Effect of pH on Semiconducting Property of Passive Film Formed on Ultra-High-Strength Corrosion-Resistant Steel in Sulfuric Acid Solution

Because Cr9Ni5MoCo14 is a new ultra-high-strength corrosion-resistant steel, it is important to study its corrosion behavior in sulfuric acid solution, which is used to simulate the aggressive environment. The effect of pH on the electrochemical and semiconducting properties of passive films formed on ultra-high-strength corrosion-resistant steel in sulfuric acid solution was investigated by means of the potentiodynamic polarization technique, electrochemical impedance spectroscopy (EIS), Mott-Schottky analysis, and X-ray photoelectron spectroscopy (XPS). The results indicated that Cr9Ni5MoCo14 steel showed a passive state in acid solutions. The corrosion behavior of this Cr9Ni5MoCo14 alloy was influenced by the passive film formed on the surface, including thickness, stability, and partitioning of elements of the passive film. The passive current density decreases with increasing pH, and the corrosion resistance was enhanced by the increasing thickness and depletion of the defects within the passive film. Moreover, an enrichment of chromium (primarily the oxides of Cr) and depletion of iron in the passive film led to improved corrosion resistance. These results can provide a theoretical basis for use of this alloy and further development of ultra-high-strength corrosion-resistant steel in today’s society.     

表面纳米化处理对IF钢电化学析氢行为的影响

利用阴极极化曲线、交流阻抗谱,对超音速微粒轰击（USPP）表面纳米化处理（SNC）的IF钢在30%NaOH溶液中的析氢行为进行了研究,同时利用XRD和SEM分析了表面纳米化前后IF钢的晶粒度和表面形貌。试验证明,经SNC处理后,IF钢析氢过电位比基材降低200 mV;SNC＋1%平整的IF钢比基材析氢过电位低300 mV以上;经处理后IF钢真实表面积比原IF钢板分别增大18倍和21倍,其表观析氢活化自由能分别由51.7 kJ/mol降低为26.5 kJ/mol和21.7 kJ/mol,仅为原IF钢板的50%。     

新型2Cr1Mo2Ni钢在含二氧化碳油田采出液中的腐蚀行为

为弄清Mo和Ni元素在低Cr钢耐蚀方面所起的作用,炼制了新型2Cr1Mo2Ni钢,研究其在模拟油田采出液中的腐蚀行为,实验条件为80℃,0.8 MPa CO₂分压.利用扫描电镜和能谱分析研究了2Cr1Mo2Ni钢和3Cr钢的腐蚀产物膜微观形貌和成分,测试了高温高压极化曲线和电化学阻抗谱,分析了腐蚀产物膜的生长过程.实验结果表明,Mo和Ni元素在提高抗CO₂腐蚀性能方面的作用不及Cr元素.2Cr1Mo2Ni钢腐蚀164 h后,中低频感抗弧消失,腐蚀产物膜开始完全覆盖基体表面;腐蚀240 h后,生成的腐蚀产物膜具有较好的保护性.     

温度对3Cr钢在CO2-O2环境中腐蚀的影响

摘要：为了研究注多元热流体吞吐热力采油过程中温度对油套管钢的影响,利用高温高压电化学釜模拟注多元热流体采油工况,分别在60、100和100～60℃循环的温度条件下,对3Cr钢进行失重腐蚀挂片试验和电化学腐蚀试验,利用高温高压电化学釜得到了3Cr钢在模拟工况下的腐蚀速率和极化曲线,并利用SEM、XRD、EDS分析了腐蚀产物膜形貌和成分。结果表明,温度由60升高至100℃时,腐蚀速率由0.552增长至1.920mm/a,在100-60℃高-低温循环时,腐蚀速率进一步升高至4.292mm/a;60和100℃时,腐蚀产物均为单层膜结构,且存在点蚀坑;在100-60℃高 低温循环时,腐蚀产物为双层膜结构,且存在直径约为4μm的腐蚀坑。温度主要影响3Cr钢腐蚀产物膜的结构和点蚀的形态,60和100℃时,点蚀坑内的聚集的Cl-离子使点蚀向纵深处发展,在100.60℃高 低温循环时,溶液中的O2促进了点蚀的横向发展,而腐蚀坑底部富集的Cr将阻碍点蚀的纵向发展。注多元热流体热力采油过程应充分考虑温度变化对3Cr钢腐蚀的影响,同时也要考虑温度变化引起3Cr钢点蚀的敏感性。     

