合金的钝化膜中,Cr的富集受到抑制。经计算,铬在膜中富集因子ηCr在Fe-5Cr合金为3.7,而在Fe-5Cr-3Al合金的膜中为2.2,在Fe-26Mn-3Al-6Cr合金的钝化膜中,Cr的富集未受到抑制,ηCr,为3.53,与Fe-5Cr的相当。可见,Fe-Mn-Al-Cr合金Cr、Al复合钝化膜的钝性优于同等含Cr量的Fe-Cr合金,更加优于同等Cr、Al含量的Fe-Cr-Al合金。     

Cr对Fe-Cr合金耐蚀性能影响的电子理论研究

基于固体与分子经验电子理论(EET),对Fe-Cr合金(Cr含量为0~30%,原子分数)的价电子结构进行了半定量分析,利用界面电子密度差Dr的计算方法,计算了Fe-Cr合金与Cr_2O_3、Fe_2O_3钝化膜低指数晶面间的电子密度。结果表明,Fe-Cr合金固溶体的杂化原子轨道数sn、最强键共价电子数nA和最强键键能EA均大于纯Fe,Cr能提高Fe基体的稳定性。当Cr含量达到12.52%和24.3%时,Cr原子从低阶迁移到共价电子数少的高阶状态,不稳定性增加,此时Cr易偏离平衡位置与腐蚀介质作用形成钝化膜,造成Fe-12.52%Cr和Fe-24.3%Cr合金的耐腐蚀性能发生突变。Fe-Cr合金与Cr_2O_3、Fe_2O_3钝化膜的24个低指数界面中,只有Fe-Cr(112)/Cr_2O_3(0001)、Fe-Cr(112)/Cr_2O_3(1010)_(Cr)、Fe-Cr(112)/Fe_2O_3(11 20)界面的Dr10%,对于同等Cr含量的基体,Fe-Cr(112)/Cr_2O_3(1010)_(Cr)界面Dr最小,满足Dr10%的杂化原子轨道数s最大。随着基体中Cr含量升高,Fe-Cr(112)/Cr_2O_3(0001)和Fe-Cr(112)/Fe_2O_3(11 2ˉ0)界面Dr降低,s增加,Cr_2O_3、Fe_2O_3与基体的界面更加稳定牢固,因此Fe-24.3%Cr合金的耐腐蚀性可跃迁至更高水平。价电子结构对Fe-Cr合金耐蚀性能变化的分析结果基本符合Tammann定律的描述。     

氮对00Cr18Ni5Mo3Si2双相不锈钢抗孔蚀性能的作用

用浸泡腐蚀试验、电化学测试及表面分析技术研究了合金元素氮对双相不锈钢抗孔蚀性能的作用。试验结果表明加入氮使孔蚀电位升高并有利于奥氏体中含有更多的cr、Mo及Si,因而改善了双相成份分布。氮增强了Cr及Mo在钝化膜中.特别是在奥氏体上的形成的钝化膜中的富集,从而提高了膜的稳定性。     

海水流速对经抛光和钝化表面处理的2205不锈钢点蚀的影响

采用动电位极化曲线、电化学阻抗谱以及Mott-Schottky曲线等电化学测试方法研究了2205不锈钢管路材料在流动海水中的耐点蚀性能,并对测试后的试样进行了腐蚀形貌观察。结果表明,抛光状态和钝化状态下,试样表面均出现了明显的点蚀形貌,点蚀电位在0.9～1.2 V之间。在静态环境中材料的耐点蚀性要强于流动海水中;随着流速上升,材料的耐点蚀性并未发生明显变化,但表面钝化膜在流动海水中失去了再钝化能力。2205不锈钢表面钝化膜呈现n型和p型两种半导体特征,说明不锈钢表面钝化膜呈现双层结构,主要由外层Fe的氧化物和内层Cr的氧化物组成。钝化处理后试样的耐点蚀性能有所上升,但钝化膜的半导体性质未发生明显变化。海水冲刷使得不锈钢耐点蚀性能下降,不同表面处理的2205不锈钢在海水冲刷下表面钝化膜特性差异导致不锈钢点蚀敏感性不同。     

