Chloride-induced stress corrosion cracking of Duplex stainless steels. Models,test methods and experience

Stress corrosion cracking (SCC) induced by chlorides frequently causes problems in applications where standard austenitic stainless steels are being used. Often this problem can be solved by the use of duplex stainless steels. In this report the mechanisms for SCC have been surveyed, and the cause for the high SCC resistance of duplex stainless steels has been discussed and evaluation of test methods for SCC and how duplex stainless steels respond to them, as well as practical experience of duplex stainless steels. The study shows that no single mechanism can be attributed to the good resistance to SCC of duplex stainless steels. Probably a synergistic effect of electrochemical and/or mechanical effects is responsible for the good performance. Test methods for SCC often give relatively good correspondence with real applications, but ranking is often doubtful, and comparisons of different material types should be made with caution. Numerous cases with SCC on standard austenitic stainless steels have been solved by the use of duplex stainless steels.     

Die Ermittlung der Beständigkeit gegen Spannungsrißkorrosion (SpRK) von hochlegierten Sonderstählen in chloridhaltigen wäßrigen Medien

Determination of resistance to stress corrosion cracking (SCC) of high-alloy special steels in chloride-containing aqueous media The 18 Cr 10 Ni(Mo) based stainless steels have been continually improved by raising the Cr, Ni and Mo contents. The behavior of these high-alloy steels towards SCC was determined in test media generally used in practice since the question of the resistance to stress corrosion cracking (SCC) had still remained unanswered to a large extent. SCC tests on U-bend samples in boiling 62% CaCl₂ solution showed a good differentiation depending on the Ni and Mo contents. With increasing Ni content, the susceptibility of special high-alloy steels to SCC is shifted towards longer service lives, alloys containing ≧ 42% by weight of Ni being resistant. High-Mo special alloy steels are more resistant to SCC than low-Mo special alloy steels. These results could be confirmed by tests carried out on circular cross section samples in boiling 62% CaCl₂ solution under constant load and potentiostatic control. The free corrosion potentials recorded for 25% Ni special alloy steel and Ni-based alloys are within the potentiostatically determined range of insusceptibility to SCC. The high-Mo special alloy steel X 2 NiCrMoCu 25 20 6 (1.4529) shows the same critical SCC potential on the anodic side as the Ni alloy NiCr21 Mo (2.4858). Superferrit X 1 CrNiMoNb 28 4 2 (1.4575) and austenitic ferritic steel X 2 CrNiMoN 22 5 (1.4462) showed that the SCC behavior was unsatisfactory in both tests as in the case of steel X 10 CrNiMoTi 18 10 (1.4571). Tests in boiling 4 m NaCl showed no SCC, not even under the aggrevated test conditions in the test set-up. The great influence of the oxygen content was demonstrated in tests carried out in the autoclave with defined oxygen and chloride concentrations. The resistance of the steels to SCC decreases under air-saturated conditions (8 … 10 ppm O₂) whereas the chloride concentration (200 and 2000 ppm Cl^?) does not exercise an important influence. U-bend samples should be given preference to Erichsen samples for SCC tests. SCC break characteristics could be determined metallographically and by scanning electron microscope.     

THE EFFECT OF W ON THE REPASSIVATION BEHAVIOR OF Ni-ADDED STAINLESS STEELS

The effect of W on the repassivation behavior of Ni-added stainless steels was investigated with respect to the repassivation rate and the SCC susceptibility. It was found that more stable passive film was formed on the W-modified stainless steels than that of steels without W-modification, and the repassivation rate was faster for W-modified stainless steels in acidic chloride solution （0.5M H2SO4＋3.5% Cl^-）. In neutral chloride solution （1M MgCl2）, there were no significant differences on both passivation properties and the repassivation rates for duplex stainless steels, while W-modified austenite stainless steel showed faster repassivation rate. The SCC tests verified that W-modified Ni-added stainless steels exhibited better SCC resistance than steels without W in chloride solution. Moreover, W-modification in higher Ni-added stainless steels exhibited more remarkable SCC resistance than steels with lower Ni content in chloride solution.     

