6种不锈钢的化学和电化学腐蚀行为

采用化学和电化学加速腐蚀试验方法对６种不锈钢的耐点蚀和缝隙腐蚀性能进行了评价。结果表明：两种评价方法之间具有良好的相关性;６种不锈钢按照点蚀和缝隙腐蚀抗力由大到小的顺序排列为３＾＃〉１＾＃〉６＾＃〉２＾＃〉４＾＃〉５＾＃,详细描述了６种不锈钢各自的腐蚀行为特征。     

Susceptibility of stainless steel alloys to crevice corrosion in ClO2 bleach plants

Stainless steels, including duplex stainless steels, are extensively used for equipment in pulp bleaching plants. One serious corrosion problem in chlorine dioxide bleach plants is crevice corrosion of stainless steels, which is frequently the factor that limits their use in bleach plants. Crevice corrosion susceptibility of alloys depends on various environmental factors including temperature, chemical composition of environment and resulting oxidation potential of system. Upsets in the bleaching process can dramatically change the corrosivity of the bleaching solutions leading to temperatures and chemical concentrations higher than those normally observed in the bleach process. When the environmental limits are exceeded the process equipment made of stainless steel can be severely affected. Environmental limits for crevice corrosion susceptibility of eight stainless steel alloys with PRE numbers ranging from 27 to 55 were determined in chlorine dioxide environments. Alloys used in this study included austenitic, ferritic-austenitic (duplex), and superaustenitic stainless steels. The performance of the different stainless steel alloys mostly followed the PRE numbers for the respective alloys. The 654SMO alloy with the highest PRE number of 55 showed the highest resistance to crevice corrosion in this environment. Under the most aggressive chlorine dioxide bleach plant conditions tested, even alloys Nicr3127 and 654SMO with PRE numbers 51 and 55 respectively were susceptible to crevice corrosion attack. The two factors that seem to contribute the most to crevice corrosion and pitting in the investigated environments are temperature and potential.     

Determination of critical pitting temperatures for Ni?Cr?Mo alloys using electrochemical noise measurements

The determination of critical pitting temperatures (CPT) in various test solutions like ferric chloride solution according to ASTM G48 or “Green Death” solution is a common test method for the comparative assessment of the pitting corrosion resistance of highly alloyed steels and Ni? Cr? Mo alloys. In addition to the well‐known disadvantages of standard methods, like long test times, subjective examination, and large scatter, for the highest alloyed Ni? Cr? Mo alloys no stable pitting corrosion can initiate even at the highest test temperatures. This paper describes the limitations of standard test methods and shows how these problems can be solved by an alternative test solution and an adjusted test method. By capturing and examining the current noise under potentiostatic conditions during continuous heating in a 4.5 M calcium chloride solution the transition from metastable to stable pitting corrosion as a criterion for CPT can be detected in a reproducible way.     

Einfluß von Chrom,Molybdän und Stickstoff auf die Korrosionsbeständigkeit des Ni-freien,austenitischen Edelstahles Macrofer 2515MoN (W.-Nr.: 1.4653)

Influence of chromium, molybdenum and nitrogen on the corrosion resistance of the Ni-free, austenitic stainless steel Macrofer 2515MoN (German Alloy No. 1.4653) Nitrogen alloyed, Ni-free, austenitic stainless steels comprising of more than 1 wt.-% nitrogen are a new group of alloys with promising properties. They show a very interesting combination of high strength and toughness with a high corrosion resistance. This combination of properties make the alloys not only suitable for fasteners but also for parts for medical and dental applications. This work shows the influence of chromium, molybdenum and nitrogen on the corrosion resistance of Fe25Mn-alloys in media typical for the above mentioned applications. According to these results Fe25Mn-alloys with appr. 20 wt.-% chromium, about 3 wt.-% molybdenum and appr. 1,3 wt.-% nitrogen have an excellent corrosion resistance in Ringer solution, artificial saliva and artificial sweat. The critical pitting temperature (CPT) as well as the critical crevice temperature (CCT) with 61°C respectively 37°C tested according ASTM G 48A provided significantly higher temperatures when compared to the commercially well established Ni-austenite X6CrNiMoTi17-12-2 (German Alloy No. 1.4571).     

A double‐mode cell to measure pitting and crevice corrosion

Pitting corrosion and crevice corrosion of passivated steels were measured by using a double‐mode syringe electrolyte cell built on an environment chamber. The setup, when set in noncontact mode, could measure pitting potentials and critical temperatures, and crevice corrosion potentials if in contact mode. It could be employed to distinguish the pitting and crevice corrosion damage of reinforcing steel in concrete.     

