A study of intergranular corrosion of austenitic stainless steel by electrochemical potentiodynamic reactivation, electron back-scattering diffraction and cellular automaton

The impact of solution and sensitization treatments on the intergranular corrosion (IGC) of austenitic stainless steel (316) was studied by electrochemical potentiodynamic reactivation (EPR) test, and the results showed the degree of sensitization (DOS) decreased as solution treatment temperature and time went up, but it increased as sensitization temperature prolonged. Factors that affected IGC were investigated by field emission scanning electron microscope (FE-SEM) and electron back-scattering diffraction (EBSD). Furthermore, the precipitation evolution of Cr-rich carbides and the distribution of chromium concentration were simulated by cellular automaton (CA), clearly showing the effects of solution and sensitization treatments on IGC.     

晶粒尺寸对奥氏体不锈钢晶间腐蚀敏感性的影响

采用微观形貌观察、电化学方法以及晶界分布特征分析研究316L不锈钢扩散连接接头的晶间腐蚀敏感性,探讨晶粒尺寸和微观结构对不锈钢扩散连接接头敏化的影响。结果表明,扩散连接接头在650 ℃下敏化100 h后晶界处几乎没有发现络合物的析出,而母材经过8 h敏化则析出大量络合物。随着晶粒的增大,316LSS晶间腐蚀敏感性降低。晶粒粗化和低能晶界比例的提高导致扩散连接接头的抗晶间腐蚀能力提高,但晶粒粗化是主要因素。     

Uniform corrosion and intergranular corrosion behavior of nickel‐free and manganese alloyed high nitrogen stainless steels

The uniform and intergranular corrosion behavior of two kinds of nickel‐free and manganese alloyed high nitrogen stainless steels (HNSSs) were investigated. A type of 316L stainless steel (316L SS) was also included for comparison purpose. Both solution annealed (SA) and sensitization treated (ST) steels were examined. It was found that the SA HNSSs had much weaker resistance to uniform corrosion compared to the SA 316L SS. The addition of molybdenum, to some extent, improved the uniform corrosion resistance of the HNSSs. The sensitization treatment had little influence on the uniform corrosion resistance of all the steels. The HNSSs showed an obvious susceptibility to intergranular corrosion, in particular the ST HNSSs. The intergranular corrosion rates of the sensitized HNSSs were much higher than that of the sensitized 316L SS. The degree of interganular attack for the ST HNSSs was much more serious than that for the 316L SS. The addition of molybdenum obviously improved the resistance of the ST HNSSs to intergranular corrosion. The double loop electrochemical potentiokinetic reactivation tests also proved that the HNSSs were rather susceptible to the sensitization treatment compared to the 316L SS. The relatively weak resistance of the HNSSs to uniform and intergranular corrosion may be due to high manganese promoted anodic dissolution. The improvement of uniform and intergranular corrosion resistance caused by the addition of molybdenum could be attributed to the synergistic effects of molybdenum and nitrogen in the HNSSs on the formation and stability of passive film.     

Influence of Ti,C and N concentration on the intergranular corrosion behaviour of AISI 316Ti and 321 stainless steels

Intergranular corrosion behaviour of 316Ti and 321 austenitic stainless steels has been evaluated in relation to the influence exerted by modification of Ti, C and N concentrations. For this evaluation, electrochemical measurements – double loop electrochemical potentiokinetic reactivation (DL-EPR) – were performed to produce time–temperature–sensitization (TTS) diagrams for tested materials. Transmission (TEM) and scanning electron microscopy (SEM) were used to determine the composition and nature of precipitates. The addition of Ti promotes better intergranular corrosion resistance in stainless steels. The precipitation of titanium carbides reduces the formation of chromium-rich carbides, which occurs at lower concentrations. Also, the reduction of carbon content to below 0.03 wt.% improves sensitization resistance more than does Ti content. The presence of Mo in AISI 316Ti stainless steel reduces chromium-rich carbide precipitation; the reason is that Mo increases the stability of titanium carbides and tends to replace chromium in the formation of carbides and intermetallic compounds, thus reducing the risks of chromium-depletion.     

