Zum Korrosionsverhalten nichtrostender austenitischer Chrom-Nickel-(Molybdän,Kupfer)-Stähle in nahezu wasserfreier Essigsäure

Corrosion of stainless austenitic steels in almost anhydrous acetic acid As-welded samples and looped specimens from 5 differently alloyed stainless steels were tested for up to 246 days in 99,5% to 99,95% acetic acid at 118°C (boiling temperature/normal pressure) and at 150°C; the chloride content was varied between < 1 and 100 ppm. Pitting corrosion – of shallow depth, however (approx. 0,1 mm) – was already observed at surprisingly low chloride concentrations. Only the following were found to be resistant to pitting corrosion:

• – stainless steels 1.4439 and 1.4539, containing approx. 4,5% molybdenum, in 99,5% acetic with < 1 ppm chloride at 118 and 150°C,
• – stainless steels 1.4439 and 1.4539 in 99,9% acetic acid with < 1 ppm chloride at 118°C, and
• – special stainless steel X 2 CrNiMoCuN 20 18 6, containing approx. 6% molybdenum, in 99,5% acetic acid with > 3, < 10 ppm chloride at 118 and 150°C.

Looped specimens and ground as-welded samples showed no sensitivity to transcrystalline, chloride-induced stress corrosion cracking at any of the concentration ranges. High surface-removal rates can be expected if air has access to the specimens; under this condition pitting corrosion and general corrosion may overlap. Contamination of acetic acid with chlorides must be prevented under all circumstances.     

Mikrobielle Werkstoffzerstörung – Simulation,Schadensfälle und Gegenmaßnahmen für metallische Werkstoffe: Lochfraß an Flußwasser-Rohrleitungen aus hochlegierten austenitischen Stählen durch mikrobielle Aktivität

Microbial deterioration of materials – simulation, case histories and countermeasures for metallic materials: Pitting corrosion caused by microbiological activity at austenitic stainless steel pipes used for river water Rhine River water used for cooling purposes increasingly causes pitting at circumferential welds in type 321 and 316Ti stainless steel piping. Type 321 is attacked even at ambient temperature, type 316Ti at 35 to 55°C. At these temperatures both materials did not show pitting in the past. Failure analysis and corrosion tests, both in the laboratory and in a pilot, plant (river water circuit), showed that the open circuit potential of stainless steels is shifted into a region of instable pitting resistance by a microbiological effect. Thus, pit nuclei are able to grow even at circumferential joints welded without any visible annealing colours. The actual concept to select cooling water pipe materials, therefore, has to be reconsidered.     

Pitting corrosion of Type 430 stainless steel under chloride solution droplet

To clarify the critical relative humidity (RH) to initiate pitting corrosion and the rusting mechanism in a marine atmospheric environment, pitting corrosion of Type 430 stainless steels under drops of MgCl₂ solutions were investigated. A pitting corrosion test was performed at different relative humidities under droplets with various diameters and thicknesses. The probability of pitting decreased as the diameter and thickness decreased. Pitting progressed only when the chloride concentration exceeded 4 M, which is the equilibrium concentration at 80% RH. Accordingly, pitting of Type 430 could be initiated when the RH was less than 80%. Additionally, a pitting corrosion mechanism of Type 430 stainless steel under droplets containing chloride ions is proposed.     

Novel strategies for assessing the pitting corrosion resistance of stainless steel surfaces

Pitting corrosion is one of the most common mechanisms of surface damage on stainless steels. Electrochemical methods have been preferentially applied for the evaluation of the pitting corrosion resistance of stainless steels in the laboratory. Nevertheless, some of them are not reliable enough and in general the application of electrochemical methods in the field becomes difficult because of required deep understanding of corrosive phenomena and measurement technology. Therefore, new approaches for the evaluation of the pitting corrosion susceptibility of stainless steel surfaces in the laboratory as well as in the field are necessary. In the present paper two novel strategies including electrochemical noise measurements under anodic polarization for laboratory testing, and an indicator test to assess the susceptibility of stainless steel surfaces to pitting corrosion in the field are introduced. Experimental results concerning the influence of surface treatments on the pitting corrosion resistance on stainless steels have confirmed that final surface condition has a significant effect on their future pitting corrosion susceptibility. In addition, the pitting corrosion resistance of stainless steel surfaces was observed being specifically dependent on the achieved surface topography and in some cases independent on the roughness parameters of the surface.     

Microbiologically influenced corrosion of stainless steels – What is required for pitting?