Autoklaven-Untersuchungen der Spannungsrißkorrosion von Fe-Cr-Ni-Legierungen in NaCl/Co2/H2S-Medien

Autoclave investigation of stress corrosion cracking behaviour of Fe-Cr-Ni alloys in NaCl/CO₂/H₂S-environment In oil and gas production, the corrosion problems increase as the depth of the reservoirs increases. The oil and gas products contain chloride-rich waters and mixtures of H₂S and CO₂ at high pressures and temperatures. Materials that can be used under these conditions are only high strength high alloy steels and nickel base alloys. These materials must be assessed for corrosion resistance under these conditions. The environment contain chloride ions and hydrogen sulphide, which are known to be critical components for SCC. With the aid of autoclave experiments, the fields of corrosion resistance for the materials no. 1.4462, 1.4563 and 2.4618 were determined as a function of temperature and hydrogen sulphide pressure. The base environment was a 5 Molar sodium chloride solution at 20 bar carbon dioxide. While the corrosion resistance of the duplex steel, material no. 1.4462, decreases markedly as the strength of the material and the hydrogen sulphide pressure increase, the two austenitic materials are completely resistant up to 300 °C and hydrogen sulphide pressure of 15 bar. Only at 300 °C and high partial pressures of hydrogen sulphide the material no. 1.4563 did fail, when stressed to stress levels higher than the YS. The crack path was predominantly transgranular with minute fractions of intergranular cracking. The microstructure appears to have no effect. All results indicate that a mixed mechanism of hydrogen- and chloride induced SCC is operting, while a corrosion enhancement due to interaction of both critical components takes place.     

Effect of alloy element contents on caustic stress corrosion cracking of several stainless steels

The stress corrosion cracking behavior in caustic solutions (200 g/l sodium hydroxide, 10 g/l sodium chloride) of three austenitic (18Cr-10Ni-2.5Mo, 20Cr-25Ni-4.5Mo, 27Cr-31Ni-3.5Mo) and three duplex (23Cr-4Ni, 22Cr-5Ni-3Mo, 25Cr-7Ni-4Mo-N) stainless steels was examined. U-bend and Slow Strain Rate (SSR) tests were performed at 200–250°C. The negative influence of nickel in the lower range content for the 18Cr-10Ni-2.5Mo and 20Cr-25Ni-4.5Mo has been shown; when the nickel content is significantly increased (>30%), as in the case of the steel 27Cr-31Ni-3.5Mo, an increase of SCC resistance has been detected. The negative effect of molybdenum, mainly on the behaviour of duplex stainless steels, has also been evidenced. The duplex stainless steels show better caustic SCC resistance than austenitic stainless steels type 18Cr-10Ni-2.5Mo and 20Cr-25Ni-4.5Mo. The best behaviour has been found for the less-alloyed steel 23Cr-4Ni.     

Stress-corrosion cracking of 15cr-15ni-2.2mo titanium-modified austenitic stainless steels

The stress- corrosion cracking (SCC) behavior of two alloys of titanium- modified austenitic stainless steels with different TiJC ratios in the 20% cold worked condition was studied in 45% boiling magnesium chloride (BP427 K) using the constant- extension rate testing (CERT) technique. The SCC susceptibility of the two titanium-modified alloys was assessed using the ratios of the values of ultimate tensile strength (UTS) and percent elongation in magnesium chloride and liquid paraffin, the susceptibility index (I), crack propagation rates (CPR), and stress ratios at different values of plastic strains. The results obtained on these alloys were compared with AISI type 316 stainless steel. It was observed that the two titaniummodified austenitic stainless steels had better SCC resistance than type 316 stainless steel, mainly due to their higher nickel content and, to a lesser extent, to the presence of titanium. Increasing the value of the TiJC ratio led to increased SCC resistance due to the availability of more free titanium in the solid solution. Fractography of the failed samples indicated failure by a combination of transgranular SCC and ductile fracture.     

