An ac impedance study of the de-alloying of fe---ni alloys, and its relevance to chloride scc of stainless steels

The electrochemistry of Fe---3Ni and Fe---IONi alloys has been studied using chloride and sulphate solutions at pH 1 and 80°C. There is evidence for porous de-alloyed layers in chloride solution, but not in sulphate solution. The results support the view that chloride causes stress-corrosion cracking of austenitic stainless steels because it promotes de-alloying.     

Exploring the reactivity and nanoscale morphology of de-alloyed layers

De-alloying of a 70Cu-30Pt alloy has been studied with a view to testing the thermodynamic prediction that a novel kind of underpotential or sub-potential electrodeposition may be possible in such highly curved nanoporous solids. After de-alloying in H₂SO₄ solution containing CuSO₄, successive cathodic processes of PtO monolayer reduction, UPD of Cu, and a Cu plating process were identified, all occurring at potentials above the Cu equilibrium potential. The maximum amount of charge in the third plating process was determined to be about three monolayers, averaged over the whole porous surface. This seems to rule out the possibility that this process is some kind of second UPD layer or other non-bulk form of Cu plating. A probable explanation is that small amounts of bulk Cu are plating into regions of high negative curvature within the de-alloyed material. However X-ray diffraction did not show any evidence of bulk Cu.     

Erosion-corrosion behavior of nano-particle-reinforced Ni matrix composite alloying layer by duplex surface treatment in aqueous slurry environment

The present study concerns a duplex surface treatment of AISI 316L stainless steel to enhance the erosion-corrosion resistance. The duplex surface treatment consisted of Ni/nano-SiC and Ni/nano-SiO₂ predeposited by brush plating and a subsequent surface alloying with Ni-Cr-Mo-Cu by double glow process of the substrate. Results showed that under alloying temperature (1000 °C) condition, the amorphous nano-SiO₂ particles still kept the amorphous structure, whereas the nano-SiC particles had been completely decomposed and Ni, Cr reacted with SiC to form Cr_6.5Ni_2.5Si and Cr₂₃C₆. The electrochemical corrosion behaviors of composite alloying layers compared with the single alloying layer and 316L stainless steel were measured under a range of hydrodynamic conditions by recording the current response, open circuit potential, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). Results showed that the increase of the impact velocity had significant influence on the current density of composite alloying layer with brush plating Ni/nano-SiC particles interlayer obtained under flowing condition at a potential of 200 mV, whereas there were only small fluctuations occurred at current response of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The results of potentiodynamic polarization indicated that, with increasing impact velocity under slurry flow conditions, the corrosion potentials of test materials decreased and the corrosion current densities of test materials increased. The corrosion resistance of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer was prominently superior to that of single alloying layer under slurry flow conditions; the corrosion resistance of composite alloying layer with brush plating Ni/nano-SiC particles interlayer was evidently lower than that of single alloying layer, but higher than that of 316L stainless steel under slurry flow conditions. The results of EIS indicated that, with respect to the R_tot obtained in sand-free flow, the impacts of sand particles dramatically decreased the R_tot values of composite alloying layer with brush plating Ni/nano-SiC particles interlayer, single alloying layer and 316L stainless steel, whereas the impact action slightly decreased that of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The weight loss rate studies suggested that the highly dispersive nano-SiO₂ particles were helpful to improve the erosion-corrosion resistance of composite alloying layer, whereas the carbides and silicide phase were deleterious to that of composite alloying layer due to the fact that preferential removal of matrix around the precipitated phase takes place by the chemical attack of aggressive medium.     

Corrosion properties of plasma nitrided AISI 410 martensitic stainless steel in 3.5% NaCl and 1% HCl aqueous solutions

Samples of an AISI 410 martensitic stainless steel were plasma nitrided at a temperature of 420 °C, 460 °C or 500 °C for 20 h. The composition, microstructure and hardness of the nitrided samples were characterised using a variety of analytical techniques. In particular, the corrosion properties of the untreated and plasma nitrided samples were evaluated using anodic polarisation tests in 3.5% NaCl solution and immersion tests in 1% HCl acidic water solution. The results showed that plasma nitriding produced a relatively thick nitrided case consisting of a compound layer and a nitrogen diffusion layer on the 410 stainless steel surface. Plasma nitriding not only increased the surface hardness but also improved the corrosion resistance of the martensitic stainless steel. In the immersion test, nitrided samples showed lower weight loss and lower corrosion rate than untreated one. In the electrochemical corrosion tests, the nitrided samples showed higher corrosion potentials, higher pitting potentials and greatly reduced current densities. The improved corrosion resistance was believed to be related to the iron nitride compound layer formed on the martensitic stainless steel surface during plasma nitriding, which protected the underlying metal from corrosive attack under the testing conditions.     