Pitting of stainless steels in environments normally regarded as completely harmless is often attributed to microbial activity. In this paper, attention is drawn on one hand to the basic requirements for pitting of stainless steels to be possible, and on the other hand to various ways how microbial activity could contribute to a fulfilment of these requirements. For pit growth to be possible, three basic requirements must be fulfilled: 1) the environment must contain anions that can form an aggressive solution into the pit, 2) there must be a potential difference between the interior of the pit and the open surface outside the pit, 3) the temperature must exceed a critical value. The main factors that normally influence the possibility of pitting are the chloride content and the oxidising power of the environment, presence of anions other than chloride, temperature, possible presence of deposits on the steel surface, and the composition of the steel. Anions other than chloride in the bulk solution, including sulphate, usually have an inhibiting effect. Thiosulphate, however, is known to promote pitting under certain conditions. The possible ways of microbial activity to enhance pitting could include deposit formation leading to crevice type of attack, local modification of the composition of the environment to a more concentrated one, raising the electrode potential of the steel surface (“ennoblement”), or formation of reaction products that permit active dissolution inside a pit at lower potentials. Special attention is drawn to the possible action of thiosulphate by enhancing the anodic reaction at low potentials of the dissolving surface inside the pits.     

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.     

Pitting transients analysis of stainless steels at the open circuit potential

Metastable pitting of stainless steels in chloride containing oxidising electrolytes is investigated at rest potential using a new experimental technique allowing to record simultaneously the potential and corrosion current variations. Different industrial surface conditions (BA and 2B) are tested for both ferritic (FeCr type) and austenitic (FeCrNi type) stainless steels. It was shown that the number of pitting events decreases with the exposure time and that BA condition provides better resistance to pitting than 2B. As far as pitting mechanisms are concerned, the potential recovery after pitting does not reflect the pit repassivation but rather refers to the discharge of the surface capacity. Analysing the pitting transients provides quantitative information on the cathodic reaction through the passive film (transfer resistance and surface capacitance). Differences in pitting transient shapes are discussed as well.     

Die Lochkorrosion austenitischer Chrom-Nickel- und Chrom-Nickel-Molybdän-Stähle in schwefelsaurer Bromidlösung und ihre Inhibition durch Nitrationen

Pitting corrosion of austenitic chromium nickel and chromium nickel molybdenum steels in sulfuric acid containing bromides, and its inhibition nitrate ions In acidified bromide solution CrNi steels are attacked under pitting when a certain critical potential has been exceeded; this potential is higher than in the case of chloride containing solutions. Bromides are, consequently, less active than chlorides, but the pit density is considerably higher under idential corrosion conditions. While the pitting corrosion in chloride solutions can be considerably reduced by molybdenum addition to the steel, this effect is but little pronounced in the case of bromide solutions (with Mo additions up to 4% the potential is displaced by 0.2 V toward positive values). Mo additions around 2% are even dangerous since the pitting density is considerably increased in that range. Similar to the conditions in chloride solutions corrosion in bromide solutions is inhibited by nitrate additions; the potential limit is considerably higher in the bromide solution; this phenomenon points to stronger adsorption of bromide ions at the metal surface.     

New stainiess steels for sea water applications. Part. 1: Corrosion and mechanical properties of ferritic stainless steels

Two experimental ELI ferritic stainless steels (22 Cr – 2.5 Ni – 3 Mo and 22 Cr – 2.5 Ni – 3 Mo – Ti) prepared in laboratory and a commercial one (21 Cr – 3 Mo – Ti) were investigated. Electrochemical and laboratory exposure tests were carried out to define the localized corrosion resistance (pitting and crevice) of such steels in chloride solution. Intergranular and stress corrosion resistance was also evaluated. Room temperature tension tests and impact tests were performed. 22 Cr – 2.5 Ni – 3 Mo – Ti and 21 Cr – 3 Mo – Ti steels are immune to intergranular corrosion whatever temperature they are heat treated at and have the same pitting corrosion resistance as a function of temperature; crevice corrosion of 22 Cr – 2.5 Ni – 3 Mo is decidely better than in the commercial 21 Cr – 3 Mo – Ti. The experimental steels were immune to stress corrosion in hot chloride environment.     

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.     