Application limits of stainless steels in the petroleum industry

Stainless steels have a great variety of potential applications in the petroleum industry, mainly as an alternative to carbon steel in corrosive environments. Within a number of media that can cause corrosion problems with these materials, only chloride solutions and hydrogen sulfide are of importance in oilfield service. A reliable tool that permits the proper selection of stainless steels has yet been missing. In order to provide engineering diagrams for this purpose, pitting and stress corrosion cracking (SCC) tests were performed. Specimens were exposed to NaCl solutions containing from 3 to 100,000 ppm Cl^? at temperatures from 40 to 200 °C. This test configuration was chosen to give a better representation of actual service conditions than accelerated standard test procedures do. Tested materials were the austenitic stainless steel grades 321, 316Ti (API LC30‐1812) and 254 SMO, and 22Cr duplex (austenitic‐ferritic) steel (API LC65‐2205). Based on an optical examination of the specimens, no‐risk regions of chloride concentration vs. temperature have been identified. Subsequently, service temperature limits have been deduced for each tested material. Thus, material failures by pitting and SCC can be prevented without overdesigning. The results of the testing series are applicable to all chloride environments without presence of H₂S, as they have to be handled by primary production equipment, as well as transportation and gas processing facilities.     

22Cr双相不锈钢与304L、316L钢在氯化物溶液中耐应力腐蚀性能的比较

采用恒载荷法、恒应变法研究了22Cr双相不锈钢在不同Cl-浓度、不同温度的氯化物渗液中耐应力腐蚀的性能,并与316L和304L普通奥氏体不锈钢进行了对比.结果表明,22Cr双相不锈钢在氯化物环境中具有更好的应力腐蚀破裂(SCC)抗力.     

Effect of W on stress corrosion cracking susceptibility of newly developed Ni-saving duplex stainless steels

Effect of W on stress corrosion cracking behavior (SCC) of Ni-saving duplex stainless steels (Fe18Cr6Mn3Mo0.4N (2.13, 5.27)W, in wt%) was investigated in 4 M NaCl solution using a slow strain rate test method. The change in the W content from 2.13 to 5.27 wt% marginally affected the tensile properties of the investigated DSSs. Alloying W clearly improved the pitting initiation resistance and repassivation tendency of the investigated alloys, but the SCC susceptibility was not remarkably decreased by addition of W. The slight enhancement in the SCC resistance of the alloy containing 5.27 wt% W was revealed to be correlated with the accelerated galvanic corrosion between the ferrite and austenite phases as a result of the W partitioning preferentially into the ferrite phase which could encourage the propagation of pitting.     

Localized corrosion of (lean) duplex stainless steels in immersion units of urban wastewater treatment plants

With lower alloying cost and higher mechanical properties, lean duplex stainless steels can be an alternative to the more commonly used austenitic stainless steels. However, these alloys are still not the preferred choice, probably due to a lack of field experience. A study was thus initiated in view of defining the limits of use of selected (lean) duplexes for urban wastewater treatment units. The present paper shows the localized corrosion performance of selected lean duplexes in chloride contaminated solutions. The results are compared with austenitic S30403 and S31603 and with the more standard duplexes S82441 and S32205. The effect of welding was also investigated. Exposures in field municipal wastewater plants were conducted for 1 year in low and high chloride content units. The results show that lean duplexes S32101 and S32202 can be used as alternatives to S30403 and S31603 in low chloride electrolytes. At 500 ppm of chloride content, duplex stainless steel S32304 showed better corrosion resistance than S30403 and S31603. For higher chloride contents (1000 ppm and above) the standard duplexes S82441 and S32205 shall be preferred.     

Corrosion resistance of low‐nickel duplex stainless steel rebars

The use of stainless steel bars in reinforced concrete structures may be an effective method to prevent corrosion in aggressive environments where high amounts of chlorides may penetrate in the concrete cover. For an estimation of the service life of structures where stainless steel bars are used, the chloride threshold for these rebars should be defined, and the influence of chemical composition and metallurgical factors that may affect the corrosion resistance (strengthening, welding, etc.) should be assessed. To reduce the cost of stainless steel reinforcement, duplex stainless steels with low nickel content have been recently proposed as an alternative to traditional austenitic steels, even though, few results are available regarding their corrosion performance in chloride contaminated concrete. This paper deals with the corrosion resistance of low‐nickel duplex stainless steel rebars (1.4362 and 1.4162) as a function of the chloride content. Comparison is made with traditional austenitic steels. An attempt to define a chloride threshold for the different stainless steels is made by comparing the results of several test procedures both in concrete and in solution.     

