低温缓蚀剂的成膜特性研究

利用旋转挂片失重和扫描电镜研究了咪唑啉季铵盐缓蚀剂的成膜特性。考察了缓蚀剂用量、酸浓度、温度、pH值、HCl-H2O和HCl-H2S-H2O腐蚀介质的成膜特性。探讨了缓蚀剂的缓释机理。结果表明,缓蚀剂用量超过临界浓度有利于形成致密有机膜,起到缓释作用。腐蚀液浓度越大,空白腐蚀失重越大,相应加入缓蚀剂后缓蚀率越高。温度越高,空白失重越大,但加入缓蚀剂条件下失重随温度变化较小。pH值调节说明,微酸性或微碱性环境有利于控制腐蚀。钢片的腐蚀形貌特征指出,缓蚀剂抑制大面积均匀腐蚀,但仍存在点蚀现象,说明缓蚀剂吸附膜存在缺陷,个别活性点导致局部腐蚀。     

Investigation of the deterioration of passive films in H<Subscript>2</Subscript>S-containing solutions

The effect of H₂S on the corrosion behavior of 316L stainless steel was investigated using electrochemical methods by changing the gas condition from CO₂ to H₂S and then back to CO₂. The presence of H₂S showed an acceleration effect on the corrosion of 316L stainless steel in comparison with CO₂. The acceleration effect remained even after the complete removal of H₂S by CO₂, indicating that the passive film was irreversibly damaged. X-ray photoelectron spectroscopy (XPS) analysis indicated that the passive film was composed of Cr₂O₃, Fe₂O₃, and FeS₂ after being immersed in H₂S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott-Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

金属离子对钢在没食子酸/硫酸介质中的腐蚀行为研究

 用失重法研究了4种金属离子(Na⁺,Zn²⁺,Cu²⁺,Fe³⁺)在0.5 mol/L H₂SO₄以及500 mg/L没食子酸+0.5 mol/L H₂SO₄介质中在20℃对冷轧钢腐蚀行为的影响.结果表明:Cu²⁺对钢的腐蚀起抑制作用;而其余3种金属离子(Na⁺,Zn²⁺,Fe³⁺)对钢的腐蚀起加速作用.在相同条件下,冷轧钢在0.5 mol/L H₂SO₄溶液中的腐蚀速率顺序为:Cu²⁺2++3+;而在500 mg/L没食子酸+0.5 mol/L H₂SO₄介质中,腐蚀速率顺序为:Cu²⁺2+3++.     

Corrosion behavior and characteristics of the product film of API X100 steel in acidic simulated soil solution

The short-term corrosion behavior of API X100 steel in an acidic simulated soil was investigated by electrochemical measurements and soaking experiments, followed by corrosion morphology observations and X-ray photoelectron spectroscopy analyses. The results show that X100 steel exhibits an obvious pitting susceptibility in an acidic soil environment. Pits nucleate after approximately 10 h of immersion. Along with the nucleation and growth of the pits, the charge-transfer resistance and open-circuit potential first increase sharply, then decrease slowly, and eventually reach a steady state. The maxima of the charge-transfer resistance and open-circuit potential are attained at approximately 10 h. The evolution of the electrochemical process is confirmed by the analysis of the product film. The product film exhibits a porous and loose structure and could not protect the substrate well. The product film is primarily composed of ferrous carbonate and ferrous hydroxide (Fe(OH)₂). The concentration of Fe(OH)₂ in the product film increases from the inside to the outside layer.     

Effects of silty sand on CO<Subscript>2</Subscript> corrosion behavior of low-Cr tubing steel

An experimental study was carried out to assess the effects of silty sand on the CO 2 corrosion behavior of 1 wt% Cr (1Cr) and 3 wt% Cr (3Cr) tubing steel under 0.5 MPa CO 2 at 100°C and 1.5 m/s flow velocity.The 1Cr and 3Cr specimens both suffered general corrosion,but the surface was coarser in the pure CO 2 corrosion environment.Under silty sand conditions,severe pitting corrosion occurred on the 1Cr specimens and some acicular pitting appeared on the 3Cr specimens.The average corrosion rates of 1Cr and 3Cr steels increased by factors of 3 and 1.6,respectively.The corrosion products were analyzed by scanning electron microscopy (SEM),energy dispersive spectroscopy (EDS),X-ray diffraction (XRD),and electrical impedance spectroscopy (EIS).The results show that silty sand acts as an inclusion in corrosion product films and reduces the homogeneity and density of the products,rather than abrading the corrosion film.Ion-diffusion channels may build up around the irregular silty sand;this would degrade the protective capabilities of the product films and aggravate corrosion.     