A comprehensive assessment of the performance of corrosion resistant alloys in hot acidic brines for application in oil and gas production

Four stainless steels and alloys (17-4 PH, X4CrNiMo 16-5-1, F6NM and UNS N09935) were evaluated in relation to their application in the oil and gas industry. These materials were tested in solutions exhibiting a range of chloride concentrations, pH values and temperatures of interest for the oil and gas producing environments. The pitting sensitivity was investigated by means of potentiodynamic polarisation measurements, based on the ASTM G61 standard, in conjunction with a morphological study performed by scanning electron and optical microscopy. The resistance to stress corrosion cracking (SCC) was evaluated in compliance with the ASTM G123 standard. Erosion–corrosion was assessed by exposing the materials under electrochemical control to a flux of erodent glass microspheres in a rotating disc electrode device. A ranking of the materials resistance was derived, based on appropriate parameters, devised to effectively and synthetically represent the complex sets of environments of interest for the relevant application. Our results showed, as expected, that UNS N09935 displays the best performance with respect to pitting resistance and susceptibility to SCC as well as a very good resistance to erosion–corrosion. Among the other investigated materials, 17-4 PH showed higher resistance to pitting, X4CrNiMo 16-5-1 and F6NM longer time to SCC failure while 17-4 PH and X4CrNiMo 16-5-1 exhibited superior ability to withstand erosion–corrosion damaging.     

Temperature as a pitting and crevice corrosion criterion in the FeCl3 test

The FeCl₃ test is applied to an increasing extent for examining the resistance to pitting and crevice corrosion. Two methods having proved their value are described, the chemical properties of the FeCl₃ solution with regard to hydrolysis, pH and redox potential behaviour at various test temperatures are set forth and finally numerous results of the application of this test to high-alloy stainless steels and nickel alloys are presented. These results have been used to establish, be means of multiple regression, two empirical equations that allow to estimate rather accurately the critical pitting and crevice corrosion temperatures (CPT, CCT) from the contents of the decisive alloying constituents. These temperatures vary by about 2.5°C in the CPT test and by approx. 10°C in the CCT test, which can be reduced, however, by extending the test period beyond 24 hours. This is due to the fact that corrosion potentials in a 10% FeCl₃ · 6H₂O solution take a long time to stabilize. The variation of the critical crevice temperature can be further reduced by pressing the crevice blocks at a higher torque to the specimen. Another section particularly deals with the application of the CPT test for determining the influence of the matrix on the resistance to local corrosion. Consequently, the CPT test lends itself excellently to the examination of welds and as a quality control. Finally, CPT test results are compared with pitting data determined electro-chemically in artificial seawater. This shows that the ranking order with regard to corrosion resistance is identical, although media and processes differ considerably from each other.     

不锈钢海水潮汐区16年腐蚀行为

在青岛、厦门和榆林3个试验站的潮汐区对5种不锈钢暴露16年，总结其腐蚀行为和规律。在潮汐区暴露的不锈钢受点蚀和缝隙腐蚀破坏。不锈钢在潮汐区暴露1至4年的点蚀速度较大，以后点蚀速度减慢。耐点蚀性能较好的不锈钢，耐缝隙腐蚀性能也较好。不锈钢在潮汐区的腐蚀随暴露地点的海水温度升高而加重。增加Cr含量、添加Mo能明显提高不锈钢在潮汐区的耐蚀性。Ni对提高的耐蚀性有效，但影响效果较小。海生物污损能引起不锈钢的局部腐蚀，它对不锈钢在潮汐区的腐蚀有显著影响。     

Corrosion resistance properties of glow-discharge nitrided AISI 316L austenitic stainless steel in NaCl solutions

Glow-discharge nitriding treatments can modify the hardness and the corrosion resistance properties of austenitic stainless steels. The modified layer characteristics mainly depend on the treatment temperature. In the present paper the results relative to glow-discharge nitriding treatments carried out on AISI 316L austenitic stainless steel samples at temperatures ranging from 673 to 773 K are reported. Treated and untreated samples were characterized by means of microstructural and morphological analysis, surface microhardness measurements and corrosion tests in NaCl solutions. The electrochemical characterization was carried out by means of linear polarizations, free corrosion potential-time curves and prolonged crevice corrosion tests. Nitriding treatments performed at higher temperatures (>723 K) can largely increase the surface hardness of AISI 316L stainless steel samples, but decrease the corrosion resistance properties due to the CrN precipitation. Nevertheless nitriding treatments performed at lower temperatures (?723 K) avoid a large CrN precipitation and allow to produce modified layers essentially composed by a nitrogen super-saturated austenitic metastable phase (S-phase) that shows high hardness and very high pitting and crevice corrosion resistance; at the same polarization potentials the anodic current density values are reduced up to three orders of magnitude in comparison with untreated samples and no crevice corrosion event can be detected after 60 days of immersion in 10% NaCl solution at 328 K.     