Zu einem Phänomen der Lochkorrosionsbegrenzung bei hochlegierten Sonderedelstählen und NiCrMo-Legierungen in Chloridlösungen

On a phenomenon of the limitation of pitting corrosion at high alloyed special stainless steels and NiCrMo-alloys in chloride solutions Testing the pitting corrosion resistance of high alloyed special stainless steels and NiCrMo-alloys in chloride solutions there was observed a limitation of the pitting corrosion range toward more positive potentials. Above this limitation, the so-called pitting corrosion limitation potential, the pit initiation by all means is prevented, but the growth of pits which had been initiated before in the pitting corrosion range not necessarily comes to a stop. Therefore current density-potential curves which are obtained by downward polarization after an initial potential jump into the transpassive region and chronopotentiostatic tests are more suitable to investigate this phenomenon than cyclic polarization measurements and potentiostatic alteration tests. There is indicated a dependence of this phenomenon on temperature. The phenomenon of a limitation of the pitting corrosion range toward more positive potentials has been found until now at alloy 926, alloy 31, alloy 28, alloy 59 and alloy C-276.     

Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions

Pitting corrosion of Type 304 stainless steel under drops of MgCl₂ solution has been investigated to clarify the rusting mechanism in marine atmospheres. A pitting corrosion test was performed under the droplets with various combinations of the diameter and thickness (height) by exposure to a constant relative humidity. Probability of occurrence of pitting corrosion decreased with decreasing the diameter and thickness. Pitting corrosion progressed only when the [Cl⁻] exceeded 6 M (RH < 65%). In almost cases, there was a small hole (∼10 μm diameter) in the center of a single pit, which may be the trace of an inclusion particle like MnS dissolved out. The pitting corrosion mechanism of Type 304 under droplets containing chloride ions has been proposed.     

Pitting,Crevice and stress corrosion resistance of high chromium und molybdenum alloy stainless steels

This paper presents new data on the resistance of recently developed high-alloy stainless steels to localised corrosion in chloride solutions. Pitting potential was determined in artificial sea water, and critical pitting temperature CPT in very aggressive FeCl₃ solution. Critical crevice corrosion temperature CCT was tested in the same FeCl₃ solution. Stress corrosion measurements, made in a more familiar NaCl solution by the drop evaporation method, demonstrate that alloy stainless steels with high chromium and molybdenum have very long failure times, comparable with those of nickel alloys found to be SCC-resistant under practical conditions. Stainless steels of 20 Cr 25 Ni 6 Mo type showed the best resistance to localised corrosion.     

Corrosion studies of austenitic and duplex stainless steels in aqueous lithium bromide solution at different temperatures

The corrosion behavior of three stainless steels EN 14311, EN 14429 (austenitic stainless steels) and EN 14462 (duplex stainless steel) was studied in a commercial LiBr solution (850 g/l LiBr solution containing chromate as inhibitor) at different temperatures (25, 50, 75 and 85 °C) by electrochemical methods.Open circuit potentials shifted towards more active values as temperature increased, while corrosion potentials presented the opposite tendency. The most resistant alloys to general corrosion were EN 14429 and EN 14462 because they had the lowest corrosion current for all temperatures. In all the cases corrosion current increases with temperature.Pitting corrosion resistance is improved by the EN 14462, which presented the highest pitting potential, and the lowest passivation current for the whole range of temperatures studied. The duplex alloy also presents the worst repassivation behavior (in terms of the narrowest difference between corrosion potential and pitting potential); it does not repassivate from 50 °C.     

Determination of the weaker phase in the pitting corrosion of non‐standard low‐Ni high‐Mn‐N duplex stainless steels

In this paper, the use of Energy Dispersive Spectrometry (EDS) is proposed to determine the partition coefficients of the elements of a new family of duplex stainless steels that are characterized by having low contents of nickel, together with high levels of manganese and nitrogen. From the values of the partition coefficients, the chemical compositions of the constituting phases have been determined, in order subsequently to calculate the value of the Pitting Resistance Equivalent Number (PREN) of each phase. The proposition put forward in this study is that the phase having the lower PREN determines the pitting corrosion behaviour of these types of steels. Results obtained by means of optical and scanning electron microscopy have provided confirmation that the pitting corrosion behaviour of these new materials gets determined by the resistance of the weaker phase and consequently by the phase having the lower PREN value. Lastly it has been proved possible to determine the existence of an exponential relationship between the alloys pitting potential (Ep) and the weaker phase PREN; this can be utilized for the low‐nickel duplex stainless steels design in which the pitting corrosion resistance is controlled.     

Die Oberflächenbehandlung von Schweißverbindungen hochkorrosionsbeständiger 6% Mo-Stähle und Nickel-Basis-Legierungen

Surface treatments of high alloy 6 Mo stainless steel and nickel alloy weldments High alloy stainless steels (6% Mo) and a high nickel alloy (alloy 625) weldment have been tested in order to answer the question whether post-treatment of the weldment has an effect on the corrosion resistance, especially on pitting corrosion. Therefore, the critical pitting temperature of weldments was tested in acidic chloride solution (standard tests). As a result grinding with rough emery paper as well as sand blasting lowers the localized corrosion resistance in the weldment area, while pickling has a positive effect, especially after blasting. Pickling can be done either by a solution of nitric + hydrofluoric acid or by a commercial pickling paste. In any event pickling is recommended as a final surface treatment for high alloy stainless steels and nickel alloys, especially in case of prevailing highly corrosive conditions such as pitting and crevice corrosion.     