316L不锈钢表面激光熔覆Stellite-F合金层的电化学腐蚀行为

采用CO₂激光器在316L不锈钢表面熔覆Stellite-F合金,通过电化学方法研究了Stellite-F熔覆合金层在5wt%NaCl溶液中的腐蚀行为。结果表明:与316L不锈钢相比,与基材呈冶金结合的Stellite-F合金层自腐蚀电位较正、自腐蚀电流密度较小,无点腐蚀现象出现,耐海水腐蚀性能较好;研究发现,熔覆合金层物相主要由γ-Co固溶体与Ni₃C、Cr₂₃C₆碳化物构成,在盐溶液中其腐蚀失效机制为选择性腐蚀,即固溶体合金相作为阳极被腐蚀浸出,碳化物相得到阴极保护暴露析出,同时固溶体相中的Co、Ni组分优先被腐蚀浸出,其余组分形成海绵状结构。     

00Cr22Ni13Mn5Mo2N奥氏体不锈钢的精轧工艺

为了研究00Cr22Ni13Mn5Mo2N奥氏体不锈钢的精轧工艺,使用Gleeble-3800热模拟试验机模拟00Cr22Ni13Mn5Mo2N奥氏体不锈钢在变形温度为800、850、900、950 ℃,变形量为40%、50%、60%,应变速率为50 s^-1条件下的热压缩变形行为,并对其进行1080、1120、1160 ℃的固溶热处理,观察固溶热处理前后的组织形貌。结果表明:在800~950 ℃热压缩温度下,随变形量增大,再结晶越完全,再结晶平均晶粒尺寸越细小;经固溶处理1 h后,静态再结晶就越充分。在40%~60%变形量下,随热压缩温度升高,再结晶越完全,再结晶平均晶粒尺寸越大。热压缩变形试验钢随固溶处理温度升高,再结晶平均晶粒尺寸越大。00Cr22Ni13Mn5Mo2N奥氏体不锈钢的精轧最佳轧制温度为800 ℃,压缩变形量为60%,固溶温度为1080 ℃。     

AISI304奥氏体不锈钢低温离子渗碳工艺优化研究

用正交实验法研究了AISI304奥氏体不锈钢低温离子渗碳工艺。结果表明,优化后的奥氏体不锈钢低温离子渗碳工艺参数为渗碳温度500℃、C3H8：H2=1：30、氩气流量20ml／min、渗碳时间6h。用优化工艺参数处理的奥氏体不锈钢表面可获得单一的Sc相组织,硬度高达780HV0．05。     

Improvement of corrosion and wear resistances of AISI 420 martensitic stainless steel using plasma nitriding at low temperature

The influence of low temperature plasma nitriding on the wear and corrosion resistance of AISI 420 martensitic stainless steel was investigated. Plasma nitriding experiments were carried out with DC-pulsed plasma in 25% N₂ + 75% H₂ atmosphere at 350 °C, 450 °C and 550 °C for 15 h. The composition, microstructure and hardness of the nitrided samples were examined. The wear resistances of plasma nitrided samples were determined with a ball-on-disc wear tester. The corrosion behaviors of plasma nitrided AISI420 stainless steel were evaluated using anodic polarization tests and salt fog spray tests in the simulated industrial environment.The results show that plasma nitriding produces a relatively thick nitrided layer consisting of a compound layer and an adjacent nitrogen diffusion layer on the AISI 420 stainless steel surface. Plasma nitriding not only increases the surface hardness but also improves the wear resistance of the martensitic stainless steel. Furthermore, the anti-wear property of the steel nitrided at 350 °C is much more excellent than that at 550 °C. In addition, the corrosion resistance of AISI420 martensitic stainless steel is considerably improved by 350 °C low temperature plasma nitriding. The improved corrosion resistance is considered to be related to the combined effect of the solid solution of Cr and the high chemical stable phases of ?-Fe₃N and α_N formed on the martensitic stainless steel surface during 350 °C low temperature plasma nitriding. However, plasma nitriding carried out at 450 °C or 550 °C reduces the corrosion resistance of samples, because of the formation of CrN and leading to the depletion of Cr in the solid solution phase of the nitrided layer.     