In vitro electrochemical investigations of advanced stainless steels for applications as orthopaedic implants

Potentiodynamic anodic polarization experiments on advanced stainless steels (SS), such as nitrogenbearing type 316L and 317L SS, were carried out in Hank’s solution (8 g NaCl, 0.14 g CaCl₂, 0.4 g KC1, 0.35 g NaHCO₃, 1 g glucose, 0.1 g NaH₂PO₄, 0.1 g MgCl₂, 0.06 g Na₂HPO₄ 2H₂O, 0.06 g MgSO₄ 7H₂O/1000 mL) in order to assess the pitting and crevice corrosion resistance. The results showed a significant improvement in the pitting and crevice corrosion resistance than the commonly used type 316L stainless steel implant material. The corrosion resistance was higher in austenitic stainless steels containing higher amounts of nitrogen. The pit-protection potential for nitrogen-bearing stainless steels was more noble than the corrosion potential indicating the higher repassivation tendency of actively growing pits in these alloys. The accelerated leaching study conducted for the above alloys showed very little tendency for leaching of metal ions, such as iron, chromium, and nickel, at different impressed potentials. This may be due to the enrichment of nitrogen and molybdenum at the passive film and metal interface, which could have impeded the releasing of metal ions through passive film.     

Atmospheric corrosion of ASTM A-242 and ASTM A-588 weathering steels in different types of atmosphere

The work analyses the atmospheric corrosion resistance of two widely used weathering steels: ASTM A-242 and ASTM A-588. The steels were exposed for up to 5 years in different types of atmosphere: rural, urban, industrial and marine. The atmospheric corrosion resistance of the steels was evaluated and the rust layers formed on them were characterised by X-ray diffraction, optical microscopy and scanning electron microscopy. The most relevant conclusions reached include the following: (a) the visual appearance (colouring) of the rust, rust texture, nature of the corrosion products and compactness of the rust layers formed are similar in both types of weathering steel. (b) No great differences are observed in the corrosion resistance. Slight differences occur in the industrial atmosphere, where ASTM A-242 presents 10–13% less corrosion than ASTM A-588. (c) In the C2-C3 ISO corrosivity atmosphere both types of weathering steels are adequate for unpainted use. However are not suitable in higher ISO corrosivity atmosphere.     

Corrosion behaviour of carbon S-phase created on Ni-free biomedical stainless steel

Following the success of forming a carbon S-phase (expanded austenite) surface layer on medical grade Ni-free austenitic stainless steel by DC plasma carburising, the established commercial carburising process Kolsterising® was performed on both Ni-containing (AISI 304) and Ni-free austenitic stainless steels. While the Ni-containing stainless steel responded very well to Kolsterising®, the Ni-free alloy did not. The carbon absorption and the hardness of the Kolsterised® Ni-free alloy are inferior to Kolsterised® AISI 304 Ni-containing stainless steel, however, the hardness of the untreated Ni-free alloy was doubled by Kolsterising®. The response of both Kolsterised® Ni-free and Ni-containing alloys to pitting, crevice corrosion and intergranular corrosion resistance was similar. From this work it can be concluded that the Kolsterised® austenitic stainless steels do not suffer from intergranular corrosion but are susceptible to intragranular pitting when tested in boiling sulphuric acid and copper sulphate solution. It was also observed that Kolsterising® improves significantly the pitting and crevice corrosion resistance of the alloys used in this study.     

