The corrosion behavior of AISI 304L stainless steel in 0.1 M HCl at room temperature—II. The effect of cold working

This paper describes the results of a study concerning the influence of cold working upon the corrosion behaviour of an AISI 304L in HCl 0.1 M at room temperature. Potentiostatic tests, with test times of ≥ 150 h, followed by SEM observations, revealed that even though cold working lowers the critical pitting potential, it does not impair the susceptibility to localized corrosion. Evidence is provided for (1) pitting activity below the primary passivation potential, and (2) preferential attack on either the austenitic matrix or the martensitic phase, depending upon the corrosion potential below the protection field. It can be hypothesized that the above-mentioned behaviour is a consequence of the formation of corrosion products favoured by the presence of two metallic phases. Such products have inhibiting properties which determine pitting corrosion below the primary passivation potential and, in addition, they hinder the formation of passivity films and facilitate their local destruction.     

Über den Einfluß der Austenitstabilität von 18/8-Chrom-Nickel-Stählen auf die Verformungseigenschaften und auf das Korrosionsverhalten dieser Stähle

Influence of austenite stability of 18-8 Cr-Ni-steels on the cold working and corrosion properties of these steels The martensite formed during cold working has a negative effect on uniform corrosion only when the specimen is active in the particular medium; if so, corrosion current density increases with the degree of cold working. The martensite generated by cold working reduces on the other hand the susceptibility to intercrystalline corrosion and – in amounts up tn 2% – increases the time to failure in stress corrosion cracking (15 and 45 kp/mm²). The pitting potential is not shifted by the martensite, but pit density increases with the martensite content. In the Kesternich test no negative effect of the martensite is found. It is therefore concluded that reducing the Ni content in 18-8 steels improves workability without having a pronounced deleterions bearing on corrosion behaviour.     

Der Einfluß martensitischer Gefügeausbildung in Cr?Ni-Stählen auf das Lochfraßverhalten

Effect of martensitic structures in Cr? Ni-steels on pitting corrosion The paper describes the influence of martensitic microstructures, which were produced in austenitic CrNi steels by directed kryoforming at ?196°C, on pitting corrosion. The investigations were carried out with a series of alloyed steels with a basis content of 17% chromium and nickel contents between 8% and 20%. The microstructures were characterized by means of radiographic, magnetic, metallografic, mechanical and chrono-potentiostatic techniques which revealed correlations between martensite transformation and properties. The comparison of measurement results obtained for the strain hardening, flow and corrosion behaviour has shown similarities in the change of hardening characteristics and pitting potentials in dependence on the degree of deformation. The pitting behaviour is improved if α′-martensite is primarily formed by a sufficient degree of plastic deformation. In contrast, microstructures with ?-martensite and derived portions of α′-martensite display a less favorable pitting behaviour.     

氮对马氏体不锈钢00Cr13Ni4Mo组织和性能的影响

采用热膨胀仪、光学显微镜以及CM12型透射电子显微镜研究了添加0.04%N(质量分数)对00Cr13Ni4Mo马氏体不锈钢相变以及正火和回火后不锈钢组织变化的影响;通过拉伸、冲击实验和阳极极化曲线测定研究了N对正火和回火后马氏体不锈钢力学性能以及点蚀点位的影响。结果表明:1050℃正火后,N全部固溶于马氏体基体中,有效提高了实验钢的强度,同时降低了韧性;550℃以上回火后,在马氏体板条内部以及板条之间形成逆变奥氏体,有效提高了马氏体不锈钢的塑性和韧性;N抑制逆变奥氏体的形成,从而抑制了不锈钢在回火过程中的软化;同时,回火过程中,Cr2N在马氏体板条界面及内部大量析出,造成不锈钢韧性和点蚀点位下降。采用传统的正火+Ac1温度以上回火热处理工艺不利于含N马氏体不锈钢获得良好综合性能。     

Influence of heat treatments on microstructure and pitting corrosion resistance of 15%Cr supermartensitic stainless steel

Supermartensitic is a new class of stainless steels in development and consolidation as commercial products. Significant changes on chemical composition of conventional martensitic stainless steels, such as the reduction of the carbon content to <0·03 wt-%, and the addition of Ni and Mo, marked the development of this new group of alloys. New grades containing higher amounts of Cr and small additions of Ti and/or Nb were developed recently. As a result, supermartensitic steels offer an interesting combination of high strength, toughness, weldability and corrosion resistance. In this work, the pitting corrosion resistance of a 15Cr supermartensitic steel with Ni, Mo and Cu additions was studied. It is well known that the mechanical properties and corrosion resistance of martensitic steels are adjusted by the final tempering treatment. Several single tempering treatments in the 300–650°C range and double tempering treatments were performed in order to obtain different microstructures. The pitting corrosion resistance was investigated by electrochemical test in 3·5%NaCl solution. It was found that the pitting potential slightly decreased with the increase in temperature and time of tempering. The analysis of pits formed during the corrosion tests showed that ferrite islands are more corrosion resistant than the martensitic matrix due to the higher Cr and Mo contents.     