Effects of Sulphate-reducing Bacteria on Corrosion Behaviour of 2205 Duplex Stainless Steel

The effects of sulphate-reducing bacteria(SRB)on the 2205 duplex stainless steel in the sea water and oil industry environments were studied by electrochemical impedance spectroscopy(EIS),potentiodynamic polarization and microorganism analysis.The results showed that the detected SRB was the non-spore bacillus of about 0.8μm×(1.8-2.2)μm in size and the content of S was about 7.59% in the corrosion products.SRB contributed to the corrosion evolution which caused the corrosion failure of 2205 duplex stainless steel pipe in the liquid hydrocarbon cooler.During the corrosion process,the produced H2S could significantly influence the anodic process and finally accelerate the corrosion.SEM observation indicated that the distribution of SRB on the surface of 2205 duplex stainless steel was nonuniform.X-ray photoelectron spectroscopy analysis revealed that the surface film was composed of Cr2O3,MoO3,FeS,FeS2,Fe(OH)2 and FeO after immersing the sample in the SRB medium for 14d.     

NaCl+HCl溶液中Ce对双相不锈钢腐蚀行为的影响

为了研究酸性NaCl溶液中双相不锈钢的耐腐蚀性能,以含微量稀土Ce的UNS S31803双相不锈钢为研究对象,采用电化学阳极极化和交流阻抗相结合的方法测试其在NaCl+HCl混合溶液中的耐腐蚀性能。利用扫描电镜(SEM)观测腐蚀后的形貌特征,采用电子探针(EPMA)检测合金元素与杂质元素的分布特征,分析Ce元素的加入对双相不锈钢电化学腐蚀行为的影响机制。结果表明,钢中存在两相的选择性腐蚀并伴有局部点蚀,其中铁素体相是腐蚀较严重的相;阳极极化测试与交流阻抗测试结果相吻合,Ce拓宽了试验钢的钝化区间;Ce通过净化钢液、降低S和P元素在相界的偏聚及使Cr、Ni和Mo等合金元素在两相中的分布更均匀等作用,提高了钢的耐腐蚀性能。     

稀土Ce对1Cr18Mn8Ni5N不锈钢耐均匀腐蚀性能影响

利用电化学的极化曲线及交流阻抗技术研究了不同稀土含量的1Cr18Mn8Ni5N不锈钢在硫酸介质中的腐蚀行为。应用扫描电镜对试样的腐蚀形貌及夹杂物形态进行了观察,利用EDS对夹杂物成分进行了分析。结果表明:钢中加入稀土Ce可改变夹杂物形态,并使其交流阻抗的极化电阻增大,极化曲线的腐蚀电位正移,降低了腐蚀电流密度,抵制了均匀腐蚀,改善了1Cr18Mn8Ni5N不锈钢的耐蚀性。当钢中稀土Ce质量分数为0.022%时,1Cr18Mn8Ni5N不锈钢可获得最好的耐均匀腐蚀性能。     

Effects of Different Oxidants on HCl-based Pickling Process of 430 Stainless Steel

To shorten the time required for the pickling process and to enhance the quality of ferritic stainless steel plates,the effects of oxidants including hydrogen peroxide(H2O2),potassium permanganate(KMnO4),and potassium chlorate(KClO3)on the pickling behavior in HCl-based electrolyte as well as the surface quality of hot-rolled and blasted 430 stainless steel(430-SS)were studied.Experiments were conducted using mass-loss tests,microstructure analyses,potentiodynamic polarization curves,and electrochemical impedance spectroscopy measurements.The results showed that the addition of oxidants substantially accelerated the pickling process of 430-SS by enhancing the cathodic reaction rate and reducing the charge transfer resistance.In electrolytes comprising 5-8mass% HCl at a temperature of 40-60 ℃ and at the same concentration within the range from 0to 2mass%,H2O2 was demonstrated to be superior to KMnO4 and KClO3in accelerating the pickling process.The surface quality of 430-SS pickled in the presence of H2O2 was better than those of specimens pickled in the presence of KMnO4 and KClO3 when the removal of the oxide layer,intergranular corrosion,and surface roughness were collectively considered.When 1mass% H2O2 was added,the mass loss rate of 430-SS was increased by 629%and no residual oxide layer or intergranular corrosion was observed on the surface of the steel;in addition,the roughness was only 1.7μm.H2O2 was determined to be a better oxidant than KMnO4 and KClO3 when the pickling process,surface quality,solution recycling,and environment protection were considered as a whole.     

