Grain boundary engineering of titanium-stabilized 321 austenitic stainless steel

Grain boundary engineering (GBE) primarily aims to prevent the initiation and propagation of intergranular degradation along grain boundaries by frequent introduction of coincidence site lattice (CSL) boundaries into the grain boundary networks in materials. It has been reported that GBE is effective to prevent intergranular corrosion due to sensitization in unstabilized 304 and 316 austenitic stainless steels, but the effect of GBE on intergranular corrosion in stabilized austenitic stainless steels has not been clarified. In this study, a twin-induced GBE utilizing optimized thermomechanical processing with small pre-strain and subsequent annealing was applied to introduce very high frequencies of CSL boundaries into a titanium-stabilized 321 austenitic stainless steel. The resulting steel showed much higher resistance to intergranular corrosion after sensitization subsequent to carbon re-dissolution heat treatment during the ferric sulfate–sulfuric acid test than the as-received one. The high CSL frequency resulted in a very low percolation probability of random boundary networks in the over-threshold region and remarkable suppression of intergranular corrosion during GBE.     

Sensitization induced stress corrosion failure of AISI 347 stainless steel fractionator furnace tubes

Austenitic stainless steel tubes are used as furnace tubes in petrochemical industries mainly because of their corrosion resistance and mechanical strength. AISI 347 grade stainless steel is used as furnace heater tubes in the fractionator of hydrocracker unit. Even though this stainless steel is stabilized with the addition of niobium thus preventing sensitization related corrosion failures, operational and maintenance errors may result in premature failures if conditions prevail. The present work reports the premature failure of AISI 347 grade fractionator furnace tubes after nearly 8 years of service. The failure occurred after shutdown. Carbonaceous deposits were found on the inner walls of the tube and circumferential cracks were found beneath the deposit. The service exposed 347 SS alloy tube was in the sensitized condition as confirmed by microstructure and double loop electrochemical potentiodynamic reactivation test. The tube material got sensitized possibly by localized overheating at the carbon layer deposited site. During shutdown of hydrocracker unit polythionic acid formation occurred possibly due to errors in shutdown procedures. Sensitized alloy 347 tube undergone polythionic acid induced intergranular stress corrosion cracking (PASCC).     

哈氏C-276合金与16MnR钢在盐酸中的电偶腐蚀行为

石化厂急冷塔中的哈氏C-276合金和16MnR钢易形成电偶对,在塔中HCl气氛下发生腐蚀。测定了哈氏C-276合金与16MnR钢在10%盐酸中的自腐蚀速率、电偶腐蚀速率和稳态极化曲线,探讨了偶接时间、阴阳极面积比、环境温度及腐蚀液流速对阳极电流密度的影响。结果表明:2种金属偶接后,阴极哈氏C-276合金腐蚀速率得到抑制,阳极16MnR钢腐蚀速率急剧增大;2种金属自腐蚀电位相差超过200 mV,电偶电位接近16MnR钢的自腐蚀电位;随偶接时间延长,电偶电流不断衰减,24 h后趋于稳定;阳极电流密度随阴阳极面积比增大、温度升高而增大,但呈非线性增长,一定程度后增长趋势变缓;流动的腐蚀液中的阳极电流密度大于静止腐蚀液中的。     

Failure of a Secondary Superheater Tube in a 140-MW Thermal Power Plant

This investigation was conducted to determine the cause of failure of a welded joint of a secondary superheater tube from a 140-MW thermal power plant. Chemical analyses along with detailed optical microscopic examination of a secondary superheater tube were carried out to predict the probable cause of failure. Microstructure of the secondary superheater tube welded between austenitic stainless steel to low alloy steel revealed presence of a thin layer of metal carbide along the weld interface which eventually led to intergranular cracking at austenite grain boundaries. It was concluded that the formation of brittle carbide layer was due to migration of carbon at elevated temperature led to failure of the tube.     

316L不锈钢表面纳米化后腐蚀性能研究

对表面纳米化和未经表面纳米化处理的316L不锈钢的样品分别进行点蚀实验和应力腐蚀对比实验,在3.5%(质量分数)NaCl水溶液中分别测出它们的极化曲线.结果表明,316L不锈钢表面纳米化后抗点蚀性能下降,抗应力腐蚀性能提高.对应力腐蚀断口的SEM 分析发现,316L不锈钢应力腐蚀断口有明显分区现象,断裂形式为韧性断裂,开裂通道既有穿晶型也有沿晶型.     