Long-term corrosion behaviour of stainless reinforcing steel in mortar exposed to chloride environment

Long-term corrosion behaviour of six stainless reinforcing steels embedded in mortar and exposed to chloride media was monitored by electrochemical impedance spectroscopy at the open circuit potential during the period of 2 years. Corrosion behaviour of studied steels was divided into two phases characterized by different interfacial behaviour: (i) passive phase and (ii) pitting propagation phase. After 2 years, duplex steel 1.4362 showed very good corrosion performance similar to austenitic steel 1.4401. Steel types with low Ni content but with high N and Mn content, 1.4597 and 1.4162, showed lower corrosion resistance compared to austenitic steel 1.4301.     

Relationship Between Microstructure and Corrosion Behavior of Cr12Ni3Co12Mo4W Ultra-High-Strength Martensitic Stainless Steel

The effect of tempering temperature on the microstructure and corrosion behavior of Cr12Ni3Co12Mo4W ultra-high-strength martensitic stainless steel was investigated using transmission electron microscopy, atomic force microscopy, X-ray diffraction, and electrochemical tests. The microstructures of the ultra-high-strength martensitic stainless steel consisted of some retained austenite and lath/plant martensite with the carbides distributed within the matrix and at the grain boundaries. Tempering of the steel for 4 h at various temperatures resulted in various carbide grain sizes and different amounts of the retained austenite. The results showed that larger carbide grains led to diminished corrosion resistance, whereas larger amounts of the retained austenite resulted in improved corrosion resistance. The steels exhibited good corrosion resistance in 0.017 mol/L NaCl solution and exhibited pitting corrosion in 0.17 mol/L Na Cl solution. The martensite and prior austenite crystal boundaries dissolved in solution with pH 1.     

节镍型奥氏体不锈钢组织性能及控制机理研究

节镍型奥氏体不锈钢生产中合理控制其C、N含量和Cr、Ni当量,使其冷加工硬化小,拉深成形性能优异,形变诱导马氏体量少,时效开裂风险小,室温下奥氏体组织稳定是其生产应用的关键技术难点。为此,研究了不同化学成分节镍型奥氏体不锈钢在热轧、退火、冷轧退火后的金相组织及力学性能,分析了奥氏体稳定性和冷轧形变诱导马氏体相变的控制规律。结果表明:试验钢在热轧后奥氏体组织呈未完全再结晶状态,退火后奥氏体组织再结晶充分,晶粒尺寸为12～14 μm,且低的碳含量有利于改善碳化物的析出情况;试验钢冷轧变形过程中马氏体转变受奥氏体稳定性的影响,即受M_d30/50温度控制及化学成分的影响,M_d30/50温度值越高,镍当量越小,奥氏体稳定性越差,形变诱导马氏体含量越高,冷轧变形抗力越大,在退火过程越容易发生马氏体向奥氏体的逆转变,形成晶粒尺寸呈“双峰”状分布的混晶组织。因此,化学成分设计是实现节镍型奥氏体不锈钢性能的基础;同时,将本试验钢冷轧退火温度从1 080 ℃提高到1 100 ℃,且降低退火工艺速度,以延长带钢在退火炉内的时间,使奥氏体晶粒充分长大,控制晶粒尺寸为8.0～9.0级,才能保证钢卷获得良好的使用性能。     

1Cr18Ni9Ti不锈钢形变诱发马氏体相变规律及其对孔蚀敏感性的影响

通过低温（－７０℃）拉伸制备不同马氏体相交量的１Ｃｒ１８Ｎｉ９Ｔｉ试样,用ＸＲＤ、ＴＥＭ及金相观察研究形变诱发马氏体相变的规律。用电化学方法研究。α’马氏体（铁磁相）含量对１Ｃｒ１８Ｎｉ９Ｔｉ钢在含Ｃｌ－溶液中孔蚀敏感性的影响。结果表明：随试样变形量加大,形变诱发马氏体中铁磁性的α’马氏体含量不断增大,而ε马氏体相的量始终较小。材料的孔蚀敏感性先随铁磁相含量的增大而增大;当铁磁相含量达到４．５８％以后,孔蚀敏感性反而渐降;当铁磁相含量超过２５．５％后,孔蚀敏感性又增加。     

