Sulfidation Behavior of Rhenium and Cobalt-Rhenium Alloys

The sulfidation behavior of Re and three Co-Realloys, 15, 30, and 45 w/o, was studied over thetemperature range 700-800^°C at sulfurpressures of 10^-4 and 10^-2 atm. The kinetics of sulfidation followed theparabolic rate law and the activation energies for allalloys were similar to that of pure cobalt. A positiverate dependency on sulfur pressure was observed and Pt markers were located at the metal-scaleinterface, both observations clearly suggesting thatoutward cation diffusion through a P-type sulfide scaleoccurred. Two dominant sulfides,Co₉S₈ and ReS₂, formed. Weight gainsdecreased for a given set of conditions with increasingrhenium content. An order of magnitude decrease in thesulfidation rate occurred as the rhenium content increased from 15 to 45 w/o. Preferentialsulfidation of cobalt initially occurred, causing arhenium-enriched zone to form in the substrate beneaththe cobalt-sulfide scale. Steep Re-concentrationgradients developed, the zone depth increasing withrhenium content. Significant sulfur diffusion into thesubstrate also occurred, with greater sulfur penetrationtaking place as the rhenium content increased. Sulfides formed at all temperatures were the same on thethree alloys, but the scales were denser on thehigher-rhenium alloys. The initial sulfide to form wasCo₃S₄, but, subsequently,Co₉S₈ became the dominant sulfide, forming beneaththe outer Co₃S₄ layer.ReS₂ formed at lower cobalt levels. Pure Rewas also studied, the sulfidation rate being about10⁴ times slower than that of cobalt. Thedecreasing rate of sulfidation with increasing Recontent is attributed primarily to slower cobaltdiffusion outward through the Reenriched substrate, aphenomenon similar to that observed by C. Wagner for theoxidation of Ni-Pt alloys.     

Effects of Mo and Al Additions on the Sulfidation Behavior of 310 Stainless Steel

The high-temperature sulfidation behavior of 310stainless steel (310SS) with Mo and Al additions (up to10 at.%) was studied over the temperature range700-900°C in pure-sulfur vapor over the range of 10^-3 to 10^-1 atm. Thecorrosion kinetics followed the parabolic rate law inall cases and the sulfidation rates increased withincreasing temperature and sulfur pressure. Thesulfidation rates decreased with increasing Mo and Al contents and it wasfound that the addition of 10 at.% Mo resulted in themost pronounced reduction among the alloys studied. Thescales formed on 310SS with Mo additions were complex, consisting of an outer layer of ironsulfide (with dissolved Cr), (Fe,Ni)₉S₈, andCr₂S₃/Cr₃S₄(with dissolved Fe), and an inner heterophasic layer ofFe_1-xS,Cr₂S₃/Cr₃S₄,NiCr₂S₄,Fe_1.25Mo₆S_7.7, FeMo₂S₄, andMoS₂. The scales formed on 310SS with Mo andAl additions had a similar mixture as above, except thatAl_0.55Mo₂S₄ was alsoobserved in the inner layer. The formation ofMoS₂ andAl_0.55Mo₂S₄ partly blocked the transport of cations throughthe inner scale, resulting in the reduction of thesulfidation rates compared to 310SS.     

Corrosion of Three Commercial Steels Under ZnCl2 –KCl Deposits in a Reducing Atmosphere Containing HCl and H2S at 400–500°C

The corrosion of three commercial steels in a reducing atmosphere containing HCl plus H₂S in the presence of ZnCl₂–KCl deposits has been investigated at 400–500°C and compared with the corrosion of the same materials in a similar gas mixture free from H₂S. The presence of H₂S in the gas accelerated the corrosion of the three commercial steels beneath ZnCl₂–KCl deposits. All materials suffered from severe corrosion with partial detachment and spalling of the external scales. Degradation of the steels resulted from the penetration of chlorine-containing species through the scale formed initially down to the metal matrix, because chorine-rich species were detected close to the alloy/scale interface. Although the corrosion resistance generally increased with increasing Cr content, even the high-Cr stainless steel SS304 is still unable to provide good corrosion resistance against the ZnCl₂–KCl deposits in the presence of H₂S due to the bad adherence of the scales to the alloy. The mechanisms of attack are discussed on the basis of thermodynamic considerations and of the active-oxidation model.     

The high-temperature corrosion behavior of Co-Nb alloys in mixed-gas atmospheres

The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H₂-H₂S-H₂O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb₂O₅ in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb₃S₆, a small amount of NbO₂ was found in the inner layer. The reason for the formation of NbO₂ over that of Nb₂O₅ in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO₂-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO₂ particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.     