Effect of Ca on CO2 corrosion properties of X65 pipeline steel

The effect of Ca²⁺ on CO₂ corrosion to X65 pipeline steel was investigated in the simulated stratum water of an oil field containing different concentrations of Ca²⁺. It is found that Ca²⁺ can enhance the corrosion rate, especially in the Ca²⁺ concentration from 256 to 512 mg/L, which can be attributed to the growing grain size and loosing structure of corrosion scales with increasing Ca²⁺ concentration. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) investigations reveal that a complex carbonate (Fe, Ca)CO₃ forms at high Ca²⁺ concentration due to the gradual replacement of Fe²⁺ in FeCO₃ by Ca²⁺.     

低碳微合金钢抗CO2/H2S腐蚀性能研究

针对用于可膨胀套管的低碳微合金钢CO₂/H₂S腐蚀问题,采用电极化实验、失重法及SEM等方法和手段对低碳微合金钢分别在单一H₂S（pH=2.9）、CO₂/H₂S流量比为1∶1（pH=2.9）、CO₂/H₂S流量比为1∶1（pH=5.3）条件下的腐蚀行为和规律进行研究。结果表明：低碳微合金钢在单一H2S条件下,生成了铁的硫化物,使腐蚀速率高;在有CO2存在的情况下,由于CO₂吸附在钢材表面,形成致密的吸附膜,提高了自腐蚀电位,减缓了CO₂/H₂S的腐蚀速率;由于组织不均匀及MnS的偏析,造成腐蚀后试样表面不平整,腐蚀产物膜存在微裂纹,pH值越低,腐蚀后试样表面越不平整,裂纹越明显,腐蚀越严重。     

EIS法研究16Mn钢在含H2S薄层液膜下的缓蚀行为

用交流阻抗(EIS)技术研究了硫脲和溴化十六烷基吡啶在复配前后对含H2S薄层液膜下16Mn钢的缓蚀行为．结果表明，硫脲和溴化十六烷基吡啶分别都表现出一定的缓蚀效果，复配后具有缓蚀协同效应，存在一个最佳缓蚀浓度极值和一个最佳缓蚀浓度比．对交流阻抗行为进行了解释和讨论。     

冷凝液硫含量对SUS444铁素体不锈钢腐蚀行为的影响

利用冷凝液浸蚀-高温氧化循环腐蚀法模拟汽车排气系统内部服役环境,借助失重分析、腐蚀形貌观察及腐蚀产物分析,研究了SUS444不锈钢在不同硫含量的冷凝液中的腐蚀行为。结果表明,随着腐蚀循环次数的增加,不锈钢表面不断沉积的FeSO_4·7H_2O、Fe(NH_4)(SO_4)_2及Fe_4(SO_4)_5(OH)_2·18H_2O等硫酸盐物质加速了不锈钢的腐蚀进程,其点蚀深度及腐蚀速率均随冷凝液中硫含量的升高而增加。     

N80油管钢的CO_2高温高压腐蚀电化学行为与机理研究

在高温高压釜中模拟油气井腐蚀环境 ,采用电化学交流阻抗和动电位扫描极化曲线测试技术 ,研究了N80钢在温度为 10 0℃ ,CO2 分压为 1.18MPa条件下的腐蚀电化学行为和阳极与阴极反应机理 ,实时监测了腐蚀产物膜对腐蚀行为和腐蚀反应机理的影响 .研究结果表明 :N80钢的阳极反应过程服从Bockris机理 ;N80钢的阴极反应以H2 CO3的还原为主 ;反应中间产物吸附与腐蚀产物膜覆盖的竞争导致交流阻抗谱随腐蚀时间而变化 ,影响着钢的腐蚀行为 ,产物膜对钢基体具有一定的保护作用     

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.     