Influence of Sulfur Content on the Corrosion Resistance of 17-4PH Stainless Steel

According to specification standards, the basic chemical composition of steel 17-4PH for special and critical applications is 15-17% Cr, 3.0-5.0% Ni, 3.0-5.0% Cu, 0.07% C (max) and 0.15-0.45% (Nb + Ta) (wt.%). The maximum sulfur content is 0.030%. However, as it will be shown in this work, this maximum limit for sulfur is too high for services where high corrosion resistance is necessary. Two samples of 17-4PH steel with similar base compositions, but quite different sulfur contents (0.027% and 0.001%S), were compared with respect to pitting corrosion and sensitization. Both materials were heat treated according to commercial treatments A, H900, H1100, H1150 and H1150D (ASTM A-1082). Two corrosion tests were applied to compare the steels. The first one was the double-loop electrochemical potentiodynamic reactivation (DL-EPR) test in 0.25 M H₂SO₄ + 0.01 KSCN solution, which is used to measure the degree of sensitization. The second test was the anodic polarization in 3.5%NaCl solution, commonly used to evaluate the pitting corrosion resistance. Detailed microstructural characterization by magnetic measurements, light optical and scanning electron microscopy was performed. As main conclusion, despite that both steels have chemical compositions in accordance with the standards, the steel with higher sulfur was much more susceptible to pitting and sensitization.     

Hochfeste Stangen aus NiCr23Mo16Al – Einfluss der Kaltverfestigung auf die mechanischen Eigenschaften und das Korrosionsverhalten

High‐strength NiCr23Mo16Al bars – Influence of cold reduction on mechanical properties and corrosion behaviour For application in highly corrosive environments with high demands on the mechanical properties of the alloys, cold reduced NiCrMo alloys are often the alloys of choice. This work examines the influence of cold reduction up to 42%, introduced by cold drawing on the mechanical properties and the corrosion behaviour of the alloy NiCr23Mo16Al. Tensile tests performed at 20°C, 204°C and 371°C show a linear increase in 0.2% yield strength up the maximum cold reduction of 42%. For all cold reductions and all test temperatures at least 16% elongation to fracture were achieved. Also the impact strength was as high as approx. 200 J even for the lowest test temperature of ? 40°C. Corrosion tests performed according to ASTM G 28 A/B and G 48 C/D showed no deterioration of the 42% cold reduced alloy in comparison to the solution annealed condition. Only for material, which was 15–30% cold reduced a minor, slightly unsatisfactory behaviour was observed, which was attributed to the strong inhomogenity of the microstructure, thus resulting in the formation of a local element between the severe deformed rim and the undeformed centre of the material. Current density‐potential curves measured in 1 M NaCl according to ASTM G 61/98 revealed no influence of cold deformation on the electrochemical behaviour of the alloy.     

Loch- und Spaltkorrosion von Chrom- und Chromnickelstählen in chloridhaltigen Lösungen

Pitting and crevice corrosion of stainless steels in chloride solutions In practice stainless steels in chloride containing waters are found to be susceptible to crevice corrosion and pitting. Corrosion tests were carried out on AISI 304 L stainless using a simulated crevice and the compositions of the electrolyte in the crevice determined. Long term potentiostatic tests were used to determine the critical potentials for crevice corrosion (U_S), for various steels in sodium chloride solutions at different concentrations and temperatures. The steels studied were 22 CrMo V 121, X 22 CrNi 17 and AISI 304 L. Like the critical pitting potential (U_L), U_S was found to have a strong dependence on the chloride content of the external solution. At higher concentrations the two potentials were similar. At lower concentrations the U_S was lower than U_L. The knowledge of these critical potentials together with well known rest potentials for a steel in an electrolyte of known concentration, allows conclusions to be drawn about its susceptibility to pitting and crevice corrosion. The method is suitable also for other passive metals.     

Corrosion performance of selected stainless steels in brine from reverse osmosis desalination plants

Abstract

The corrosion performances of some commercial stainless steel alloys in the brine reject solution from a reverse osmosis sea water desalination plant was studied in terms of their pitting susceptibilities (investigated under aerated conditions at ambient temperature using a cyclic polarisation technique) and crevice corrosion resistances (evaluated in the plant over a 3 month exposure period using multiple crevice test assemblies). The alloys used were four austenitic steels, UNS S31603, UNSS 31703, UNS N08904, UNS S31254, a ferritic steel UNS S44635, and a duplex steel UNS S32550. Cyclic polarisation studies show that the pitting or breakdown potentials for S31603 and S31703 occurred at more active values than for N08904, S31254, S44635, and S32550 alloys, and indicated a reduced resistance to pitting corrosion. The multiple crevice tests show that the alloys S31603, S31703, and N08904 do suffer crevice corrosion in the brine reject solution at ambient temperature, while the S44635 S32550, and S31254 alloys showed considerably higher crevice corrosion resistance.     