Corrosion behaviour of highly alloyed stainless steels in mixed chloride and fluoride aqueous solutions

Laboratory weight loss and cyclic potentiodynamic polarization corrosion tests were performed on two types of corrosion resistant alloys, a duplex alloy (ferritic-austenitic stainless steel) and two austenitic stainless steels, in mixtures of chloride (3000, 9000 and 15000 ppm) and fluoride (4800 and 15000 ppm) ions at pH 3. Two temperatures were tested, 60 and 70°C. The electrochemical results indicate that the duplex stainless steel presents high corrosion resistance. Weight loss results show low corrosion rates of the two types of stainless steels after 60 days exposure. Sonic pits-crevices were found under the corrosion crust deposits on the duplex stainless steel.     

The effect of CeCl3 inhibitor on the localized corrosion of stainless steel in chloride solutions

Stainless steels have been used extensively in many sectors such as medical and household appliances as well as construction. This has been primarily due to their high resistance to corrosion attacks, reasonable cost, and excellent mechanical properties. However, when placed in corrosive media stainless steel is susceptible to localized corrosion attacks, especially when placed in chloride solutions. The paper explores the issue of corrosion liability of austenitic (AISI 316) and duplex (UNS S32205) stainless steels in et aconditions of seawater environment as well as under the influence of an inhibitor in the same environmental conditions. The behavior of stainless steels was examined via electrochemical testing relying on DC and AC techniques, optical metallographic analysis, scanning electron microscopy, and X‐ray diffraction analysis. Duplex stainless steel showed better resistance to localized corrosion but a higher tendency toward general corrosion in all examined solutions. Cerium chloride in a chloride solution showed inhibiting properties for both the AISI 316 and the UNS S32205.     

Untersuchungen zur transkristallinen und interkristallinen Spannungsrißkorrosion austenitischer Chrom-Nickel-Stähle in heißen Magnesiumchlorid-Lösungen

Investigations Into transgranular and intergranular stress corrosion cracking of austenitic stainless steels In hot magnesium chloride solutions The stress corrosion cracking (SCC) of austenitic stainless steels in hot magnesium chloride solutions is known to be transgranular. Therefore the slip-step-dissolution model is most favourable when explaining the failure mechanism. Constant load and constant extension rate tests (CERT) show that both methodes are almost equivalent. Moreover constant extension rate tests in more concentrated magnesium chloride solutions at 135°C reveal a small potential range of intergranular stress corrosion cracking more negative than the range of transgranular SCC. Observations of crack nucleation and crack propagation make plain that crack nucleation is a localized corrosion process. Pitting produces crack nucleis in the elastic range whereas cracks start along slip lines after plastic deformation. Fractography of specimens which failed by intergranular and transgranular SCC show macroscopically brittle fracture surfaces. Therefore a model is proposed which explains crack propagation by hydrogen-induced intermitted cracking at high-stressed sites at the crack tip.     

H2S 分压对 13Cr 不锈钢在 CO2注气井环空环境中应力腐蚀行为的影响简

利用高压下的电化学实验及U型弯浸泡实验结合微观分析手段,研究了13Cr不锈钢在不同H2S分压下CO2注气井环空环境模拟液中的电化学特征及应力腐蚀规律。结果表明:油套管钢的刺漏现象以及环境中硫酸盐还原菌的存在使得环空环境成为复杂的高压H2S-CO2-Cl-环境,13Cr不锈钢在该种环境下具有明显的应力腐蚀敏感性。随着H2S分压的升高,13Cr不锈钢击破电位下降,应力腐蚀敏感性增强,这主要因为H2S分压的增大对不锈钢表面膜(钝化膜及腐蚀产物膜)的破坏作用加强。当H2S分压达到0.20 MPa时,13Cr不锈钢发生明显的应力腐蚀,断口表现为由沿晶应力腐蚀裂纹(IGSCC)和穿晶应力腐蚀裂纹(TGSCC)组成的混合断口,应力腐蚀受阳极溶解和氢致开裂共同控制。     

Electrochemical behaviour of duplex stainless steels in caustic environment

Recent studies have shown that duplex stainless steels can be susceptible to general corrosion and stress corrosion cracking in high pH caustic environments. This difference in the corrosion resistance can be attributed to changes in the electrochemical behaviour of steels. The present study has shown that the corrosion rates of duplex stainless steels increase with an increase in temperature and sulphide addition to caustic environments. Moreover, alloying Fe with Cr and Ni helps to raise the corrosion potential and lower critical current density of DSS in an alkaline environment whereas Mo can be detrimental to the corrosion resistance of the steel.     