热加工对复合板不锈钢表层晶间腐蚀的影响

对压力容器用低合金钢/不锈钢复合板在热加工后的晶间腐蚀行为进行研究,主要针对三种常用表层不锈钢304,321及316L热加工后的晶间腐蚀特性进行探讨。结果表明:表层不锈钢中,321钢存在少量阶梯组织,接近凹坑组织,过多的热处理工序会引起其晶间腐蚀,但程度上轻于316L钢;304钢为明显的晶间腐蚀类型,受热处理的影响较大,严格控制热加工工艺可使其晶间腐蚀的倾向相对最轻;316L钢热加工过程中的晶间腐蚀倾向最为严重,应尽量减少热处理。合金元素较多的钢种(321和316L)在敏化温度热处理后,晶间腐蚀特征改变不大;低碳不锈钢(304)经热处理后,晶间腐蚀所受影响较大。     

Die Bedeutung des Oxalsäure-Tests für die Prüfung der Korrosionsbeständigkeit nichtrostender Stähle

The meaning of the oxalic acid etch test for testing the corrosion resistance of stainless steels In the oxalic acid etch test according to ASTM A 262 practice A, precipitations of phases rich in chromium and molybdenum which can occur in stainless steels, are preferentially dissoved. The behaviour of such phases in the oxalic acid etch test was investigated taking precipitations of carbide M₂₃C₆, s?-phase, χ-phase and Laves-phase in stainless steels AISI 304 L and 316 L as examples. The chemical composition of these was evaluated with a scanning transmission electron microscope (STEM) by EDS. With coarser precipitations, it was possible to support this analytical method by EDS of metallographic cross sections in a scanning electron microscope (SEM). In oxalic acid, critical threshold potentials exist above which the above mentioned phases are preferably attacked, furthermore critical pH values, below which no selective attack of the precipitated carbides and intermetallic phases occurs. The numerical values of the threshold potentials as well as the critical pH values were evaluated. When testing stainless steels in the oxalic acid etch test, the steel specimens are polarized to a highly positive potential in the very trans passive range. In this potential range the corrosion rate of stainless steels increases with increasing chromium content, while in the active and passive range the corrosion rate decreases with increasing chromium content. Other than the nitric-hydrofluoric acid test, the copper-copper sulfate-sulfuric acid test, and the ferric sulfate-sulfuric acid test, the oxalic acid etch test does therefore not indicate any chromium depletion. Hence, an intergranular attack also occurs when precipitations of carbides rich in chromium are present at the grain boundaries of austenitic stainless steels with the carbides being precipitated without any chromium depletion of the areas adjacent to the grain boundaries. Sensitized austenitic stainless steels which are susceptible to intergranular corrosion due to the precipitation of chromium rich carbides and chromium depletion of the areas adjacent to the grain boundaries, can suffer intergranular SCC in high temperature aqueous environments when additionally critical conditions with respect to the mechanical stress level and the oxygen concentration in the environment are given. For the detection of sensitized microstructures, the oxalic acid etch test must be valued critically due to the dependence of the corrosion rate on the chromium content mentioned above, and is obviously by far less suited than the conventional tests for establishing resistance to intergranular corrosion in sulfuric acid-copper sulfate solutions with additions of metallic copper (Strauß test, severe Strauß test).     

Assessment of intergranular corrosion (IGC) in 316(N) stainless steel using electrochemical noise (EN) technique

In the present work, an attempt was made to demonstrate the use of electrochemical noise (EN) technique in assessment of intergranular corrosion (IGC) in 316(N) stainless steel (SS). Degree of sensitization (DOS) in the specimens aged at 923 K for 24, 40, 50 and 100 h was determined using double loop electrochemical potentiodynamic reactivation (DLEPR) technique. Immediately after applying a prior preconditioning treatment, current and potential noise measurements were made. The DOS was determined from standard deviation of current noise (σ_I) versus time plot and it was found to bear a good correlation with the values obtained by DLEPR. Shot noise analysis of the EN data confirmed the above results.     