Einfluss der Halbzeugform auf die Korrosionsbeständigkeit hochlegierter Ni‐Cr‐Mo‐Werkstoffe

Effect of semi‐finished products on the corrosion resistance of high‐alloyed Ni‐Cr‐Mo materials The corrosion resistance of different semi‐finished products of six superaustenitic steels and nickel based alloys in the condition of delivery was investigated in some typical standard corrosion tests. The resistance of sheets, plates, strips, seamless tubes and welded tubes to intercrystalline corrosion was tested according to ASTM G 28 methods A and B, as well the resistance to pitting corrosion according to ASTM G 48 method C. The nickel based alloys 625, C‐276 and alloy 59 are resistant to the FeCl₃‐test according to ASTM G 48 method C and therefore a differentiation of these types in regard to their localized corrosion resistance was achieved only in the more aggressive ‘Green‐Death’‐solution. The laboratory experiments confirmed that the corrosion resistance is identical for all semi‐finished products and that it shows only a slight dependence of the surface condition of the materials tested. Additionally, some typical industrial and practical applications of the six high performance materials are presented to demonstrate the excellent corrosion resistance in the manufactured condition.     

Corrosion characteristics of the wrought Ni‐Cr‐Mo alloys

This paper concerns the wrought, nickel‐chromium‐molybdenum (Ni‐Cr‐Mo) alloys, a family of materials with a long history of use in the chemical process industries. Their attributes include resistance to the halogen acids and resistance to pitting, crevice attack, and stress corrosion cracking in hot, halide salt solutions. The purpose of this paper is to characterize the performance of the Ni‐Cr‐Mo alloys in several key chemicals, using iso‐corrosion diagrams. These indicate the expected corrosion rates over wide ranges of concentration and temperature. Furthermore, the differences between individual Ni‐Cr‐Mo alloys, and their behavior relative to the stainless steels are defined. The data indicate benefits of both a high chromium content and a copper addition, as used in Hastelloy® C‐2000® alloy.     

Localized Corrosion Characteristics of Nickel Alloys:A Review

There are a great variety of commercial nickel alloys mainly because nickel is able to dissolve a large amount of alloying elements while maintaining a single ductile austenitic phase.Nickel alloys are generally designed for and used in highly aggressive environments,for example,those where stainless steels may experience pitting corrosion or environmentally assisted cracking.While nickel alloys are generally resistant to pitting corrosion in chloride-containing environments,they may be prone to crevice corrosion attack.Addition of chromium,molybdenum and tungsten increases the localized corrosion resistance of nickel alloys.This review on the resistance to localized corrosion of nickel alloys includes specific environments such as those present in oil and gas upstream operations,in the chemical process industry and in seawater service.     

The influence of Mn compared to that of Cr,Mo and S on the resistance to initiation of pitting and crevice corrosion in austenitic stainless steels

A large number of production and laboratory heats in grades AISI 304 and 316 with normal and extremely low managanese and sulphur contents and a number of production heats in more highly alloyed austenitic stainless steels have been studied with regard to their resistance to initiation of pitting and crevice corrosion at various temperatures. The criteria for resistance to initiation was the potentiodynamic pitting potential in 0.1 M NaCl and synthetic seawater and the time to attack initiation for crevice corrosion in 0.5 and 5% NaCl solutions. A large number of production and laboratory heats in grades AISI 304 and 316 with normal and extremely low managanese and sulphur contents and a number of production heats in more highly alloyed austenitic stainless steels have been studied with regard to their resistance to initiation of pitting and crevice corrosion at various temperatures. The critieria for resistance to initiation was the potentiodynamic pitting potential in 0.1 M NaCl and synthetic seawater and the time to attack initiation for crevice corrosion in 0.5 and 5% NaCl solutions. The main aims of the study were to examine both the effect of manganese relative to that of chromium, molybdenum and sulphur and the effect of heat treatment and sulphide composition on steels with low manganese contents. Mathematical models for calculation of the pitting potentials have been constructed and multiple linear regression analysis gave the equations and their reliabilities. Lowering of the Mn content in austenitic stainless steels to 0.2% gives rise to a material of interest for constructions where pitting or crevice corrosion are judged to be the only potential types of attack, where operational disturbances leading to greatly increased corrosivity do not occur, where attack can not be tolerated, and where steel with normal managanese content has not exhibited fully satisfactory corrosion resistance. If the above conditions are fulfilled the low manganese content can be said to correspond to the same positive effect as is obtained by an addition of the least 1.5% Mo.