Corrosion resistance properties of glow-discharge nitrided AISI 316L austenitic stainless steel in NaCl solutions

Glow-discharge nitriding treatments can modify the hardness and the corrosion resistance properties of austenitic stainless steels. The modified layer characteristics mainly depend on the treatment temperature. In the present paper the results relative to glow-discharge nitriding treatments carried out on AISI 316L austenitic stainless steel samples at temperatures ranging from 673 to 773 K are reported. Treated and untreated samples were characterized by means of microstructural and morphological analysis, surface microhardness measurements and corrosion tests in NaCl solutions. The electrochemical characterization was carried out by means of linear polarizations, free corrosion potential-time curves and prolonged crevice corrosion tests. Nitriding treatments performed at higher temperatures (>723 K) can largely increase the surface hardness of AISI 316L stainless steel samples, but decrease the corrosion resistance properties due to the CrN precipitation. Nevertheless nitriding treatments performed at lower temperatures (?723 K) avoid a large CrN precipitation and allow to produce modified layers essentially composed by a nitrogen super-saturated austenitic metastable phase (S-phase) that shows high hardness and very high pitting and crevice corrosion resistance; at the same polarization potentials the anodic current density values are reduced up to three orders of magnitude in comparison with untreated samples and no crevice corrosion event can be detected after 60 days of immersion in 10% NaCl solution at 328 K.     

Changes in the passive layer of corrugated austenitic stainless steel of low nickel content due to exposure to simulated pore solutions

In this work, changes undergone at the passive layer of a new type of corrugated austenitic stainless steel (low Ni, high Mn 204Cu type) when exposed to solutions simulating that contained in the pores of concrete have been studied. Changes in the nature of the passive layer have been characterized by X-ray photoelectronic spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Particular focus has been put on the influence of the presence of chlorides and/or carbonation in the solution. Changes in the passive layer due to the passivation treatment that is often applied to corrugated stainless steels during manufacturing processes have also been considered. The results obtained on the 204Cu type steel have been compared with those obtained on more traditional, high Ni, austenitic AISI 304 grade and duplex SAF 2205 grade. During the immersion in simulated pore solutions, 204Cu type suffers more intense redox processes than other studied stainless steels. Moreover, it shows less Cr-rich protective passive layers in these media.     

Fe—Mn─Al合金的腐蚀性能与钝化膜的研究

应用阳极极化及ＡＥＳ／ＸＰＳ技术,研究了Ｆｅ－３０．８Ｍｎ－８．２Ａｌ奥氏体合金在ｐＨ值为－０．８至１５．３的水溶液中的腐蚀性能,并与Ｆｅ－３０Ｍｎ合金、低碳钢、９％Ｎｉ低温钢及１Ｃｒ１３不锈钢进行对比。在所测试的水溶液中,该合金的腐蚀抗力优于低碳钢和Ｆｅ－３０Ｍｎ合金,与９％Ｎｉ钢相当,但不及１Ｃｒ１３不锈钢。Ｆｅ－３０．８Ｍｎ－８．２Ａｌ合金在１ｍｏｌ／ＬＮａ２ＳＯ个中形成的钝化膜的最表层可能为氢氧化物,而膜的主体由Ｆｅ２Ｏ３、Ｍｎ２Ｏ３及Ａｌ２Ｏ３组成。     

Nb对00Cr21Ni6Mn9N不锈钢显微组织和晶间腐蚀敏感性的影响

为了研究Nb对00Cr21Ni6Mn9N不锈钢固溶后显微组织和耐晶间腐蚀性能的影响,分别在950、1000、1050、1100、1150和1200 ℃对含Nb量(质量分数,下同)为0.057%和不含Nb的00Cr21Ni6Mn9N不锈钢进行1 h固溶处理,并观察其微观组织。结果表明,固溶温度在950~1200 ℃时,00Cr21Ni6Mn9N不锈钢的晶粒尺寸随着固溶温度的升高而增大,Nb的加入促进00Cr21Ni6Mn9N不锈钢中混晶组织的出现,提高其完全再结晶温度。不含Nb的试验钢在1000 ℃以上固溶后即可获得晶粒大小均匀的组织,而含0.057%Nb的试验钢则需要在1100 ℃以上才可以获得均匀组织,且其尺寸略大于无Nb钢在1000 ℃时完全再结晶的晶粒。随着固溶温度的升高和晶粒尺寸的长大,析出的Z相含量降低,晶粒界面能减小,在1150 ℃和1200 ℃固溶1 h后,Nb对晶粒的细化作用和温度升高造成的晶粒长大程度变得不再明显。两种成分的钢均具有较低的晶间腐蚀敏感性,含Nb量为0.057%的00Cr21Ni6Mn9N不锈钢其再活化率R_a值较不含Nb的钢进一步降低。     

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.     