Der Einfluß programmierter Schweißtemperaturzyklen auf die Gefügeausbildung und das Korrosionsverhalten von austenitischen korrosionsbeständigen Stählen

Influence of programmed welding temperature cycles on the resulting structure and the corrosion behavior of austenitic steel Studies on corrosion resistant austenitic steels subjected to simulated welding temperature cycles have shown that even after very short annealing times the corrosion resistance is decreased. In the temperature range between 700 and 900 °C carbides are precipitated, while grain growth and twinning are observed at temperatures between 900 and 1100 °C. Above 1280 °C delta-ferrite is formed as early as after 15 sec. Potentiokinetic current density/potential curves have been traced on the basis of tests in 1 N sulfuric acid at room temperature. The passivation current density has turned out to be a suitable corrosion resistance criterion.     

Zur Lochkorrosionsneigung von austenitischen CrNiMo-Stählen in konzentrierten Ammoniumrhodanidlösungen

Pitting corrosion of austenitic CrNiMo-steels in concentrated ammoniumrhodanide solutions Quasipotentiostatic and potentiokinetic polarisation measurements at various 18 Cr-10 Ni steels with molybdenum contents up to 4,3% were performed in 25 and 45% ammoniumrhodanide solutions. It was found that pitting corrosion is caused by incomplete passivation in the potential range of –300 to +250 m V _H. At these potentials the formation of stable passive layers is hindered by the formation and local oxidative dissolution of sulfidic layers. Above +250 m V _H rhodanide ions act in these weak acidic ammoniumrhodanide solutions as agents which destroy passive layers, comparable with chloride ions. The limiting potentials for stable pitting corrosion, obtained from potentiostatic experiments, are shifted from –300 to –150 m V _H with increasing molybdenum content of the steel. The least tendency of pitting corrosion was found for that steel with the highest molybdenum content.     

Kühlwasserseitige Korrosionsbeständigkeit von metallischen Werkstoffen zur Handhabung von Schwefelsäure

Cooling water side corrosion resistance of high alloyed materials for handling of process side sulfuric acid The approved materials for use in sulfuric acid alloy 825 (German material No. 2.4858) and alloy 20 (German mater. No. 2.4660) have only a low resistance against localized corrosion in chloride containing water and are unsuitable for handling of sulfuric acid. The newly developed austenitic Cr-base alloy, alloy 33, (X1CrNiMoCuN 33-32-1, German mater. No. 1.4591) with 33 % Cr, 31 % Ni, 0,6 % Mo and 0.4 % N should have an excellent resistance against pitting and crevice corrosion additional to its high sulfuric acid resistance, too, because its Pitting Resistance Equivalent No. calculated according to PREN = %Cr + 3,3 · %Mo + 30%N runs to 50. Pitting and crevice corrosion properties of the alloy 33 are tested in comparison to those of reference materials in high chloride containing solutions (1M NaCl, artificial and modified sea water, 10% FeCl₃ · 6H₂O; 500 g/l CaCl₂ ). Pitting potentials and potentials of repassivation of pitting, critical temperatures of localized corrosion (FeCl₃-test, CaCl₂-test, artificial sea water), potentials of repassivation of crevice corrosion as well as depassivation pH values of crevice corrosion following Crolet have been determined. The results confirm that the localized corrosion behaviour of the alloy 33 corresponds to its PREN. With regard to pitting corrosion alloy 33 is comparable with the special stainless steel alloy 31 (mater. No. 1.4562), with regard to crevice corrosion it is comparable with alloy 926 (German mater. No. 1.4529).     

正火温度对低活化马氏体钢组织及力学性能的影响

对低活化马氏体钢丝材进行1000~1100 ℃保温60 min的正火处理,随后在790 ℃保温90 min进行回火处理,研究正火温度对低活化马氏体钢丝的显微组织及力学性能的影响。结果表明,正火后,丝材的显微组织由粒状珠光体转变为板条状马氏体,碳化物粒子大部分回溶于基体中,正火温度的升高加速碳化物粒子的回溶,在1100 ℃实现完全回溶;原奥氏体晶粒尺寸随正火温度升高显著增大(由1000 ℃的7.4 μm增至1100 ℃的34.9 μm)。回火处理后,马氏体板条尺寸变宽,板条间的位错密度显著降低,析出相沿晶界、晶粒内部析出、球化及长大,其中M₂₃C₆(M以Cr为主)相为短棒状,分布在晶界,而MX(M以Ta为主)相为椭球状,分布在马氏体板条内部。经1000 ℃×60 min正火+790 ℃×90 min回火后能够获得最佳的综合力学性能,其抗拉强度为745.7 MPa,断后伸长率为18.9%。     