南海大气环境下304不锈钢的点蚀特性研究

目的 研究南海大气环境中服役的304不锈钢的点蚀原因与机理。方法 以不同暴露周期的304不锈钢试样为研究对象,采用动电位极化、电化学交流阻抗谱、扫描电镜和Kelvin 探针技术对其进行分析研究。结果 随着暴露时间的延长,304不锈钢表面的点蚀坑数量和深度均逐渐增加,其极化曲线中,钝化区间缩短,点蚀电位负移,阳极极化曲线斜率明显减小,并出现反复再钝化现象,钝化曲线逐渐消失,同时阻抗测试中的膜层电阻越来越小。SEM分析表明,304不锈钢暴露初期出现不连续的点蚀,点蚀坑向纵深发展,暴露后期出现点蚀群,局部有多个点蚀坑连成一片形成溃疡状的腐蚀表面,同时随暴露时间的延长,扫描试样微区的Kelvin表面电位不均匀性逐渐增强。结论 304不锈钢试样的耐蚀能力随暴露时间的增加而不断下降,点蚀现象不断增加。暴露初期,点蚀坑主要向纵深发展;暴露后期,点蚀坑的宽度达到一定程度后,本体溶液向坑内迁移,稀释了坑内溶液的酸度,点蚀坑向纵深和横向同时发展。     

Untersuchungen über die Lochfraßkorrosion des passiven Eisens in chlorionenhaltiger Schwefelsäure

Investigation into pitting corrosion of passive iron in sulphuric acid containing chloride ions Pitting corrosion of metallic materials is generally connected with presence of a surface layer giving rise to a local differentiation of the electrochemical behaviour of the metal surface. The pitting corrosion by halogen ions on passive metals is investigated using passive iron in chloride ion-containing sulphuric acid as the model system. Quantitative data are presented concerning the mechanism and kinetics of the individual processes giving rise to pitting corrosion in a chloride ion concentration range covering three powers of ten, and in the whole potential range of iron passivity, from the Flade potential to the transpassive breakthrough potential. Pit formation normally follows a linear kinetic law, the rate depending in particular from the chloride ion concentration and from the thickness of the passive layer. The growth of pit diameters follows a linear kinetic law, too; the dissolution current density in the pits depends from the chloride ion concentration. Comparative investigations carried out on active iron, and potential distribution as measured in the pits show that the metal is active in the pits, too. The heterogeneous mixed electrode condition — active pit/passive metal surface — is stabilised by resistance polarisation. The investigations so far do not permit any statement concerning the specific effect of the chloride ions.     

磷、硅、锰和铜对高纯18Cr－14Ni不锈钢在氯化物介质中抗孔蚀性能的影响

应用浸蚀腐蚀试验和阳极极化曲线研究了不同Ｐ、Ｓｉ、Ｍｎ和Ｃｕ含量的高纯１８Ｃｒ－１４Ｎｉ不锈钢在氯化物介质中的抗孔蚀行为．结果表明合金元素Ｐ、Ｓｉ和Ｃｕ的加入可改善高纯１８Ｃｒ－１４Ｎｉ钢的抗孔蚀能力．而Ｍｎ含量的增加对不锈钢的抗孔蚀性能是有害的．     

Contribution to the discussion on Localized Corrosion of Stainless Steels in natural sea water

Electrochemical hysteresis methods are employed to develop experimental potential-pH diagrams for some commercial austenitic and ferritic stainless steels in 3% sodium chloride solutions at room temperature. The results were compared with the electrochemical and the gravimetric behaviour of the single stainless steels in natural sea water. The comparison suggested some considerations about the mechanism of initiation and growth of pitting and crevice corrosion prevailing in natural environment. The higher probability of pits observed in field exposure was correlated to the deposit of a microbiological slime on metal surface that ennobles the free corrosion potentials of passive surfaces up to +400 ÷ +450 m V SCE. The crevice corrosion initiation was in turn attributed to a moderate local acidification originating in conditions of reduced diffusion under the action of passivity current that makes possible pit nucleation which is otherwise unlikely to occur. The pitting growth speeds up the acidification process in the interstice until it causes general corrosion of the walls.