Effect of Hf Additions on the Isothermal-Oxidation Behavior of TiAl at High Temperatures

The isothermal-oxidation behavior of TiAlcoupons containing Hf of up to 5.2 mass % has beenstudied in the temperature range 1100-1400 K in a flowof purified oxygen under atmospheric pressure. Theaddition of 0.2% Hf is very effective to decrease theoxidation rate at 1200 and 1300 K. Metallographicexamination using conventional methods revealed that theinitially-formed Al₂O₃ scale ismaintained very sound by the addition. However, further additions ofHf result in a slight enhancement of oxidation at 1200K and a gradual decrease of the effect at 1300 K.Finally, there is almost no effect by the addition of 5.2% Hf at 1300 K. Excess amounts of Hf leadto the formation of oxide mounds on theAl₂O₃ scale. They grow in size andnumber during subsequent oxidation until the wholespecimen surface is covered with a thick scale. Such a scale is notprotective having a structure often reported in theliterature. The effect of the addition of 0.2% Hfbecomes small at 1350 K and at 1400 K it is inverted.Possible mechanisms for the improvement attained by thesuitable addition are discussed.     

Influence of Zr or Hf additions to Fe-23Cr-5Al on the protectiveness of preformed Al2O3 scales against sulfidation

An Fe-23Cr-5Al alloy and those containing 0.17 w/o Zr or 0.12 w/o Hf were oxidized to form -Al₂O₃ scales in a flow of pure O₂ at 1300 K for specified periods up to 400 ks, and subsequently sulfidized at 1200 K in an H₂ –10% H₂S atmosphere without intermittent cooling. The protectiveness of the preformed scale was evaluated by the protection time after which a remarkable mass gain takes place owing to the rapid growth of sulfides. In general, the protection time increases as the scale thickens. Both additives increase the protection time to some degree by forming more structurally perfect scales. However, ZrO₂ particles on or near the outer surface of the scale on the Zr-containing alloy provide sites for sulfide formation. The scales formed on the grain boundaries of the Hf-containing alloy are ridged. The tops of the ridges are associated with cracks, which provide preferential sites for sulfide growth.     

模拟油田工况条件低Cr钢抗H2S应力腐蚀开裂行为研究

    运用四点弯曲试验方法,参照NACE 0177-2005标准研究了低Cr钢在模拟塔里木油田工况条件下的抗H₂S应力腐蚀开裂（SSC）行为.结果表明：经720小时试验后,0.5 Cr试样表面未发现宏观及微观裂纹,表现出良好的抗SSC能力,而普通3 Cr、5 Cr试样表面均发现宏观及微观裂纹,没有通过抗SSC性能检测;应从成分设计及适当的热处理等方面着手,获得理想的显微组织,来提高3 Cr、5 Cr钢的抗SSC性能.     

长期时效N10276合金在CO2/H2S/Cl- 环境中的腐蚀行为

通过电化学阻抗与循环动电位极化的方法研究了在CO₂/Cl^-以及CO₂/H₂S/Cl^-溶液体系中、长期时效前后N10276合金的腐蚀机理。结果表明,阻抗弧的低频区间出现了一个不完整的容抗弧,并且随H₂S浓度的增加（10~100 μL/L）转变为Warburg阻抗,其主要原因是高含量H₂S相关吸附物。H₂S可以增加合金腐蚀速率。相比较而言,长期时效处理主要作用于合金点蚀的形成,其中,经过长期时效处理的奥氏体组织内存在大量的第二相（富含Mo与Ni的μ相）,而析出物周围的区域成为优先腐蚀区域,进而导致了N10276合金点蚀的发生。     

Corrosion behavior of three iron-based model alloys in reducing atmospheres containing HCl and H2S at 600 °C

The corrosion of three Fe-xCr alloys (x = 8, 12, 18 wt.%) was examined at 600 °C in reducing atmospheres containing HCl and H₂S with two different H₂S contents and compared with the behavior of the same materials in H₂S-free H₂-CO₂ and H₂-HCl-CO₂ mixtures producing similar oxygen and chlorine pressures. Exposure to the low-H₂S gas mixture had only a reduced effect on the behavior of Fe-8Cr and Fe-18Cr, but increased significantly the corrosion rate of Fe-12Cr. Increasing the H₂S level accelerated the corrosion of all the alloys, but particularly that of Fe-18Cr. In both cases only minor amounts of sulfur and chlorine were present close to the alloy/scale interface. An increase of the Cr content reduced the corrosion rate in both H₂S gas mixtures, especially in the range 8-12 wt.% Cr, due to a larger volume fraction of Cr₂O₃ in the scale. The results have been discussed on the basis of the thermodynamic stability diagrams of the Fe-O-Cl-S and Cr-O-Cl-S systems.     