Effects of Cu on Corrosion Resistance of Low Alloyed Steels in Acid Chloride Media

The corrosion resistance of two kinds of low alloyed steels was studied according to the test procedures for qualification of corrosion resistant steel for cargo oil tanks issued by International Maritime Organization.The results indicated that the addition of Cu improved the corrosion resistance of the NS-D36 steel to more than three times that of the conventional D36 steel in the strong acid solution containing chloride(10% NaCl,pH=0.85).The anodic polarization behavior of the copper-bearing steel was studied by polarization curves and electrochemical impedance spectroscopy(EIS),and alloying element Cu showed beneficial effects including an active potential range,low current density and high transfer resistance of electric charge.The rust layer was analyzed by scanning electron microscopy(SEM)and Auger electron spectroscopy(AES),and the results pointed out that the mechanism of copper′s beneficial effects was based on the suppression of anodic dissolution by metallic copper re-deposition on the steel surface immersed in the strong acid chloride media.     

外加拉应力对13Cr马氏体不锈钢的腐蚀行为影响

采用电化学测试手段(开路电位、交流阻抗谱及动电位极化曲线测试), 结合接触角测试及体视显微镜微观形貌观察探究在80 g·L-1 NaCl溶液中拉应力对L80-13Cr马氏体不锈钢钝化膜溶解与再修复机制的影响.结果表明, 拉应力大小与L80-13Cr的钝化特性存在正相关关系.随着外加拉应力的增大, L80-13Cr马氏体不锈钢的开路电位负移, 电子转移电阻减小, 线性极化电阻减小, 反应速率随着拉应力的增大而增大.而L80-13Cr马氏体不锈钢在高电位下再钝化形成的钝化区会缩短, 自腐蚀电位降低, 维钝电流密度增加.接触角测试和体视显微镜微观形貌观察发现, 拉应力使得表面接触角减小, 不锈钢表面容易发生点蚀.外加拉应力使得L80-13Cr马氏体不锈钢的表面能增加, 促进钝化膜的溶解, 并且抑制钝化膜的再生, 导致材料耐蚀性降低.      

Cr对低合金钢在流动NaCl溶液中耐蚀性的影响

对碳钢和Cr含量不同的实验钢在流速为0.8m/s的流动的3.5％(质量分数)NaCl溶液中的腐蚀行为进行研究,最长腐蚀周期为192h.对4种实验钢的腐蚀失重进行了比较,并利用动电位极化曲线、SEM、EPMA和TEM等分析手段,对实验钢表面形成锈层的特征进行了系统研究.结果表明,含Cr实验钢的腐蚀失重低于碳钢,并且随Cr的质量分数由0.5％提高至2％,腐蚀失重亦降低.Cr元素在内锈层中的富集是含Cr钢耐蚀性改善的重要原因.这种富集可使腐蚀产物颗粒获得细小的尺寸,致密内锈层形成的原因就是由于这种尺寸细小的腐蚀产物的形成,使内锈层的保护性获得明显的改善.     

Influence of Chromium on Mechanical Properties and CO2/H2S Corrosion Behavior of P110 Grade Tube Steel

Four kinds of P110 grade tube steels containing different chromium contents were designed to probe the in- fluence of Cr on the properties of tube steel. The microstrueture, mechanical properties and corrosion behavior of the four kinds of P110 grade tube steels were studied deeply and thoroughly. The analysis of the mechanical properties indicated that tensile strength and yield strength of the steel plates were improved, while transverse and longitudinal impact energy and elongation first increased and then decreased when Cr content rose. The impact energy and elonga tion reached the peak when Cr content was 1 ~. Cr precipitates were found only in 3 ~ Cr steel, with （Nb, Ti）（C, N） or Nb（C,N） as the core of precipitation and then grew up. The corrosion experiments demonstrated that the scales on the four steels had a two layer structure under the corrosion of CO2 and H2 S. The outer layer was mainly com- posed of FeS or FeS1 x and the inner layer consisted of FeCOa and Cr compounds. Cr was rich in the inner layer and the Cr content of the inner layer increased with the Cr content in matrix. The enriched Cr enhanced the compactness of the scales, further hindering the diffusion of ions from liquid to the surface of steel, thus reducing corrosion rate.     

