HCO3–对超级13Cr马氏体不锈钢钝化行为及点蚀行为的影响

目的研究在0.1 mol/L NaCl硼酸缓冲溶液中,研究HCO_3~–对超级13Cr马氏体不锈钢的钝化及点蚀行为的影响。方法采用动电位极化、恒电位极化、Mott-Schottky曲线、电化学阻抗谱等电化学测试手段,并结合3D超景深显微镜进行点蚀形貌观察,研究超级13Cr马氏体不锈钢的电化学腐蚀行为。结果随着HCO_3~–浓度的增加,超级13Cr的钝化区间变宽,点蚀电位向正向移动,稳态点蚀发生的敏感性降低。HCO_3~–减少了超级13Cr亚稳态点蚀数量,降低了亚稳态点蚀电流密度峰值的平均值。随着HCO_3~–浓度的增大,超级13Cr钝化膜电阻Rf升高,电荷转移电阻Rct升高,钝化膜电容Cf逐渐减小。HCO_3~–使得超级13Cr钝化膜半导体特性由n型转变为n+p型双极性,且随着溶液中HCO_3~–浓度的增大,钝化膜中的施主密度ND和受主密度NA减小。结论 HCO_3~–的加入使得超级13Cr不锈钢钝化膜厚度增大,钝化膜内点缺陷密度降低,对基体的保护作用增强,抑制了超级13Cr的亚稳态和稳态点蚀发生。     

超级13Cr钢在不同温度NaCl溶液中的膜层电特性与腐蚀行为*

采用全浸泡腐蚀实验方法和扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)、失重法、极化曲线、交流阻抗等分析手段,对超级13Cr油管钢在不同温度NaCl溶液中的腐蚀速率、腐蚀形貌、腐蚀产物及其膜层的电性能进行了分析,研究了溶液温度对其膜层电性能和腐蚀行为的影响。结果显示:超级13Cr油管钢在温度低于80℃的NaCl溶液中具有较好的耐腐蚀性,其表面膜层具有钝化特性,温度对其腐蚀有一定程度的影响,随溶液温度的升高,钝化膜层对基体的保护作用降低,其抗腐蚀性能降低,发生腐蚀的倾向性增大,当溶液温度高于60℃时尤为显著。超级13Cr在不同温度NaCl溶液中由点蚀引发了局部腐蚀,进而导致了全面腐蚀的发生,其腐蚀产物均由Fe和Cr的氧化物组成,且表面的腐蚀产物疏松不致密。     

高温高压条件下13Cr钢的乙酸腐蚀

研究了13Cr钢在高温高压环境中的乙酸腐蚀行为。13Cr钢腐蚀速率随乙酸浓度增加而增大。不含乙酸时,基体铬发生溶解并在表面形成Cr(OH)3钝化膜,溶液中侵蚀性离子(Cl-)的存在是发生点蚀的重要原因。加入乙酸后,乙酸电离H+使得溶液酸性增强,钝化膜稳定性降低。H+和Cl-更容易通过钝化膜与基体接触,促进局部酸性增强以及侵蚀性离子浓度增加,加快点蚀的发生和发展过程。随着乙酸浓度增加,酸性增强越明显,对点蚀的促进作用越强,腐蚀速率增加。     

温度对超级13Cr油套管钢在NaCl溶液中腐蚀行为的影响

采用线性极化曲线、阻抗谱电化学技术等分析方法,研究了不同温度下,超级13Cr油套管钢在NaCl溶液中的腐蚀行为。结果表明:60、80和100℃对应的点蚀电位分别:-0.24、-0.27、-0.36 V,随温度升高,超级13Cr的点蚀电位下降,点蚀的尺寸逐渐增大,到100℃时,由点蚀引发了局部腐蚀,腐蚀速率增大;温度升高导致超级13Cr油套管钢在NaCl溶液中的耐腐蚀性降低。     

不同温度下超级13Cr在Cl~-/CO_2环境中的腐蚀行为

模拟油田现场Cl~-/CO_2腐蚀环境,对超级13Cr不锈钢在不同温度下的耐均匀腐蚀及点蚀的性能进行了研究。利用金相、扫描电镜(SEM)、能谱分析(EDS)及X射线衍射(XRD)等方法对试样进行了分析。结果表明,温度升高,超级13Cr均匀腐蚀速率增大,温度升高到150℃时,均匀腐蚀由轻微腐蚀转变成中度腐蚀。在Cl~-/CO_2腐蚀环境中,超级13Cr不锈钢极易发生点蚀,且温度升高,点蚀程度先加重后减弱,在120℃时,点蚀坑数量最多,尺寸最大,点蚀最严重。XRD结果显示,所有温度条件下材料均无CO_2腐蚀产物FeCO_3产生,超级13Cr不锈钢依靠表面形成的钝化膜抵抗CO_2腐蚀。     

温度对Cr26Mol超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响

通过循环极化曲线、Mott-Schottky曲线以及电化学阻抗谱等方法研究了温度对Cr26Mo1超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响.结果表明:随着温度升高,Cr26Mo1超纯高铬铁素体不锈钢的自腐蚀电位降低,腐蚀电流密度增大,点蚀电位下降,钝化膜阻抗降低.Cr26Mo1不锈钢钝化膜的半导体类型和性质在不同温度下发生改变.Cr26Mo1不锈钢发生点蚀的孕育期随着温度的升高而缩短,点蚀敏感性增加,已发生点蚀的试样不能够自修复.     