Influence of tempering treatment on microstructure and pitting corrosion resistance of a new super ferritic–martensitic–austenitic stainless steels with 17%Cr

Supermartensitic stainless steels (SMSSs) allow high mechanical strength with better corrosion resistance and toughness than conventional martensitic stainless steels. The SMSS steels with 12–13%Cr have been studied and applied in the oil and gas offshore production. The increase of Cr content, and the addition of Mo and W is now being investigated to increase mechanical and pitting corrosion resistance. In this work, a new 17%Cr steel, with Mo and W additions was studied. Depending on the final tempering treatment, the steel has a complex microstructure of austenite, ferrite, martensite and precipitates. The pitting corrosion resistance also depends on the microstructure produced by tempering. It was found that the pitting potential slightly decreases with the increase of tempering temperature and is further decreased by the double-tempering treatment. The pits initiate and grow preferentially in the martensite or tempered martensite islands, due to the lower Cr, Mo and W contents of these areas.     

Das Ausscheidungsverhalten von hochlegierten austenitischen Stählen mit 6% Molybdän und sein Einfluß auf die Korrosionsbeständigkeit

Precipitation behaviour of high-alloyed austenitic steels with 6% molybdenum and its influence on the corrosion resistance The high-alloy austenitic steels with 6 to 7% Mo, 20 to 21% Cr and 18 to 25% Ni are increasingly used in seawater and chemical applications. This is due to the excellent resistance to pitting and crevice corrosion in chloride-containing neutral and acidic environments. It is the high chromium and molybdenum content which provides the excellent corrosion behaviour but, at the same time favors the tendency to precipitation of intermetallic phases. Therefore, time-temperature-precipitation diagrams have been established for two steels with 6% Mo, 21% Cr, 25% Ni, 0.14 and 0.19% N and for one steel with 6% Mo, 20% Cr, 18% Ni and 0.21% N. The corresponding time-temperature-sensitization diagrams (in accordance to SEP 1877/II) and time-temperature-pitting diagrams (testing in 6% FeCl₃ solution) have been evaluated as well. Precipitation of intermetallics occurs rapidly especially in the range between 700 and 1000°C. In case of the 18% Ni steel and the 25% Ni/0.14% N steel grain boundaries are covered to a large extent with precipitates after only 15 min at 850 or 950°C. In case of the 25% Ni/0.19% N steel precipitation is considerably slower. The precipitates are interpreted to be chi-phase. After very long annealing times additionally small amounts of Laves phase appear. Neither carbides nor nitrides were observed. In spite of the rapid precipitation, sensitization in terms of the 50 m?m grain boundary penetration criterion is observed not before 0.7 h at 850 °C and not before about 2 h at 800°C in case of the 25% Ni/0.19% N steel. After about the same times of annealing also the critical pitting temperature as observed in the FeCl₃-test is dropping below 50°C. Therefore, when welding according to established rules and recommendations, no deterioration of the corrosion resistance in the heat-affected zone is to be expected. If high heat inputs will occur during manufacturing because of hot forming operations or welding of heavy sections, or if more severe test conditions are a requirement, a steel with 25% Ni and about 0.2% N (UNS N 08925, Cronifer hMo) is recommended due to its retarded precipitation and sensitization behaviour when compared to steels with only 18% Ni (UNS S 31 254). Additionally, the steel with 25% Ni has an increased resistance to general corrosion in acids. Notch impact strength of the materials under consideration is increased by the initial precipitation of the intermetallic phases and decreases only after longer times of annealing below the ductility of the solution annealed material.     

恒电位脉冲法检测奥氏体不锈钢敏化

不锈钢在一定温度范围内经热处理敏化，在晶界附近形成贫铬区，引起晶间腐蚀，本文采用恒电位脉冲技术对奥氏体不锈钢的敏化进行检测，并讨论了该法检测敏化的最佳实验条件。与常用的双环ERP法相比较，恒电位脉冲法具有测定速度快、对试样损伤小、测定结果更准确等特点。根据扫描电子显微镜（SEM）的观察，敏化度较高的不锈钢电极，经过双环EPR实验后在电极表面发生较严重的孔蚀，这可能就是EPR法测定常会出现偏差的原因；而经恒电位脉冲法实验后的同类电极，则未发现明显的孔蚀现象，从而保证了检测方法的准确性。     