合金调控对钢筋耐蚀性能的影响北大核心CSCD

采用通过微合金调控技术,合理控制钢中C、Cu、Cr和P等元素的含量,研发了一种比普通HRB400aE具有更高耐工业大气和含Cl^(-)污染物综合内陆自然环境腐蚀的400 MPa级低合金耐蚀抗震钢筋(NS-HRB400aE)。通过周浸试验、电化学极化曲线和电化学阻抗谱测试试验,对2种钢筋的耐蚀性进行了评价,结果表明合金化后的NS-HRB400AE低合金耐蚀抗震钢筋表面的腐蚀形貌为均匀腐蚀,而普通HRB400AE钢筋的腐蚀形貌主要为点蚀,NS-HRB400aE钢筋相比HRB400aE钢筋具有更低的腐蚀速率、更高的点蚀电位、更低的维钝电流密度和更高的临界Cl^(-)含量,表明微合金调控后钢筋的耐蚀性能显著提升。     

Characterization of Passive Film Formed on AISI 316L Stainless Steel after Magnetoelectropolishing in a Broad Range of Polarization Parameters

The aim of the paper is to present the changes in the surface film composition on AISI 316L stainless steel (SS) after electropolishing (EP) and magnetoelectropolishing (MEP) in a broad range of the process conditions. The X‐ray photoelectron spectroscopy surface analyses were performed to reveal the effect of MEP. The EP process has been performed under natural convection (in a stagnant electrolyte), much above the polarization plateau. A series of experiments were carried out on AISI 316L SS samples in accordance with the five‐level composite rotary statistical plan with the variables being the magnetic field intensity B (mT), and the anodic current density i (A dm^?2). XP high resolution spectra have been obtained on AISI 316L SS surface concerning Fe 2p, Cr 2p, O 1s, S 2p, P 2p, and C 1s, respectively. The Cr:Fe ratio regarding both metallic M and compound X was also studied and calculated. At the end, the summary results of Cr/Fe = f(B, i) in relation to the corrosion potential, have been compared. The conclusions, concerning the selection of MEP process conditions, regarding the optimum Cr/Fe ratio and corrosion behavior, have been formulated. It was found the Cr:Fe ratio well correlates with the pitting corrosion potential. MEP process can modify not only the rate of dissolution to a determined extent, but also control the corrosion behavior and Cr:Fe ratio results.     

冷轧IF钢表面纳米化后的组织与性能

利用机械研磨处理（SMAT）在冷轧IF钢表面制备出具有纳米晶体结构特征的表面层．利用金相观察和透射电镜分析研究了表面纳米层的结构特征,测定了硬度沿厚度的变化,并分析了表面纳米化（SNC）对力学性能的影响．结果表明：（1）表面机械研磨处理后,冷轧（CR）IF钢表面形成了平均晶粒尺寸为7～9nm、晶粒取向呈随机分布的纳米晶组织;（2）表面层附近的硬度显著提高;（3）纳米表层的存在使得材料强化的同时成形极限也得到提高．     

硫化氢质量浓度和温度对碳钢在NACE溶液中腐蚀行为的影响

采用动电位极化曲线和电化学阻抗谱等电化学实验方法以及扫描电镜和能谱等表面分析技术对20^#碳钢在不同H₂S质量浓度(0,95.61,103.22,224.16 mg·L^-1)、不同温度(25,35,45℃)下的NACE溶液(含CO₂)中腐蚀行为进行了研究,同时对该环境下腐蚀产物的形成机制进行了探讨.发现在含有CO₂的NACE溶液中,加入少量H₂S,能加剧碳钢腐蚀,加速阳极铁的溶解和阴极氢气的析出.随着H₂S质量浓度的增加,腐蚀电流密度增大,碳钢腐蚀加剧.温度升高,腐蚀极化电阻变小,腐蚀也会加剧.腐蚀试样外层絮状腐蚀产物主要是铁碳化物,接近基体表面的腐蚀产物主要是铁硫化物.     