温度对Cr26Mo1超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响

通过循环极化曲线、Mott-Schottky曲线以及电化学阻抗谱等方法研究了温度对Cr26Mol超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响.结果表明:随着温度升高,Cr26Mol超纯高铬铁素体不锈钢的自腐蚀电位降低,腐蚀电流密度增大,点蚀电位下降,钝化膜阻抗降低.Cr26Mol不锈钢钝化膜的半导体类型和性质在不同温度下发生改变.Cr26Mol不锈钢发生点蚀的孕育期随着温度的升高而缩短,点蚀敏感性增加,已发生点蚀的试样不能够自修复.     

SZ36-1油田某低含CO_2水源井油管材料的选择

模拟SZ36-1油田某低含CO_2水源井生产油管的现场环境,在高温高压釜中对5种油管材料N80钢、3Cr钢、13Cr钢、超级13Cr钢以及钨钢进行72h腐蚀浸泡试验,确定油管材料的腐蚀速率,以比较各钢材的耐蚀性;采用光学显微镜观察试样腐蚀形貌,以评价各钢材的局部腐蚀情况;利用动电位极化曲线和电化学阻抗谱分析待选材料的电化学性能。结果表明:N80钢的腐蚀速率高达0.223mm/a,表面有大量点蚀坑,其电化学腐蚀反应受阳极活化控制,并且阻抗最小,不满足选材要求;钨钢因其较差的耐点蚀性也不满足要求;3Cr钢、13Cr钢和超级13Cr钢的腐蚀速率低,具有显著的阳极钝化特征,耐点蚀性好,电化学阻抗高,可以满足选材要求。     

微观调控对13Cr15Ni4Mo3N高强不锈钢电化学行为钝化膜性能的影响

采用极化曲线,电化学阻抗谱和Mott-Schottky曲线研究了不同时效温度下,13Cr15Ni4Mo3N高强不锈钢在3.5%NaCl溶液中形成的钝化膜性能。结果表明:相同时效时间下,随时效温度升高,于350~625℃温度区间,点蚀电位先降低后升高。电化学阻抗结果表明:随时效温度升高或时效时间延长,钝化膜的致密性先降低后升高。Mott-Schottky曲线计算表明:钝化膜缺陷扩散系数随时效温度升高先增加后减小,表面钝化膜的稳定性随时效温度先降低后升高,与极化曲线、电化学阻抗谱测试结果一致。     

时效处理对PH13-8Mo高强不锈钢耐局部腐蚀行为的电化学研究

采用极化曲线,电化学阻抗谱和Mott-Schottky曲线研究了不同时效温度下,PH13-8Mo高强不锈钢在3.5%NaCl溶液中形成的钝化膜性能。结果表明:时效温度对PH13-8Mo高强不锈钢耐点蚀性能有影响,具体表现为:时效时间为4 h,随时效温度升高,于480~595℃温度区间点蚀电位持续降低,温度升至621℃时,点蚀电位升高。电化学阻抗谱结果表明:随时效温度升高,钝化膜表面阻抗先增大后减小,温度升高到621℃,阻抗增大,与极化曲线测试结果一致。Mott-Schottky测试结果表明,不同时效温度下PH13-8Mo高强不锈钢表面钝化膜的致密性不同。     

Enhancements of Passive Film and Pitting Resistance in Chloride Solution for 316LX Austenitic Stainless Steel After Sn Alloying

In the present work, the electrochemical behavior and properties of the passive film of a new Sn-alloyed 316 LX austenitic stainless steel were investigated. With the increase in Sn content in 316 LX austenitic stainless steel from 0 to 0.21%, the critical pitting temperature value increased from 32.6 to 38.8 °C, and the pitting potential increased from 0.252 V_(SCE) to 0.317 V_(SCE). Electrochemical impedance spectroscopy results showed that the corrosion resistance of passive film rose with the increase in Sn content, indicating a more stable passive film. The Mott–Schottky measurement revealed an n-type passive film with a decreased carrier concentration on the 316 LX austenitic stainless steel surface. The Cr, Sn~(2+) and Sn~(4+)(SnO, SnOHCl or SnO_2) enrichments were observed in the passive layer by X-ray photoelectron spectroscopy. The enrichment of Sn and Cr in the passive film can account for the enhanced pitting resistance of 316 LX austenitic stainless steel in chloride solution.     

Passivation Behavior of 2507 Super Duplex Stainless Steel in Hot Concentrated Seawater: Influence of Temperature and Seawater Concentration

The electrochemical behavior and passivation properties of 2507 super duplex stainless steel (SDSS) in the hot concentrated seawater with different concentrations at different temperatures are characterized by electrochemical methods and X-ray photoelectron spectroscopy. The passive film formed on 2507 SDSS belongs to n-type semiconductor and mainly composed of hydroxides and oxides of Fe and Cr under all circumstances. The protectiveness of the passive film decreases with the increase in temperature mainly because of the increase in defect density in the passive film. The corrosion resistance of 2507 decreases with the increase in seawater concentration, and the critical pitting temperature also decreases.     