Comparative study on the corrosion behavior of X52, 3Cr,and 13Cr steel in an O2-H2O-CO2 system:products,reaction kinetics,and pitting sensitivity

The corrosion behaviors of X52, 3Cr low-alloy steel, and 13Cr stainless steel were investigated in an O₂-H₂O-CO₂ environment at various temperatures and O₂-CO₂ partial-pressure ratios. The results showed that the corrosion rates of X52, 3Cr, and 13Cr steels increased with increasing temperature. The corrosion rates slowly increased at temperatures less than 100℃ and increased sharply when the temperature exceeded 100℃. In the absence of O₂, X52, 3Cr, and 13Cr exhibited uniform corrosion morphology and FeCO₃ was the main corrosion product. When O₂ was introduced into the system, various forms of Fe₂O₃ appeared on the surface of the samples. The Cr content strongly influenced the corrosion resistance. The 3Cr steel with a low Cr content was more sensitive to pitting than the X52 or 13Cr steel. Thus, pitting occurred on the surface of 3Cr when 1.25 MPa of O₂ was added; this phenomenon is related to the non-uniform distribution of Cr in 3Cr.     

Corrosion behavior and mechanism of the automotive hot-dip galvanized steel with alkaline mud adhesion

The corrosion behavior and mechanism of hot-dip galvanized steel and interstitial-free (IF) substrate with alkaline mud adhesion were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and linear polarization. The results show that non-uniform corrosion occurs on the galvanized steel and IF substrate during 250 h with the mud adhesion. The corrosion products on the galvanized steel are very loose and porous, which are mainly ZnO, Zn₅(OH)₈C₁₂·H₂O and Zn(OH)₂, and Fe-Zn alloy layer with a lower corrosion rate is exposed on the galvanized steel surface; however, the corrosion products on IF substrate are considerably harder and denser, whose compositions of rust are mainly FeOOH and Fe₃O₄, and several pits appear on their surface. The results of continuous EIS and linear polarization measurements exhibit a corrosion mechanism, that is, under activation control, the charge transfer resistances present different tendencies between the galvanized steel and IF substrate; in addition, the evolution of linear polarization resistances is similar to that of charge transfer resistances. The higher contents of dissolved oxygen and Cl- ions in the mud play an important role in accelerating the corrosion.     

CO2/H2S共存条件下集输管道选材的新方法及应用

在CO₂/H₂S共存条件下集输管道中,管道发生腐蚀的可能性急剧增大,因此集输管道的选材至关重要。若选择管材级别较低,则会严重影响管道的正常生产;若管材级别较高,会引起经济成本的浪费。为了使集输管道在CO₂/H₂S共存条件下选材更加合理。在CO₂/H₂S共存腐蚀速率预测模型的基础上,提出了一种新的集输管道选材方法,新方法的步骤为：计算材质的均匀腐蚀速率,腐蚀速率应满足NACE 标准中腐蚀速率的控制值(小于0.076mm/a),结合管道的设计寿命、剩余强度和经济性评价,确定在CO₂/H₂S共存体系下集输管道的材质。以某油田集输管道为示例,根据新方法选择的材质与实验得到的管材结果一致,验证了新方法的准确性。集输管道选材新方法在保证集输管道安全运行的前提下,能够有效降低管材质选择的成本,有利于保证集输管道的安全性和经济性。     

非金属离子对S31603不锈钢表面锈蚀的影响

S31603不锈钢具有优异的耐腐蚀性能,广泛应用于化工、沿海设施等领域。在使用过程中,长期经历内部应力、苛刻环境的腐蚀作用。其中,水溶液中的离子对S31603不锈钢的耐腐蚀性能有着重要影响。通过分析锈蚀S31603不锈钢的微观形貌、元素组成及化学状态等,研究非金属离子对其表面锈蚀的影响。结果表明,NO³⁻、NO²⁻、SO₄²⁻对S31603不锈钢锈蚀起关键作用,Cl^-起辅助作用,且锈蚀主要发生在S31603不锈钢与水溶液长期接触的界面。通过对锈蚀表面进行物质鉴定,发现锈蚀表面含有Fe₂(SO₄)₃、FeSO₄、CrO₂等多种化合物。     