Intergranular stress corrosion cracking of acoustic-filter hooks used in car

Some acoustic-filter hooks used in car fractured in service. The failure mechanism of the hooks is intergranular stress corrosion cracking. The necessary conditions (susceptible composition of the hook materials; presence of chloride in service environment; presence of residual tensile stress and occurrence of sensitization in the fracture region) caused intergranular stress corrosion mechanism. Non-qualified chemical composition of the hooks (much higher carbon content than the specified of AISI 304 stainless steel) is mainly responsible for the failure of the hooks, which is a key inherent factor.     

原子力显微镜评价奥氏体不锈钢晶间腐蚀敏感性的研究

由13Cr可焊马氏体不锈钢(WMSGSS)制造的油气管线由于价格便宜,相对于昂贵的耐腐蚀合金来说是一个很有竞争力的选择。但是实验室试验和现场经历表明,13Cr马氏体不锈钢焊接接头热影响区发生了沿晶应力腐蚀开裂(IGSCC)。对于低等级的马氏体不锈钢来说,沿晶应力腐蚀开裂机理被认为是在晶界的碳化物附近存在贫铬区。对于中等级和高等级马氏体不锈钢来说,只在实验室试验发现有应力腐蚀开裂。它们的应力腐蚀开裂机理还没有明确,虽然最可能的应力腐蚀开裂机理也被认为和低等级马氏体不锈钢的应力腐蚀开裂机理类似。原子力显微镜(AFM)已开始广泛用于材料显微组织和环境敏感断裂的研究中。高等级马氏体不锈钢焊接接头对晶间腐蚀/应力腐蚀开裂敏感性很有希望由原子力显微镜检测到。在原子力显微镜技术应用于这项研究之前,用由304不锈钢准备的不同敏化度的试样来确定它的适用性是十分有益的。本文用原子力显微镜研究了不同敏化程度的304不锈钢的晶间腐蚀敏感性并和SEM和EDS结果进行了对比。     

316L和Hastelloy C合金在不同温度循环废酸中的耐蚀性能

为了解316L和HastelloyC合金在不同温度的循环废酸中的耐蚀性能,利用静态挂片试验、电化学试验和扫描电镜研究了2种合金在不同温度循环废酸中的腐蚀速率及形貌。结果表明：在50℃的循环废酸中,316L和HastelloyC合金均具有优异的耐蚀性,且耐蚀性相当;316L和HastelloyC合金的腐蚀速率均随循环废酸温度的升高而增加,316L合金的增加缓慢,HastelloyC合金的增加急剧;当温度由50℃升高到80℃时,循环废酸的氧化性增加,Mo含量较高的HastelloyC合金在循环废酸中不能形成完整、致密的钝化膜,从而使其耐蚀性急剧下降。     

16Cr奥氏体不锈钢晶间腐蚀的敏感性

为了研究1Cr17Mn6Ni5N奥氏体不锈钢(16Cr奥氏体不锈钢)的晶间腐蚀行为,通过光学显微镜(OM)、X射线衍射仪(XRD)和晶间腐蚀试验研究了其在不同敏化温度和冷却方式下,晶间碳化物的析出和耐晶间腐蚀性能的变化。结果表明:16Cr奥氏体不锈钢在敏化温度区间内加热时,晶界碳化物随加热温度的上升而增加,加热温度为850℃左右时晶界析出碳化物最多,主要为Cr_(23)C_6和Cr_7C_3;在敏化温度区间内相同加热温度时,水冷可显著减少其晶界碳化物的析出;16Cr奥氏体不锈钢对晶间腐蚀不敏感。     

奥氏体不锈钢在石油精炼环境中应力腐蚀破裂

通过恒变形和恒载荷试验研究了敏化18—8型奥氏体不锈钢在连多硫酸介质中的应力腐蚀行为。研究表明,介质浓度在2.0～6.0％,PH 值在0.8～1.8范围是材料出现应力腐蚀破裂的敏感介质。断口分析表明,在该体系中破裂属晶间型。钢中晶界贫铬区的存在是产生晶间型应力腐蚀破裂的主要原因。     

Intergranular attack during crevice corrosion of stainless steels

The crevice corrosion resistance of AISI type 316 stainless steel was investigated as a function of carbide precipitation and grain size in 0.5 M NaCl solution using a potentiodynamic technique and a specially designed crevice assembly. It has been found that if there is chromium depletion along the grain boundaries (for sensitized material) or if there is a large grain boundary area per unit volume (for fine grained material), the intergranular attack takes place in the crevice due to the presence of more active areas along the grain boundaries.     