AISI 201奥氏体不锈钢低温离子渗碳

利用低温等离子体辉光放电技术对AISI 201奥氏体不锈钢进行低温离子渗碳(DCPC)处理,处理后的不锈钢表面可以形成一层无碳化铬析出的碳的过饱和固溶体(SC相)。由于渗入钢中的过饱和碳原子引起奥氏体晶格发生畸变,结果使渗层的硬度和耐蚀性都有较大幅度的提高。     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

利用双层辉光等离子技术进行镍基耐蚀合金表面合金化的研究

研究了在 2 0钢和不锈钢基材上 ,利用双层辉光离子渗金属技术进行Ni Cr Mo Cu多元共渗表面合金化 ,采用电化学方法对两种基材表面形成的渗层在 5 %HCl中的腐蚀性能进行了测定。结果表明 :在两种基材上都能得到类似于源极HastelloyC - 2 0 0 0合金的表面合金渗层 ,在不锈钢表面上形成的渗层的耐蚀性能接近HastelloyC - 2 0 0 0合金并且优于Alloy 5 9合金 ,在 2 0钢表面上形成的渗层耐蚀性能优于不锈钢Cr18Ni9     

等离子合成TiN渗镀层组织结构及耐蚀性研究

采用等离子合成TiN渗镀层方法,在碳钢表面形成TiN沉积层＋含TiN的扩散层组织,Ti和N原子由表及里呈梯度分布,表面是均匀、致密的TiN胞状组织,显微硬度在20 GPa～25 GPa之间;沉积层与基体之间有一扩散过渡区,结合力好,无剥落现象.X射线衍射结果表明：渗镀层表面为TiN层,(200)晶面的衍射峰最强,具有明显的择优取向.将TiN渗镀试样与不锈钢1Cr18Ni9Ti和Q235钢在1 mol/L H2SO4溶液中进行电化学腐蚀对比实验表明：TiN渗镀层的耐蚀性能比不锈钢和Q235钢基体分别提高了1.4和4.2倍.      

双层辉光等离子制备TiN渗镀层的耐蚀性能

利用双层辉光等离子表面合金化技术,在Q235钢表面直接合成TiN渗镀层,该渗镀层由TiN颗粒均匀分布的扩散层及表面TiN沉积层组成。将TiN渗镀层与Q235钢基体和1Cr18Ni9Ti不锈钢在4%的NaOH溶液、l mol/L H2SO4溶液和3.5%NaCl溶液中分别进行电化学腐蚀对比试验。结果表明:在4%的NaOH溶液中,TiN渗镀层的耐蚀性能比Q235钢提高了26.8倍,与1Cr18Ni9Ti不锈钢相当;在l mol/L H2 S04溶液中,TiN渗镀层耐腐蚀性能比Q235钢提高了10.5倍,比1Crl8Ni9Ti不锈钢提高了1.65倍;在3.5%的NaCl溶液中,TiN渗镀层耐腐蚀性能比Q235钢提高了10.3倍,但比1Crl8Ni9Ti不锈钢稍差。TiN渗镀层耐酸碱性溶液腐蚀性能要比耐盐溶液腐蚀性能强。     

Poly(ortho-ethoxyaniline) in corrosion protection of stainless steel

Corrosion protection of stainless steel (13% Cr) coated with poly(ortho-ethoxyaniline) (POEA) has been investigated. The layers of POEA were synthesised from sulphuric and phosphoric acid solutions by means of cyclic voltammetry. The protecting properties of the layers in supporting electrolytes were investigated by monitoring the open circuit potential (E_oc) vs. time, and by electrochemical impedance spectroscopy (EIS). It was found that polymer layers provide corrosion protection, i.e. they help to stabilise the potential of the metal in the passive potential region. The protective properties of POEA layers have shown to be superior to polyaniline (PANI) layers, which is explained by a denser morphology of POEA. The behaviour of POEA obtained on stainless steel, examined by EIS, is different from the one obtained for POEA on Pt electrode. The registered resistance in the case of POEA on stainless steel represents the charge transfer resistance at polymer/solution interface, i.e. the polymer resistance. These measurements show that a part of the layer is reduced, i.e. that there is an interaction between polymer layer and stainless steel. EIS measurements prove the influence of monomer on stainless steel oxide formation and suggest that polymer is partly incorporated into the oxide film.     

Ni含量对0Cr17Ni4Cu4Nb不锈钢富铜相析出的影响

研究了不同Ni含量的0Cr17Ni4Cu4Nb不锈钢在1040℃固溶后油冷和炉冷(均进行480℃时效,分别表示为OC、FC试样)两种热处理工艺下的力学性能和微观组织变化规律,通过力学性能测试、SEM和TEM观察,探讨了Ni含量对力学性能和富铜相析出的影响.研究表明:FC试样的强度由于炉冷过程中析出了粗大的富铜相而显著低于OC试样的;随Ni含量的提高,两种试样的强度均增加,但差距在缩小,其原因是炉冷过程中析出的富铜相尺寸逐渐细小,表明Ni可以提高了Cu在γ相区的溶解度,延缓了固溶后炉冷过程中的富铜相析出;随时效温度的提高,不同Ni含量试验钢的强度降低,且Ni含量高的试验钢强度降低更显著;随Ni含量的提高,时效过程中富铜相的形核速率和长大速度增加,表明Ni降低了Cu在钢中的扩散激活能.