X65管线钢抗H_2S腐蚀的试验研究

研究了不同显微组织管线钢抗H2S腐蚀的行为·结果表明,酒钢生产的X65管线钢,当显微组织是以针状铁素体为主的混合型组织时,管线钢具有优良的抗H2S腐蚀性能·经硫化氢腐蚀试验后,除出现程度不等的氢鼓泡外,试样断面上基本没有产生裂纹·氢鼓泡是由于钢中夹杂物处吸收由腐蚀而产生的氢所引起的·当钢表面上因腐蚀而释放出原子态氢后,由于硫化氢的催化作用,促进原子氢向钢中扩散,并在夹杂物与基体的界面上聚集形成分子氢·随着过程的进行,产生很高的压力,从而形成鼓泡·     

X65MS钢在饱和H2S/CO2环境下的腐蚀产物研究

利用高温高压反应釜模拟酸性油气输送环境,研究X65MS管线钢在饱和H₂S/CO₂环境下的腐蚀行为.采用加速腐蚀实验法评测不同浸泡周期下的平均腐蚀速率.借助X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱仪(EDS)和电子探针(EPMA)等测试技术,分析了不同实验周期下氧化产物膜层的物相组成、表面形貌和截面形貌.结果表明,根据平均腐蚀速率随时间变化曲线的走势与氧化膜层的结构特征,腐蚀过程分为三个阶段.腐蚀过程以H₂S腐蚀为主,氧化产物主要为硫铁化合物(Fe_○xS_○y).随着浸泡时间的增加,铁元素比例减小,富S相比例增大,腐蚀产物膜层厚度增加,结构由疏松逐渐变为均匀、致密,腐蚀产物顺序为马基诺矿(Mackinawite)→过渡相陨硫铁(Troilite)→磁黄铁矿(Pyrrhotite),稳定的磁黄铁矿对X65MS管线钢基体的耐蚀性起到保护作用.     

Investigation of the deterioration of passive films in H2S-containing solutions

The effect of H2S on the corrosion behavior of 316L stainless steel was investigated using electrochemical methods by changing the gas condition from CO2 to H2S and then back to CO2. The presence of H2S showed an acceleration effect on the corrosion of 316L stain-less steel in comparison with CO2. The acceleration effect remained even after the complete removal of H2S by CO2, indicating that the pas-sive film was irreversibly damaged. X-ray photoelectron spectroscopy (XPS) analysis indicated that the passive film was composed of Cr2O3, Fe2O3, and FeS2 after being immersed in H2S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott–Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

丙烷储罐湿硫化氢腐蚀监测技术

钯合金膜氢传感器、恒电势仪、电脑等构成腐蚀监测系统.钯合金膜氢传感器的信号稳定、可靠,由氢传感器检测氢渗透的稳态电流密度,通过16MnR钢的腐蚀速率随稳态氢渗透电流密度变化的方程,计算设备内部湿硫化氢腐蚀速率.现场试验证明该监测系统可用于监测丙烷储罐的硫化氢腐蚀速率和评估设备的安全运行状态.     

玻璃粉对混凝土酸侵蚀性能的影响

采用试验方法,研究了玻璃粉替代胶凝材料在不同掺量(0、5%、8%、15%)时对混凝土抗压强度和耐酸侵蚀性的影响。对比了各个试样在5%H2SO4溶液和5%CH3COOH溶液中腐蚀28 d后的质量亏损和抗压强度损失,并采用SEM分析了试样腐蚀后的表面形貌。结果表明,玻璃粉有利于提高混凝土的耐H2SO4和CH3COOH侵蚀性,耐CH3COOH侵蚀差于耐H2SO4腐蚀,H2SO4侵蚀后的试样表面形成了大量石膏,CH3COOH侵蚀后试样表面疏松并出现了大量孔洞和裂纹。当玻璃粉掺量为8%时,试样的耐H2SO4和CH3COOH侵蚀性最佳。