Fe-20Cr溅射纳米涂层的腐蚀电化学性能研究

利用电化学方法与表面分析技术，考察了平面磁控溅射Fe—20Cr纳米涂层的腐蚀电化学性能及耐蚀机制．研究表明，尽管溅射纳米涂层钝化膜的溶解速度高于铸态合金，但其钝化趋势较强，即使在含有0．5mo1／L NaCl的H2SO4溶液中仍能自钝化，而此时铸态合金的钝化趋势非常微弱；纳米涂层的耐点蚀能力也远优于铸态合金；晶粒细化以及铬元素分布均匀性是决定溅射纳米涂层耐点蚀能力的关键因素．     

铁基非晶合金和13Cr不锈钢在超临界CO2环境的腐蚀行为

非晶合金由于其独特的结构、优异的耐磨耐蚀性能在海洋及CO₂地质封存领域展现出广阔的应用前景,有望成为超临界CO₂环境下钢构件的耐蚀涂层材料,但关于非晶合金在该环境下的腐蚀行为鲜有报道。利用高温高压反应釜对SAM2X5铁基非晶合金与13Cr马氏体不锈钢在温度80℃,压力10 MPa的模拟环境下进行腐蚀行为对比研究。通过XRD、DSC、CLSM、SEM、XPS以及电化学Mott-Schottky测试等方法对两种材料的微观结构、腐蚀形貌以及表面膜成分及结构进行表征与分析。研究结果表明：在高温高压的超临界CO₂环境下进行168 h腐蚀试验后,13Cr不锈钢表面发生严重的点蚀,而铁基非晶合金表面无点蚀发生;非晶合金表面膜除Fe和Cr外,富含大量的Si元素,会促进形成稳定致密的钝化膜;13Cr不锈钢表面膜为p型半导体,非晶合金表面膜为n型半导体,13Cr不锈钢钝化膜载流子密度远高于铁基非晶合金。证实了在该环境下铁基非晶合金的耐蚀性能远优于13Cr不锈钢。     

304不锈钢环保型酸洗钝化工艺及其性能研究

采用化学浸泡法和动电位扫描法研究了304不锈钢在环保型酸洗钝化工艺下所得钝化膜的耐点蚀性能,运用X射线光电子能谱(XPS)分析了钝化膜的组成和结构.结果表明:由正交试验优选出的最优配方和工艺可大大提高304不锈钢表面钝化膜的耐点蚀性能;304不锈钢表面钝化膜中的Cr、Fe、Ni分别以Cr2O3、FeO、NiO的形式存在;钝化处理后,试片表面钝化膜中的铬元素和镍元素的含量明显增加.综合考虑,不锈钢柠檬酸钝化的最佳工艺为:柠檬酸质量分数4%,氧化剂X体积分数5%,乙醇体积分数2.5%,温度40℃,钝化时间60min.     

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 .     

镍基合金G3在高含H2S和CO2环境中的腐蚀行为

采用高温高压模拟腐蚀试验、动电位扫描技术和X射线光电子能谱仪(XPS)等手段研究了镍基合金G3在高含H2S和CO2腐蚀环境中的腐蚀行为。结果表明,在高温高压(90℃,32 MPa,pH2S为3.4 MPa,体积分数10.49%,pCO2为3.3MPa,体积分数为10.41%)的模拟气田采出液中,镍基合金G3发生了明显腐蚀,腐蚀产物由片状晶粒构成;在含50%H2S气田采出水中加入CO2促进了合金的腐蚀,当CO2的体积分数进一步提高到50%,合金点蚀敏感性下降;在50%H2S和50%CO2环境中,Cl-提高了合金点蚀敏感性,同时高浓度Cl-破坏了合金钝化膜自修复能力,G3在该腐蚀环境中形成的钝化膜由Cr2S3,Cr2O3,FeS,Fe2O3,Ni(OH)2和MoO3等组成。随着使用环境条件的恶化,合金钝化膜遭到破坏,腐蚀加速。     