深冷处理后回火温度对15Cr超级马氏体不锈钢组织及耐点蚀性能的影响

利用场发射扫描电镜、透射电镜以及电化学综合测试系统对15Cr超级马氏体不锈钢(SMSS)经不同热处理工艺处理后的显微组织变化和第二相碳化物及其对该钢腐蚀行为的影响进行了研究。结果表明,试验钢经不同热处理工艺处理后组织均由板条马氏体、奥氏体以及M₂₃C₆型碳化物颗粒组成,随着回火温度的增加,试验钢中逆变奥氏体含量增加,且在650 ℃回火时达到体积分数最大值41.41%。当回火温度高于600 ℃时第二相碳化物开始析出,且650 ℃回火后碳化物数量及尺寸较600 ℃增多。点蚀电位随着回火温度的增加而降低,第二相碳化物的析出降低了试验钢的点蚀电位,促进了亚稳点蚀位置的形成,从而降低了试验钢的耐腐蚀性能。     

Zum Einfluß von Mangan auf die Korrosionseigenschaften von austenitischen 18.10-CrNi-Stählen

Influence of manganese on the corrosion properties of austenitic 18.10-CrNi stainless steels The influence of manganese in the range of 0.25 to 1.5 mass-% on the passivation and pitting corrosion behaviour of unstabilized and Tistabilized austenitic 18/10 CrNi stainless steels is examined by determination of useful characteristical electrochemical dates using potentiodynamical polarization measurements in H₂SO₄-acidic and neutral model electrolytes. In the case of Ti-stabilized steels, a trend to an improved ability to passivation and to an increased pitting corrosion resistance is signified with increased Mn-content. This is in agreement with the austenite stabilizing effect of manganese. In the case of unstabilized steels, a significant deterioration of the passivation and pitting corrosion behaviour is observed, if the Mn-content of the steel is increased from less than 0.7 to more than 1.0 mass-%. These observations are discussed in the viewpoint of segregation of Mn-rich sulfide inclusions in the steel, which are essentially influenced by the presence of titanium in the steel.     

Galvanic Series of Metals and Effect of Alloy Compositions on Corrosion Resistance in Sanya SeawaterEI北大核心CSCD

With the development of ocean engineering, various metallic materials have been applied to the marine environment. It is an urgent requirement to study the galvanic series and alloy composition optimization of metallic materials in the tropical marine environment. In this work, open circuit potentials (OCP) and galvanic series of 36 kinds of metallic materials in Sanya seawater were studied. By considering the response of OCP to tidal changes, the anti-corrosion effects of alloying elements were also ana lyzed. The results show that the OCP of metallic materials in Sanya seawater has a large range. The galvanic series order of metallic materials from high to low in Sanya seawater is: nickel alloy, duplex stainless steel, austenitic stainless steel and pure copper, ferritic stainless steel, martensitic stainless steel, copper alloy, low alloy steel, carbon steel, cast iron, aluminum alloy and aluminum anode. Low-carbon high-alloy content carbon steel and high Cr, Ni contents stainless steel have higher OCP. The potential fluctuations of carbon steel with tidal changes involves two phases: (1) under the dynamics control, the OCP of carbon steel is more negative at high tide; (2) under the diffusion control, the OCP is more positive at high tide. The potential fluctuations of metallic materials reflect the effect of the corrosion product film on the change of ionization balance, and metals with less potential fluctuations have better inhibition on ion diffusion. In Sanya seawater, the carbon steel, which has more alloying content and less carbon content, has less potential fluctuations with the tidal changes and has good oxygen diffusion resistance. The potential fluctuations of austenitic stainless steel with tidal changes are less than that of ferritic stainless steel and martensitic stainless steel. After 2700 h immersion, austenitic stainless steel and martensitic stainless steel, which have a higher content of Mo, have more stable OCP. In other words, the corrosion film gets a better corrosion resistance. The OCP of aluminum anode in Sanya seawater environment increases when the oxygen content is brought up. The OCP of Zn-containing or Ga-containing aluminum anode remains relatively stable. Al bronze and T2 copper have less potential fluctuations with tidal changes, and perform good corrosion resistance in Sanya seawater.     

Eigenschaften eines neuen nichtrostenden austenitischen Stahles mit erhöhter Festigkeit

Properties of a new stainless austenitic steel with improved tensile strength The paper presented a new nitrogen-alloyed stainless austenitic steel-grade X 4 CrNiMnN 18 6 3 with improved strength compared with grade 1.4306 as concerns: mechanical properties at room and elevated temperature, intercrystalline corrosion, corrosion rate in solutions of nitric, hydrochloric and sulfuric acids, weldability. Essential increase of mechanical properties in steel-grade X 4 CrNiMnN 18 6 3 compared with traditional 18Cr8Ni steels, without change in corrosion resistance and weldability was achieved by addition of nitrogen (0,11–0,26%).