P110钢在CO2／H2S环境中的适用性研究

采用高温高压实验设备辅以失重法,研究了CO2／H2S腐蚀环境中P110钢的腐蚀性能,用SEM、EDS和XRD等分析了腐蚀产物．分别用电化学充氢及NACE TM0177A法对P110钢进行耐氢损伤试验．结果表明,虽然P110钢在试验环境中的均匀腐蚀速率很小,未发生点蚀,但随着充氢量的增加,强度、伸长率及断面收缩率均降低．...     

Electrochemistry of deformed smooth surfaces and short corrosion fatigue crack growth behaviour

Abstract

The polarisation characteristics for a deformed smooth surface of a 0·2% carbon steel in an artificial sea water have been determined under static and cyclic loading conditions. The influence of strain level and loading frequency on anodic and cathodic Tafel constants, corrosion current density, and corrosion potential is described. Based on these data, the conditions for corrosion fatigue testing which corresponded to a maximum synergism between surface deformation and anodic dissolution were determined. Corrosion fatigue tests, which were conducted under both constant potential and constant current density conditions have shown that a process of metal dissolution plays a determining role in the short corrosion fatigue crack growth behaviour. An experimentally based criterion is proposed involving the development of a short corrosion fatigue crack, of characteristic size, which is associated with the spacing between the major microstructural barriers. This criterion is a function of both shear stress and the parameters controlling the anodic dissolution process on a cyclically deformed smooth suiface. An expression predicting the formation of short corrosion fatigue cracks is presented which takes into account the synergistic action of shear stress and the corrosion process.     

Comparison of corrosion scales formed on KO8OSS and N8O steels in CO2/H2S environment

Abstract

Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) were applied to analyse the microstructure and composition of the corrosion scale formed on KO80SS and N80 tubes with carbon dioxide (CO₂) and hydrogen sulphide (SO₂). The corrosion scales of both KO80SS and N80 tubes were of the double layer structure, and not only uniform corrosion but also localised corrosion was observed. The crystal of the surface layer is laminar. The main phase in the outer layer is calcium carbonate (CaCO₃), and the inner scale consisted of iron carbonate (FeCO₃) for KO80SS steel and FeS_0·9 with a little amount of FeCO₃ for N80 steel respectively. Additionally, the electrochemical techniques were used to investigate the characteristics of the corrosion scales. The results indicated that the polarisation resistance R_p of KO80SS steel film was nobler than that of N80 steel film. Finally, the corrosion current I_corr of KO80SS steels was lower than that of N80 steels. Corrosion scale of KO80SS tube steels is more protective to the matrix than that of N80 tube steels.     

B101连续油管应力腐蚀开裂行为分析

研究了连续油管的抗H2S环境应力腐蚀开裂(SSCC)行为.利用扫描电镜(SEM)观察了断口形貌,用能谱仪(EDS)分析了断口元素组成,从环境因素、材料组织、化学成分等方面分析了断裂机理.结果表明,母材对应力腐蚀不敏感,焊缝是应力腐蚀的薄弱区域.焊缝断裂可分为裂纹孕育期、裂纹发展期、裂纹快速增长期、完全破坏期.应力在72...     

2205双相不锈钢在酸性H2S环境下的应力腐蚀行为及开裂机理研究

_{摘要:采用C型环实验研究了2205双相不锈钢在饱和H2S环境下的应力腐蚀行为及开裂机理。研究结果表明,2205双相不锈钢在NACE标准A溶液中有良好的抗应力腐蚀能力。通过OM}、_{SEM、EDS及电化学手段分析得出2205双相不锈钢的应力腐蚀开裂经历了表面点蚀,蚀坑形成,H2S解离,H原子吸附并从蚀坑位置扩散进入金属基体,在金属基体中聚集,通过氢致开裂机制导致裂纹萌生,并逐渐扩展。}     

Effect of flow velocity on pipeline steel corrosion behaviour in H2S/CO2 environment with sulphur deposition

The effect of element sulphur on the performance of corrosion inhibitor in H₂S/CO₂ gas field solution was investigated at different velocities. The morphology and composition of corrosion products were characterised by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) methods. The results indicated that L360 QS steel surface suffered from sulphur-induced pitting corrosion at a low velocity due to insufficient sulphur-carrying fluid power. At high flow velocities, the steel surface is likely to be suffered high fluid power which can remove the inhibitor film and corrosion scales by the mechanical erosion effect. The sulphur corrosion mechanism model and the flow-induced corrosion model due to the high wall shear force have been proposed in the study. This work suggested that the gas production rate should be controlled at an acceptable level to guarantee the service safety of pipeline system.     