Lateral and radial corrosion propagation behavior of 9–21% Cr and 18% Cr + 2.8% Mo stainless steel reinforcing materials in simulated concrete environments

The life of a concrete structure exposed to deicing compounds or seawater is often been limited by chloride induced corrosion of the steel reinforcement. A complete assessment of the potential benefits afforded by new candidate rebar alloys must address both the lateral and radial corrosion propagation behavior in comparison to conventional steel as well as other factors that might affect the risk of corrosion‐induced concrete cracking. The radial (depth) and lateral (length) corrosion propagation behavior of 18% Cr + 2.8% Mo (S31653) stainless steel, 21% Cr (S32101) duplex stainless steel, and 9% Cr steel compared to plain ASTM A615 carbon steel were characterized in saturated Ca(OH)₂ solution. Radial pit growth was found to be Ohmically controlled for all materials but repassivation occurred more readily at high applied potentials for 18% Cr + 2.8% Mo and 21% Cr stainless steels. Conversely, pit growth on plain steel propagated at all applied anodic potentials and did not repassivate until deactivation by cathodic polarization. Stainless steel also showed the highest resistance to lateral corrosion propagation from an active site during microelectrode array testing. 21% Cr duplex stainless and 9% Cr steel showed similar radial propagation behavior and corrosion morphology, which was intermediate to that of plain steel and S31653 stainless steel. Based on an existing concrete cracking model, it is expected that 9–21% Cr and 18% Cr + 2.8% Mo corrosion resistant rebar materials would require a greater depth of corrosion attack than carbon steel before damaging concrete via corrosion product formation.     

Stress corrosion cracking susceptibility of stainless steels in pulp cooking processes—online capillary electrophoresis,potentiostatic and chromatographic studies

An online high temperature capillary electrophoresis instrument (HotUCE), a potentiometer and an ion chromatograph were used in studies on corrosive ions and changes in potential at normal pulping process temperatures in experimental liquors modelling pulp cooking processes at mills. The aim was to evaluate the stress corrosion cracking (SCC) susceptibility of stainless steels. The HotUCE instrument and the potentiometer were online coupled with an autoclave, where welded duplex stainless steel samples were immersed for 500 h in simulated high ionic strength hot black liquor (HBL), hot white liquor (HWL) or green liquor (GL) at 130, 150 or 170 °C, respectively. The results showed that only minor amounts of oxidized sulphur compounds were formed. The concentrations of corrosive sulphur anions were calculated against sulphur standards. Amounts of sulphur species in the liquor correlated with the changes in the potential of the duplex stainless steel specimens during the cooking experiments. The formation of sulphite during cooking was greater in HWL than in HBL. Changes in the potential showed that reduction processes occurred during the SCC tests. The results indicate that the SCC risk is enhanced at higher temperatures, probably, due to the increased formation of thiosulphate.     

氮化处理改善1Cr18Ni9Ti钢在MgCl_2溶液中应力腐蚀破裂性能的研究

<正> 一、前言 利用表面处理作为防止不锈钢应力腐蚀破裂(SCC)的有效途径已得到人们的普遍重视。我们以1Cr18Ni9Ti钢为基材,分别进行了电镀Ni-P、喷铝、离子氮化等表面处理,然后在42％MgCl_2沸腾(143℃)溶液中作恒载荷拉伸试验,结果表明离子氮化处理对改善不锈钢抗SCC性能的效果最明显。     

Electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment

The electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment was investigated by potentiodynamic polarization technique, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results show that uniform corrosion occurs on 300M steel during the electrochemical measurements because no anodic passivation phenomenon is observed on polarization curves within the measurement range. The tests also show that 300M steel is highly susceptible to chloride containing solution, which is characterized by corrosion current density increasing with the addition of chlorides, and corrosion potential shifting towards positive direction and corrosion resistance decreasing, positively suggesting that chloride ions speed up the corrosion rate of 300M steel. Meanwhile corrosion products on the 300M steel surface formed during the salt spray test are too loose and porous to effectively slow down the corrosion rate. Additionally, a schematic structure of uniform corrosion mechanism can explain that 300M steel has better property of stress corrosion cracking (SCC) resistance than stainless steels.