Intergranular corrosion susceptibility in supermartensitic stainless steel weldments

The intergranular corrosion susceptibility in supermartensitic stainless steel (SMSS) weldments was investigated by the double loop – electrochemical potentiokinetic reactivation (DL-EPR) technique through the degree of sensitization (DOS). The results showed that the DOS decreased from the base metal (BM) to the weld metal (WM). The heat affected zone (HAZ) presented lower levels of DOS, despite of its complex precipitation mechanism along the HAZ length. Chromium carbide precipitate redissolution is likely to occur due to the attained temperature at certain regions of the HAZ during the electron beam welding (EBW). Scanning electron microscopy (SEM) images showed preferential oxidation sites in the BM microstructure.     

Sensitization Behavior of Type 409 Ferritic Stainless Steel: Confronting DL-EPR Test and Practice W of ASTM A763

Stainless steels employed for manufacturing automotive exhaust systems must withstand severe thermal cycles, corrosive environment due to urea decomposition, and welding operations. AISI 409 ferritic stainless steel can be considered a low-cost alternative for this application. However, depending on the manufacturing conditions during welding cycles, this material can be sensitized due to the precipitation of chromium carbides at grain boundaries. In this work, the intergranular corrosion resistances of the AISI 409 ferritic stainless steel were evaluated after annealing at 300, 500, and 700 °C for 2, 4, and 6 h. Solution-annealed samples were also tested for comparison purposes. Two methodologies were used to assess the sensitization behavior of the 409 stainless steel samples: the first one was based on the ASTM A763 (practice W), while the second one was based on the double-loop electrochemical potentiodynamic reactivation test. It was possible to identify that the annealing treatment performed at 500 °C was more critical to the occurrence of intergranular corrosion.     

Intergranular corrosion of welded joints of austenitic stainless steels studied by using an electrochemical minicell

An intergranular corrosion study of welded joints of austenitic stainless steels (AISI 304 and 316L) has been addressed. A specific small-scale electrochemical cell (minicell) has been used. Four different weldment zones have been studied. The electrochemical methods applied were the electrochemical potentiokinetic reactivation test and electrochemical potentiokinetic reactivation double loop test. These techniques showed that the HAZ was the most critical zone to intergranular corrosion for both materials. The weld metal was susceptible to interdendritic corrosion and the fusion line showed a mixture of intergranular and interdendritic corrosion. The effect of pre- and post-welding heat treatments for AISI 316L was analyzed. The HAZ was again the most critical zone in every heat treatment condition. The results were correlated to the microstructural features of the materials.     

Investigation on Pitting Corrosion of Nickel-Free and Manganese-Alloyed High-Nitrogen Stainless Steels

Pitting corrosion behavior of three kinds of nickel-free and manganese-alloyed high-nitrogen (N) stainless steels (HNSSs) was investigated using electrochemical and immersion testing methods. Type 316L stainless steel (316L SS) was also included for comparison purpose. Both solution-annealed and sensitization-treated steels were examined. The solution-annealed HNSSs showed much better resistance to pitting corrosion than the 316L SS in both neutral and acidic sodium chloride solutions. The addition of molybdenum (Mo) had no further improvement on the pitting corrosion resistance of the solution-annealed HNSSs. The sensitization treatment resulted in significant degradation of the pitting corrosion resistance of the HNSSs, but not for the 316L SS. Typical large size of corrosion pits was observed on the surface of solution-annealed 316L SS, while small and dispersed corrosion pits on the surfaces of solution-annealed HNSSs. The sensitization-treated HNSSs suffered very severe pitting corrosion, accompanying the intergranular attack. The addition of Mo significantly improved the resistance of the sensitization-treated HNSSs to pitting corrosion, particularly in acidic solution. The good resistance of the solution-annealed HNSSs to pitting corrosion could be attributed to the passive film contributed by N, Cr, and Mo. The sensitization treatment degraded the passive film by decreasing anti-corrosion elements and Cr-bearing oxides in the passive film.     