Grain boundary engineering of 304 austenitic stainless steel by laser surface melting and annealing

In order to improve the intergranular corrosion resistance of 304 stainless steel, laser surface remelting experiments were conducted using a 2 kW continuous wave Nd: YAG laser. The grain boundary character distribution (GBCD) and microstructures of the materials were analyzed using EBSD, SEM and OM. The experimental results showed that combination of laser surface melting and annealing on 304 stainless steel resulted in a high frequency of twin boundaries and consequent discontinuity of random boundary network in the materials, which led to an improvement of resistance to intergranular corrosion. The maximum CSL density could reach 88.6% under optimal processing conditions: 1220 K and 28 h.     

Failure of Hastelloy C-276 pump impeller in hydrochloric acid

This paper presents the results of a failure investigation carried out on a cast Hastelloy C-276 pump impeller that suffered general corrosion in 32% hydrochloric acid at ambient temperature in a chemical plant. Microscopic examination revealed that the attack was crystallographic in nature. The attack was more enhanced at the interdendritic arm spacing as well as the boundaries of columnar grains, resulting in deep grooves. Taking into consideration that the local temperature could reach up to 50 °C in the summer months, Hastelloy C-276 was judged to be unsuitable material for applications involving 32% HCl. A search into a suitable alternative alloy did not provide a satisfactory answer. Therefore, rubber-lined pump impeller was considered the better alternative.     

20/316L双金属管的腐蚀失效原因分析

随着20/316L双金属管在油气生产中的推广应用,关于内衬316L不锈钢的腐蚀失效问题日益突出,尤其是条件苛刻的酸性集输环境下,目前相关研究不多.利用扫描电镜(SEM)、能谱仪(EDS)等测试手段对20/316L双金属管在含H2S-Cl-的酸性集输环境中出现的腐蚀失效问题进行了系统分析,探讨了腐蚀失效的原因.结果表明:20/316L双金属管腐蚀类型为局部腐蚀,主要分布于内衬管316L的底部.腐蚀失效的主要原因是腐蚀介质中存在高浓度的H2S与Cl-,共同促进了钝化膜的破裂与点蚀的发展.当存在较高浓度的H2S与Cl-时,钝化膜薄弱处与电位较低的非金属夹杂物处易发生钝化膜的破裂与金属基体的快速溶解而成为点蚀源,形成点蚀.     

Intergranular corrosion of a stud used in safety relief valve

In the present paper, a failure case study on intergranular corrosion of stainless steel stud is discussed. The stud was in the assembly under marine environment, for a period of 11 years. Detailed investigation revealed that the crack had propagated in an intergranular manner, after initiation at threaded region of the stud, leaving behind widespread grain dissolution. The presence of chloride ions in deposits on central region of stud, exposed to marine environment was also established. The high carbon content, coupled with exposure to sensitization range of stainless steel during processing caused corrosion along intergranular corrosion.This paper brings out the details of investigation carried out on the failed stud.     

Grain-size and heat-treatment effects in hydrogen-assisted cracking of austenitic stainless steels

Hydrogen embrittlement of 304L and 316L types austenitic stainless steels has been studied by charging thin tensile specimens with hydrogen through cathodic polarization. Throughout this study we have compared solution-annealed samples, having various prior austenite grain size, with samples given the additional sensitization treatment. The results of the tensile tests while undergoing cathodic charging show that the additional sensitization treatment and coarse-grained samples together, lower the mechanical properties in both 304L and 316L types, and the sensitized steel is more susceptible to hydrogen-assisted cracking. However, the room-temperature yield and ultimate strengths, and the elongation of type 316L, were much less affected depending on the heat treatment and prior austenitic grain size. The fracture surfaces of the specimens tested while cathodically charged show considerable differences between the annealed and the sensitized specimens. The sensitized coarse-grained specimens were predominantly intergranular in both 304L and 316L types, while the annealed 316L type specimens fracture shows massive regions of microvoid coalescence producing ductile rupture and the annealed 304L type specimens fracture were primarily transgranular and cleavage-like. Sensitization seems both to facilitate the penetration of hydrogen along the grain boundaries into the steel and to introduce susceptibility to fracture along grain boundaries while refined grain size improves resistance regardless of the failure mode.     