Adsorption and Corrosion Inhibition Performances of 1-Tetradecylphosphonic Acid Self-Assembled Monolayers on 430 Stainless Steel Surface

The self-assembled monolayers (SAMs) of 1-tetradecylphosphonic acid (TDPA) formed on the 130 stainless steel (SS430) were studied. Surface and morphological characterizations were studied by Fourier transformed infrared spectroscopy (FTIR), water contact angle measurement and atomic force microscopy (AFM). And the electrochemical study on the corrosion inhibition of the SAMs was performed by polarization curve and electrochemical impedance spectroscopy (EIS) for evaluating the corrosion protection of the SAMs. The results show that TDPA was able to form a film spontaneously on the SS430 surface and the hydrophobic SAMs could protect SS430 from corrosion effectively. In addition, the oxide surface formed by the heat pretreatment could accelerate the rate of adsorption, but had little effect on improving the inhibition efficiency.     

超级13Cr不锈钢的钝化膜耐蚀性与半导体特性

利用极化曲线和Mott-Schottky曲线,研究了超级13Cr马氏体不锈钢在100、130、150和170℃且含CO2和Cl^-的腐蚀介质中浸泡7 d所形成的钝化膜的电化学行为和半导体性质.同时应用光电子能谱表面分析技术分析了超级13Cr钝化膜中的元素价态.结果表明,超级13Cr马氏体不锈钢经腐蚀过后形成的钝化膜表层中Mo和Ni以各自硫化物的形式富集,而Cr以Cr的氧化物的形式富集.在100℃和130℃形成的钝化膜具有良好的耐蚀性,而在150℃和170℃形成的钝化膜耐蚀性下降.产生这种现象的原因与表面钝化膜的半导体性能密切相关,在100℃和130℃中形成的钝化膜具有双极性n-p型半导体特征,且随着温度升高掺杂数量增多,而150℃和170℃介质中形成的钝化膜为p型半导体,故随着温度升高,超级13Cr马氏体不锈钢的耐蚀性能下降.     

Influence of Surface Roughness of Galvanized Steel Sheet on Self-lubricated Coating

Three different thicknesses of self-lubricated coatings were prepared on galvanized steel sheets with different surface roughness(Ra).Performances of the coatings were evaluated by various laboratory tests.Scanning electron microscopy(SEM),atomic force microscope(AFM),neutral salt spraying test(NSST),reciprocating friction and wear test were taken in order to characterize the coatings.Results show that the self-lubricated coating has good corrosion resistance and lubricating property.In 0.857-1.629μm of Ravalue,the relationship between friction coefficients of the self-lubricated steel sheets and the surface roughness of the galvanized steel sheets likes a parabolic curve,and has a peak value of friction coefficient in certain range of Ra.Affected by the hereditary surface topography of the galvanized steel sheet,dents on the surface of self-lubricated steel become deeper and larger with the increase of the surface roughness of the galvanized steel sheets.The influence of the surface roughness of the galvanized steel sheet on the corrosion resistance of the self-lubricated coating steel is similar to that on friction coefficient of self-lubricated coatings,like a parabolic curve.     

Inhibition Effects of Chloroquinolines on Corrosion of Mild Steel in Hydrochloric Acid Solution

The corrosion inhibition efficiencies of four compounds namely N-[(1E)-(2-chloroquinolin-3-yl)methylene]-N-phenylamine(CQMA),N-(1E)-(2-chloroquinolin-3-yl)methylene]-N-(4-fluorophenyl)amine(CQMFA),N-(4-chloro phenyl)-N-[(1E)-(2-chloroquinolin-3-yl)methylene]amine(CQMCA),and N-(4-bromo phenyl)-N-[(1E)-(2-chloroquinolin-3-yl)methylene]amine(CQMBA)on mild steel corrosion in hydrochloric acid media were investigated using mass loss,potentiodynamic polarization and electrochemical impedance spectroscopy.For all the studied inhibitors the inhibition efficiency values were found to increase with increasing concentration up to 5.00×10-4 mol·dm-3.Scanning electron microscopic technique showed the formation of a thick film on the steel surface in the presence of inhibitors.