Q125级套管钢高频电阻焊接头耐CO2/H2S腐蚀行为

采用SEM,EBSD和电化学等手段研究了Q125级石油套管钢高频电阻焊接头的耐CO₂/H2S腐蚀行为.结果表明,Q125级套管钢高频电阻焊接头处母材的耐腐蚀性能最好,热影响区次之,而焊缝的耐腐蚀性能最差,导致高频电阻焊接头在CO₂/H₂S腐蚀环境中产生了沟槽腐蚀.试验钢焊缝处的大角晶界比例高于母材和热影响区,从而使焊缝区反应速度常数高于母材和热影响区,这是焊缝区腐蚀速率最高的一个重要原因.通过电化学分析表明,焊缝处的电极反应的极化阻力最小,腐蚀反应易于发生;而母材的电极反应的极化电阻最大,腐蚀反应不易进行,这与腐蚀试验所得结果及极化曲线分析结果一致.     

油气管道CO2/H2 S腐蚀及防护技术研究进展

CO2和H2S是油气管道中主要的腐蚀介质,两者往往同时存在于原油和天然气之中,是造成油气输送管道内腐蚀发生的主要原因之一,甚至会导致管道失效、穿孔、泄漏、开裂等现象,严重威胁了管网的安全运行及正常生产。因此CO2和H2S引起的管道腐蚀问题,已成为当前研究的热点问题。针对油气管道日益严重的CO2和H2S腐蚀问题,综述了CO2单独存在、H2S单独存在以及CO2和H2S共同存在三种体系中油气管道的腐蚀过程,得出了在这三种腐蚀体系下油气管道出现的主要腐蚀行为规律以及腐蚀机理。阐述了CO2和H2S共同存在体系下,缓蚀剂、耐蚀性管材、电化学防腐技术、管道内涂层技术等先进的油气管道腐蚀防护技术,并剖析了这些防护措施各自的特点及在实际工程使用中的优势和局限性。最后,展望了CO2和H2S共存体系的进一步研究方向以及更经济、更有效的防腐措施发展前景。     

Updated CO2/H2S internal corrosion model of natural gas pipelines based on flow field calculations

The ‘A line’ of the Sichuan Natural Gas East Transportation in China was used as the subject of the study, and an existing CO₂/H₂S corrosion model was utilised to predict the uniform corrosion rate. Then, the flow parameters were simulated by computational fluid dynamics based on turbulence theory, and the influence on the corrosion rate of the pipeline was analysed in a detail to more accurately describe the corrosion problems of natural gas pipelines that contain CO₂/H₂S. After that, an updated CO₂/H₂S corrosion model under the influence of flow filed was proposed by modifying the existing CO₂/H₂S corrosion model. The actual condition was calculated by the updated CO₂/H₂S corrosion model. Results show that flow parameters, namely, velocity, turbulent kinetic energy and phase distribution, affect pipeline corrosion. The flow parameters did not change significantly at the small scale changes in the pipeline (5 and 15°) of a broad and smooth flow channel of the large diameter gas transport pipeline. The shape of corrosion often appears in the form of an elliptical sheet. The corrosion location and the corrosion rate calculated by the updated model are consistent with the wall thickness detection data in the site conditions, which verified that the updated CO₂/H₂S corrosion model is valid. The updated CO₂/H₂S corrosion model influenced by the flow field can predict the corrosion distribution and the corrosion rate of the three-dimensional key positions in natural gas pipelines.     

Influence of a mixed Al2O3+Cr2O3 superficial coating on the non-isothermal oxidation behavior of Fe and Fe-Cr alloys

The non-isothermal oxidation behavior of electrolytic-grade iron and Fe-Cr alloys in dry air has been studied using linear heating rates of 6 K/min, 10 K/ min, and 15 K/min up to a final temperature of 1273–1473 K. Some of the iron and iron-chromium alloy samples were given a surface treatment by dipping them in an aqueous solution containing both Cr and Al ions before their oxidation studies. This pretreatment has resulted in improved oxidation resistance and scale adherence as depicted by no scale rupture even after a second thermal cycle. Mass changes were recorded gravimetrically, and scales have been characterized by SEM, EPMA, and x-ray diffraction analyses.     

H2S/CO2环境中L360钢点蚀行为研究

利用静态挂片失重法研究了含H₂S/CO₂模拟油田水溶液中, 温度及Cl^-浓度对L360管线钢点蚀的影响, 并利用Gumbel第一类近似函数分析了最深蚀孔概率. 结果表明, 在40℃~70℃之间, Cl^-浓度为10 g/L条件下, 点蚀的严重程度随温度增高而增大. 恒定温度下, Cl^-浓度对点蚀发生也有明显的影响, 当Cl^-在10×15 g/L范围时, 腐蚀试样发生明显的点蚀; 当Cl^-浓度大于20 g/L时, 试样主要发生均匀腐蚀, 随着Cl^-浓度的增大, 腐蚀产物膜变得更加疏松, 保护性能下降, 均匀腐蚀速率增大. 最深点蚀分布服从Gumbel第一类近似函数.