Sensitization control in AISI 316L(N) austenitic stainless steel: Defining the role of the nature of grain boundary

Two grades of AISI 316L(N) austenitic stainless steels differing only in copper content (0.083 and 0.521 wt.%), showed remarkable difference in resistance to sensitization and susceptibility to intergranular corrosion. Different thermal treatments were carried out with an overall objective of altering the nature of the grain boundary. An attempt was made to correlate the degree of sensitization (DOS) with various microstructural parameters such as grain size and grain boundary nature. No clear trend could be established between the individual parameters and DOS. Effective grain boundary energy (EGBE), which is a combined parameter showed clear trend with DOS. The presence of 0.521 wt.% of copper brings down EGBE remarkably leading to improved resistance to sensitization.     

The influence of molybdenum on the intergranular corrosion of a pure ferritic steel with 17% chromium

The influence of adding 3% Mo on the restoration of the intergranular corrosion resistance of a pure ferritic steel with 17% Cr was investigated on specimens quenched from 1050°C and aged at 700°C (from 5 min to 15 h). The tests were conducted in two standard oxidizing reagents currently employed for intergranular corrosion studies (Streicher and Huey tests). Whereas the sensitivity to grain boundary corrosion of a steel without molybdenum decreases in both reagents with the holding time at 700°C, the grain boundary corrosion of a 3% Mo steel, on the contrary, increases progressively. The behaviour of the steel without molybdenum is well accounted for by the theory of chromium depletion wereas that of the steel with 3% Mo can be explained by the increased rate of electrochemical dissolution of chromium carbides in which part of the chromium is replaced by molybdenum. This interpretation then gives a new significance to the Streicher test.     

The influence of molybdenum on the intergranular corrosion of a pure ferritic steel with 17% chromium

The influence of adding 3% Mo on the restoration of the intergranular corrosion resistance of a pure ferritic steel with 17% Cr was investigated on specimens quenched from 1050°C and aged at 700°C (from 5 min to 15 h). The tests were conducted in two standard oxidizing reagents currently employed for intergranular corrosion studies (Streicher and Huey tests). Whereas the sensitivity to grain boundary corrosion of a steel without molybdenum decreases in both reagents with the holding time at 700°C, the grain boundary corrosion of a 3% Mo steel, on the contrary, increases progressively. The behaviour of the steel without molybdenum is well accounted for by the theory of chromium depletion wereas that of the steel with 3% Mo can be explained by the increased rate of electrochemical dissolution of chromium carbides in which part of the chromium is replaced by molybdenum. This interpretation then gives a new significance to the Streicher test.     

316L不锈钢在高含氯离子乙二醇中的腐蚀行为

采用失重法实验研究了温度、Cl-浓度对316L不锈钢腐蚀动力学行为的影响;实验判别了316L的晶间腐蚀倾向.结果表明:在C1-质量浓度为36 516 mg/L,Fe3+质量浓度为776 mg/L的情况下,316L的腐蚀速率随温度的升高而增大,温度超出60℃时腐蚀速率迅速增大,120℃时腐蚀速率达到最大值0.0781 m...     