生物医用Ti-Nb-Ta-Zr-Fe合金在林格溶液中的腐蚀行为（英文）

采用动电位极化方法研究Ti-25Nb-10Ta-1Zr-0.2Fe(质量分数%)(TNTZF)合金37℃下在林格溶液中的抗腐蚀性能,并在同样的条件下用Ti-6Al-4V-ELI(低间隙)合金做对比实验。结果表明:TNTZF比Ti-6Al-4V-ELI合金表现出更高的腐蚀电位,更低的腐蚀电流密度,更加稳定的钝化电流密度和更宽的钝化区间,因此具有更加优越的抗腐蚀性能。除此之外,在Ti-6Al-4VELI合金的表面钝化膜上观察到了点蚀现象,但是在TNTZF合金表面没有发现点蚀现象。XPS分析结果表明:TNTZF合金表面钝化膜由TiO_2基体以及Nb_2O_5、NbO_2、Ta_2O_5、ZrO_2、TiO和Ti_2O_3等氧化物共同组成,从而使得钝化膜更加稳定且保护作用更强,因此TNTZF合金比Ti-6Al-4V ELI合金表现出更加优越的抗腐蚀性能。     

Augerspektroskopische Untersuchungen zur Lochkorrosion von Fe-Cr-, Fe-Mo- und Fe-Cr-Mo-Legierungen

Auger-spectroscopic investigations into pitting corrosion of FeCr, FeMo and FeCrMo alloys A single pit was produced on binary iron-chromium (Fe17Cr), iron-molybdenum (Fe1Mo, Fe3Mo, and Fe5Mo) and ternary iron-chromium-molybdenum alloys (Fe17CrxMo, x = 1, 3, 7 wt.%) in 0.5 M H₂SO₄ with Cl^? additions (0.02 to 0.08 molar) at room temperature. Compositional changes at the bottom of the pit and in the surrounding passive film were determined using high resolution Auger-Electron Spectroscopy (AES). The chromium and molybdenum content of the passive layers are not changed in the presence of Cl^? and there is no incorporation of chlorine in the passive film as long as the films were formed in a chlorine-free electrolyte and Cl^? was added later. At the bottom of the pits salt films could be determined in all cases after removing the electrolyte with filter paper. These salt films are strongly enriched in chromium, molybdenum and chlorine. The salt film was not detectable for Fe-Cr after rinsing the samples with distilled water, whereas in the case of molybedenum additions the salt film could not be washed away with water.     

A mixed-conduction model for oxide films on Fe, Cr and Fe-Cr alloys in high-temperature aqueous electrolytes—II. Adaptation and justification of the model

The aim of this two-part work is to propose a model for the corrosion mechanism of ferrous alloys in high-temperature aqueous environments. In this second part, the modifications to the mixed-conduction model (MCM) are discussed on the basis of experimental data presented in the first part for Fe, Cr and two Fe-Cr alloys (12 and 25 wt% Cr) in an aqueous solution at 200 °C. Application of the MCM to fit and predict experimental behaviour both at room temperature and at 200 °C is demonstrated. The major difference between the behaviour of films at room temperature and at 200 °C is that the mobility of ionic defects is much higher at the higher temperature. Estimates show that the ratio of the electronic and ionic diffusion coefficients (D_e/D_i) is of the order of 10⁵ at room temperature and ≈30 at 200 °C for pure Fe. Such a large difference explains the higher growth rate and thickness of films formed on Fe at the higher temperature. It is also in agreement with the higher defect content and lower field strengths in high-temperature films. The application of the MCM to Fe-Cr alloys indicates that the diffusion coefficient of major ionic current carriers is smaller for the alloys than for pure Fe. Alloying with Cr thus lowers the ionic mobility in the passive film on a ferrous alloy also at 200 °C.     