Helium-induced weld cracking in austenitic and martensitic steels

Helium was uniformly implanted into type 316 stainless steel and Sandvik HT-9 (12Cr-1 MoVW) to levels of 0.18 to 256 and 0.3 to 1 a.p.p.m., respectively, using the tritium trick technique. Autogenous bead-on-plate, full penetration, welds were then produced under fully constrained conditions using the gas tungsten arc welding (GTAW) process. The control and hydrogen-charged plates of both alloys were sound and free of any weld defects. For the 316 stainless steel, catastrophic intergranular fracture occurred in the heat-affected zone (HAZ) of welds with helium levels 2.5 a.p.p.m. In addition to the HAZ cracking, brittle fracture along the centreline of the fusion zone was also observed for the welds containing greater than 100 a.p.p.m. He. For HT-9, intergranular cracking occurred in the HAZ along prior-austenite grain boundaries of welds containing 1 a.p.p.m. He. Electron microscopy observations showed that the cracking in the HAZ originated from the growth and coalescence of grain-boundary helium bubbles and that the fusion-zone cracking resulted from the growth of helium bubbles at dendrite boundaries. The bubble growth kinetics in the HAZ is dominated by stress-induced diffusion of vacancies into bubbles. Results of this study indicate that the use of conventional GTAW techniques to repair irradiation-degraded materials containing even small amounts of helium may be difficult.     

Electrochemical polarization and pitting behaviour of Fe-Al-Mn alloys in chloride solutions

The electrochemical polarization behaviour of the austenitic Fe-8.25 Al-29.95 Mn-0.85 C and Fe-9.33 AI-25.94 Mn-1.45 C alloys, either solution-annealed and/or age-treated, was investigated in 3.5 wt% NaCl solution. Potentiodynamic polarization tests showed that these alloys passivated with difficulty and had much higher anodic passive current densities than that of the conventional austenitic 316 stainless steel (SS). The susceptibility to pitting corrosion of these alloys under open-circuit potential conditions was also studied in 6% FeCl₃ solution. Metallographical examination indicated that pitting and general corrosion occurred on the specimen surfaces. The corrosion rates of these alloys were about one order of magnitude higher than that of the AlSl 316 SS. In general, the corrosion resistances of the Fe-Al-Mn alloys studied were inferior to that of the conventional stainless steel.[/p]     

Stress corrosion cracking in 316L stainless steel bellows of a pressure safety valve

There were three consecutive occurrences of bellows failure in a particular pressure safety valve (PSV) of a petroleum refinery within a time span of one week. The bellows were made of 316L grade austenitic stainless steel, and the PSV was mounted on one of the vessels of vacuum gas oil service in a hydrocracker unit. Metallurgical analysis of the failed bellows revealed that the failure had occurred by stress corrosion cracking (SCC). It was found that the SCC was promoted in the bellows due to the presence of high amount of chloride ions in the operating environment. Studies confirmed that SCC had initiated from the outer surface of the bellows and propagated inwards, resulting in leakage of hydrocarbon from the PSV. The source of chlorine in the environment was identified. It was discovered that SCC in the bellows was caused due to a previous failure in the heavy polynuclear aromatics (HPNA) absorption bed located upstream the process flow line. This failure was due to the presence of high concentrations of chlorine in the granulated activated carbon that was used in the HPNA absorption bed. During the repair of the HPNA bed, there was deposition of carbon soot on the body of the PSV. This carbon soot was the source of chloride ions for SCC to occur in the bellows. Generally, in chloride SCC, crack propagation in 316L SS takes place by transgranular mode. In the present case, however, the crack propagation was predominantly by intergranular mode. The metallurgical factors responsible for this change in micro-mechanism of crack propagation during SCC have been discussed.     

Effects of nitrogen on hydrogen embrittlement in AlSl type 316, 321 and 347 austenitic stainless steels

Hydrogen embrittlement of AlSl type 316, 321 and 347 stainless steels with nitrogen alloying has been studied by a tensile test through cathodic charging. The results show that addition of nitrogen improved resistance to hydrogen cracking regardless of the failure mode. Fracture surfaces of cathodically charged steels showed intergranular brittle zones on each side of the fracture surfaces. AlSl type 316 with nitrogen alloying stainless steel is more resistant to hydrogen embrittlement than AlSl type 321 with nitrogen alloying steel, whereas AlSl type 347 with nitrogen alloying steel is susceptible to hydrogen embrittlement. Nitrogen alloying of stainless steel increased the mechanical properties in hydrogen environments by increasing the stability of austenite.