H2S 分压对 13Cr 不锈钢在 CO2注气井环空环境中应力腐蚀行为的影响简

利用高压下的电化学实验及U型弯浸泡实验结合微观分析手段,研究了13Cr不锈钢在不同H2S分压下CO2注气井环空环境模拟液中的电化学特征及应力腐蚀规律。结果表明:油套管钢的刺漏现象以及环境中硫酸盐还原菌的存在使得环空环境成为复杂的高压H2S-CO2-Cl-环境,13Cr不锈钢在该种环境下具有明显的应力腐蚀敏感性。随着H2S分压的升高,13Cr不锈钢击破电位下降,应力腐蚀敏感性增强,这主要因为H2S分压的增大对不锈钢表面膜(钝化膜及腐蚀产物膜)的破坏作用加强。当H2S分压达到0.20 MPa时,13Cr不锈钢发生明显的应力腐蚀,断口表现为由沿晶应力腐蚀裂纹(IGSCC)和穿晶应力腐蚀裂纹(TGSCC)组成的混合断口,应力腐蚀受阳极溶解和氢致开裂共同控制。     

The influence of temperature on the passivation behaviour of a super duplex stainless steel in a boric-borate buffer solution

The passivation behaviour of a super duplex stainless steel has been investigated in a boric-borate buffer solution with and without chloride additions, at different temperatures, by means of potentiodynamic and potentiostatic techniques. X-ray photoelectron spectroscopy was used to detect surface compositional changes of anodic passive films formed as a function of electrode potential and temperature. The resulting passive films were all chromium enriched with respect to the bulk composition, and their thickness and ratio were found to vary significantly. In particular, the films formed in the passive domain were more enriched with chromium compared with those grown in the secondary passive region. At a constant potential the temperature increase produced a reduction in the chromium content of the film. These findings can be explained by the different ionic mobilities and dissolution rates at the film/solution and film/alloy interfaces. Pitting corrosion was observed only in the transpassive zone. A temperature increase from 23 to 60 °C did not produce a decrease in the pitting potential. This behaviour can be explained by the parallel action of two different phenomena, the change in the composition and structure of the passive film and the velocity increase in the process, which yield localized rupture of the passivity by the nucleation and growth of pits in connection with chromium depletion at high potentials.     

Application of polyaniline to galvanic anodic protection on stainless steel in H2SO4 solutions

A stand-alone polyaniline (PANI) film electrode was made and then applied to protect 1Cr13 stainless steel (a type of stainless steel typically used in China, 0–15% C, 13% Cr) from corrosion in highly acidic solution, up to 5 M H₂SO₄. The stand-alone PANI electrode and 1Cr13 were coupled to study their galvanic interactions. PANI is a cathode while 1Cr13 is an anodic. The results indicate that PANI with a certain area can quickly passivate the stainless steel and effectively maintain the steady passive state for a long period of time. This specific method of PANI preventing 1Cr13 from corrosion is called galvanic anodic protection (GAP). Moreover, the efficiency, mechanism, and security of GAP were discussed. The results demonstrate that the stand-alone PANI electrode may have a potential application to galvanic anodic protection on stainless steel in highly corrosive H₂SO₄ solutions.     

Effect of mercury on corrosion in production wells in Gulf of Thailand

Abstract

The effect of mercury on the corrosion of materials used for tubing in oil and gas production wells was studied. Carbon steel (L80) and 13% chromium stainless steel (13Cr) were selected for study by potentiodynamic polarisation. Simulated produced water, with the composition obtained from the Gulf of Thailand field, was used as a corrosive solution. Temperature kinetically increased the corrosion reaction. Chloride ions and carbon dioxide also enhanced the corrosion. Acidity increased the pitting corrosion of 13Cr and increased the corrosion rate of both 13Cr and L80. A concentration of 3–12 ppm of mercury lowered the current density in the passive region and increased the pitting potential of 13Cr. The corrosion rate of L80 was decreased with small amount of mercury addition. The 13Cr showed lower uniform corrosion rate than the L80 in all conditions of the simulated produced water.     

哌啶对Cr25铁素体不锈钢在中性NaCl介质中钝化膜破坏的缓蚀作用研究

采用稳态阳极极化曲线、电化学阻抗谱(EIS)方法和恒电位-恒电流(P-G)瞬态响应测试技术研究了有机缓蚀剂哌啶(PD)对Cr25铁素体不锈钢在NaCl介质中钝化膜破坏的抑制作用,以及缓蚀剂浓度和Cl~-浓度对钝化膜稳定性的影响。研究结果表明PD可有效地提高Cr25不锈钢在NaCl介质中的稳定性。得到研究体系的“临界浓度比”PD:Cl~-=1:100～170(摩尔比)。按照竞争吸咐机制,讨论了PD对Cr25的缓蚀作用,并对照PD对304不锈钢的保护作用,分析了PD对这两种不锈钢保护作用的异同。