微量Cl~-对316L不锈钢在沸腾乙酸—甲酸混合介质中的腐蚀行为的影响

通过腐蚀失重测量、极化曲线测试和AES分析,研究了微量Cl~-对316L不锈钢在沸腾的84％乙酸—10％甲酸—6％水中的腐蚀行为的影响。结果表明,微量Cl~-(50ppm)的吸附对316L的活性溶解有抑制作用。Cl~-浓度再高则腐蚀速度增大。316L在阳极极化时呈现钝化行为,阳极钝化膜富铬、贫铁,Cl~-使钝化膜的铬、铁含量降低,铬/铁比也降低,从而氧/(铬+铁)比升高,膜的保护性能降低,一定条件下可诱发孔蚀。常温下恒电位阳极极化使Cl~-在表面吸附并进入钝化膜内,温度升高则吸附作用减弱。     

电镀防护性锌基合金镀层钝化膜的耐蚀性

防护性锌基合金镀层钝化膜的耐蚀性比锌镀层钝化膜提高２－４倍。ＸＰＳ及ＡＥＳ分析表明,合金镀层钝化膜与锌镀层钝化膜均由ＣｒＯ３、Ｃｒ２Ｏ３、Ｚｎ（ＯＨ）２、ＺｎＯ及Ｈ２Ｏ等组成,并且ＣｒＯ３／Ｃｒ２Ｏ３的相对含量和Ｚｎ（ＯＨ）２／ＺｎＯ相对含量也基本相同,它们的区别在于,合金镀层钝化膜中总铬量较高,膜层完整、致密,镀层／钝化膜界面存在铁系金属的富集层,这是锌基合金镀层钝化膜具有高耐蚀性的主要原因。     

Electrochemical behavior of surface films formed on Fe in chromate solutions

The stability of passive films formed on Fe in K₂Cr₂O₇ solutions during exposure at open-circuit potential or by potential cycling is studied in a chromate-free solution. The electrochemical behavior of chromate-passivated Fe is investigated with cyclic voltammetry combined with LASER light reflectance measurements which allow an in situ determination of the thickness of the iron oxide film. The electrochemical behavior of chromate-passivated Fe in chromate-free solutions strongly depends on passivation treatment. Passivation of iron by immersion at open-circuit in chromate solution leads to a passive film, in which both Fe and Cr species dissolve almost independently of the presence of the other one: Fe oxide by reductive dissolution and Cr oxide by oxidative dissolution in the corresponding potential regions. Passivation of iron by potential cycling in chromate solutions leads to much less loss of the otherwise soluble oxidized chromate and reduced ferrous species in subsequent electrochemical experiments (trapping in a protective film). Concerning the dissolution behavior, the film formed on iron by cycling in chromate solution behaves similarly as the passive film on Fe-17Cr alloy. However, the remnant passive film after reductive or oxidative dissolution on the Fe-Cr alloy is of truely protective nature as compared to the films formed on iron in chromate solutions, which show only a small contribution to the potential drop.     

不锈钢钝化的偶极模型变角XPS在不锈钢钝化膜研究中的应用

用变角 XPS 对 Fe19Cr 9 Ni 及 Fe19Cr9Ni2.5Mo 不锈钢在除氧的0.1MHCl 溶液中形成的钝化膜进行研究,显示出不锈钢钝化膜的双层偶极特性。合金中 Mo 元素的加入,通过在膜的表层形成 MoO_4~(2-)而强化了钝化膜的偶极特性。在中性溶液中 MoO_4~(2-)也可以从溶液中引进,它们对强化已形成的钝化膜之偶极特性起着相同的作用。     

Effect of chromium content and sweep rate on passive film growth on iron-chromium alloys studied by EQCM and XPS