Intergranular corrosion resistance of microstructure- modified type 316 austenitic stainless steel

Cold working and a double aging treatment was used to produce a microstructure with fine nuclei of carbides distributed throughout the grains to improve the intergranular corrosion (IGC) resistance of austenitic stainless steel. The treatment was carried out on type 316 stainless steel as follows: cold working (20,30, and 40% reductions in thickness), sensitization (923 KJ5 h), and aging each for 1173,1223,1273, and 1323 K/l h, respectively. Specimens in the solution annealed condition (0% cold work) were also given the above treatment. All of the specimens were resensitized at 923 KJ5 h and tested for IGC resistance as per ASTM A262, Practice A(oxalic acid etch test) and Practice E (24 h immersion in boiling Cu-CuSO.₄-H₂SO₄ and the U- bend test). Microhardness measurements were also carried out on all specimens. The results indicated that at an optimum treatment (30% cold work + sensitization + aging) all the specimens showed improved IGC resistance. The 0 and 20% cold worked specimens showed improvement at higher aging temperatures only. Specimens undergoing 40% cold work exhibited a decrease in IGC resistance. Compared to as-cold-worked specimens, an improvement in IGC resistance was obtained with 30% cold working.     

Effect of ageing heat treatments on the microstructure and intergranular corrosion of powder metallurgy duplex stainless steels

The influence of ageing heat treatments (675 and 875 °C for 1.5 to 48 h) on the microstructure and intergranular corrosion resistance of sintered in nitrogen duplex stainless steels was investigated. The materials were obtained by sintering mixtures of austenitic AISI 316L and ferritic AISI 430L powders. Corrosion behaviour was evaluated by using electrochemical techniques. The beneficial effect of nitrogen on corrosion behaviour of solution annealed samples was established. During ageing, secondary phases were precipitated and the intergranular and transgranular corrosion resistance significantly decreased though repassivation was observed in specimens aged at 875 °C for times up to 8 h.     

离子渗碳温度对316L不锈钢渗层组织和性能的影响

利用低温离子渗碳技术.在不同温度下对AISI 316L奥氏体不锈钢进行渗碳处理.利用光学显微镜、显微硬度计、XRD以及电化学测试技术研究了渗碳温度对不锈钢表面显微组织和性能的影响.结果表明,渗碳温度显著影响AISI 316L奥氏体不锈钢渗碳层的组织结构与性能.渗碳温度在400～550℃之间时,可以获得无碳化物析出的、具有单一γ_c相结构的渗碳层;渗碳温度在550℃时,渗碳层为γ相+Cr_(23)C_6+Cr_7C_3+Fe_3C+Fe_2C的混合组织.渗碳层的厚度与硬度均随渗碳温度的升高而增加.550℃是AISI 316L奥氏体不锈钢中铬的碳化物析出的临界温度.为了避免铬的碳化物析出而降低不锈钢的耐蚀性能.奥氏体不锈钢渗碳必须在低于550℃的渗碳温度下进行.     

Investigation of Susceptibility to Intergranular Corrosion of Tin-Added Austenitic Stainless Steel

The intergranular corrosion(IGC) character of tin-added B316 LX and the influence of tin addition on IGC susceptibility were investigated by DL-EPR, oxalic acid etch test and transmission electron microscopy. IGC susceptibility of B316 LX is mainly caused by the precipitation of M23C6 carbide and intermetallic Laves phase. DL-EPR test is unsuitable to evaluate the IGC susceptibility of B316 LX with long-time sensitization, because more carbides and intermetallic phases are formed at grain boundaries and inside the grains, which induce more severe IGC and pits attacks. Tin addition increases the IGC susceptibility, maybe due to diffusion of tin toward grain boundaries.     

Martensitic transformation in an intergranular corrosion area of austenitic stainless steel during thermal cycling

An oxidation-assisted martensitic phase transformation was observed in an austenitic stainless steel after thermal cycling up to 970 °C in air in a solar thermal steam reformer. The intergranular corrosion areas were investigated by electron backscatter diffraction (EBSD), transmission Kikuchi diffraction (TKD) and transmission electron microscopy (TEM). The structural-and-chemical maps revealed that within intergranular corrosion areas this martensitic transformation primarily occurs in oxidation-induced chromium-depleted zones, rather than due to only sensitization. This displacive transformation may also play a significant role in the rate at which intergranular corrosion takes place.