Growth of passive films on Cr and Fe-Cr alloys with Cr concentrations ranging from 15% to 54% was studied in situ with the electrochemical quartz crystal microbalance (EQCM). Mass change and current transients were measured as the response to a potential change in the passive region from 0 to 800 mV (SHE) in a pH 1.5 sulfate electrolyte. From these measurements, the thickness change as well as integral and differential growth fractions were calculated. The growth fraction expresses the fraction of oxidized metal that remains in the film. It was found that higher Cr contents gave thicker films and an increase in the growth fraction. The thickness change curves were compared to film growth models assuming rate control at either a film interface or in the film itself through high field conductivity. The integral growth fraction for the potential change experiment was found to vary approximately linearly with the Cr bulk composition. The fraction of dissolved Cr calculated from EQCM data matched well with previous solution analysis results.     

Thermodynamic model for estimating the composition of passive films and Flade potential on Fe-Cr alloys in aqueous solutions

A thermodynamic model of a passive film is developed, in which the formation of the film on the surface of an Fe-Cr alloy in an aqueous solution is considered to be a result of the stable solid-phase chemical and adsorption equilibrium at the alloy-inner passive film layer interface. In the calculations, the Cr₂O₃ content in the passive film is determined by both the Gibbs energy change (ΔG < 0) in the chemical oxidation of the alloy components by the water oxygen and the change in the surface Gibbs energy (ΔG _S > 0) of the alloy. The ΔG _S change results in the negative adsorption of chromium atoms, which shifts the 3Fe + Cr₂O₃ ↔ 3FeO + 2Cr equilibrium toward the FeO formation in the passive film. Calculations showed that the enrichment of the passive film in chromium oxide should sharply increase in a chromium content range of 10–20% in the alloy, which agrees with the known data of X-ray photoelectron spectroscopy of the passive films. A formula is derived for estimating the Flade potential of Fe-Cr alloys, which relates the Flade potentials of individual Fe and Cr components to the FeO and Cr₂O₃ contents in the passive film.     

Thermodynamisch-kinetische Deutung der Passivierungserscheinungen bei Fe-Cr-Legierungen

Thermodynamic-kinetic interpretation of the passivation phenomena with Fe? Cr alloys By superimposing two thermodynamic kinetic current output/potential curves corresponding to iron and chromium, respectively, it is possible to plot the selfpassivation curve for Fe-Cr alloys, which is similar to the potentiostatic polarisation curve. For the ideal Fe-Cr alloy, it is possible to draw conclusions concerning the Fe and Cr passivity zones and the composition of the oxide layers on the passivated Fe-Cr alloy at the Flade reference potential.     

Synergistic effect of Ni and N on improvement of pitting corrosion resistance of high nitrogen stainless steels

Abstract

The pitting corrosion resistance of Fe18Cr10Mn(0·33–0·69)N, Fe18Cr10Mn1Ni(0·33–0·84)N, and Fe18Cr10Mn0·35N(0–3)Ni alloys were investigated. The pitting potential increased as the N content increased in both Fe18Cr10Mn(0·33–0·69)N and Fe18Cr10Mn1Ni(0·33–0·84)N alloys. The rise in the pitting potential was more pronounced in Fe18Cr10Mn1Ni(0·33–0·84)N alloys than in Fe18Cr10Mn(0·33–0·69)N alloys. However, it was found that Ni alone had no effect on the pitting corrosion resistance of Fe18Cr10Mn0·35N based alloys. Thus, it was concluded that the alloyed N worked synergistically with Ni to promote the pitting corrosion resistance in Fe18Cr10Mn based alloys. Analyses of passive films of Fe18Cr10Mn(0·33–0·69)N and Fe18Cr10Mn1Ni(0·33–0·84)N alloys revealed that N was incorporated into the passive film, with N enriched at the film/metal interface. However, the alloyed N increased the Cr cation fraction in passive films of Fe18Cr10Mn1Ni(0·33–0·84)N alloys, whereas N decreased in that of Fe18Cr10Mn(0·33–0·69)N alloys. This difference was considered as the reason for the synergistic effect between N and Ni in Fe18Cr10Mn based alloys.