Der Einfluß von Schwefeldioxid,Schwefelwasserstoff und Kohlenmonoxid auf die Lochkorrosion von austenitischen Chrom-Nickel-Stählen mit bis zu 4 Massen-% Molybdän in 1 M Natriumchlorid-Lösung

The Influence of SO₂, H₂S and CO on Pitting Corrosion of Austenitic Chromium-Nickel Stainless Steels with up to 4 wt. % Molybdenum in 1 M NaCl Active corrosion of chromium-nickel stainless steel X 5 CrNi 189 (AISI 304) in H₂SO₄ is stimulated by H₂S as well as by SO₂ (extension of the potential range of active corrosion, increase of the maximum corrosion rate in the active state and of the passivation current density), but is inhibited by CO (decrease of both maximum active corrosion rate and passivation current density). It is investigated whether likewise stimulating and inhibiting effects are valid also in case of pitting corrosion of austenitic stainless steels with molybdenum contents ranging from about zero (material no. 1.4301) to 4 wt. % (material no. 1.4449), tested in 1 M NaCl (ambient temperature) saturated with the gases mentioned above. The pitting corrosion behaviour of the materials investigated is judged by their pitting potentials measured by potentiostatically controlled experiments (testing time 24 hrs). The pitting potentials are compared with those measured in 1 M NaCl, N₂-bubbled. Pitting corrosion is stimulated by SO₂, CO and H₂S, with the stimulating efficacy increasing in the sequence given before. No stimulation is found only in 1 M NaCl, SO₂-bubbled,-with the highest Mocontent. In all other cases, stimulation of pitting corrosion increases with increasing Mo-content of the stainless steels. In coarse approximation, the critical limiting potentials of stable pitting in 1 M NaCl, bubbled with H₂S, SO₂ CO, correspond to the critical potentials of repassivating pitting corrosion found in N₂-bubbled 1 M NaCl. The chemical reactions and reaction products of SO₂ in aqueous solution are discussed. The nature of the stimulating component of the corrosive medium is not quite clear. The stimulating effects of SO₂ or one of its reaction products and of H₂S on pitting are in keeping with their stimulating effect on active corrosion of the steels investigated. The stimulating effect of CO, however, is in contradiction to the results expected and cannot be explained.     

Corrosion behaviour of Lotus-type porous high nitrogen nickel-free stainless steels

Corrosion behaviour of three austenitic Lotus-type porous high nitrogen Ni-free stainless steels exposed to an acidic chloride solution has been investigated by electrochemical tests and weight loss measurements. Polarization resistance indicates that the corrosion rate of Lotus-type porous high nitrogen Ni-free stainless steels is an order of magnitude lower than that of Lotus-type porous 316L stainless steel in acidic environment. The localised corrosion resistance of the investigated high nitrogen Ni-free stainless steels, measured as pitting potential, E_b, also resulted to be higher than that of type 316L stainless steel. The influences of porous structure, surface finish and nitrogen addition on the corrosion behaviour were discussed.     

Die Inhibition der Aktivkorrosion nichtrostender Stähle in Säuren durch Kohlenmonoxid

The inhibition of the active corrosion of stainless steels in acids due to carbon monoxide The active corrosion of stainless austenitic chrome-nickel steels in H₂SO₄ is effectively inhibited by CO below the boiling temperature of the acid. The potential range of active corrosion is narrowed down, and the passivation current density as well as the maximum dissolution rate are reduced. In the boiling solution, pitting corrosion occurs in certain potential ranges, which can be reduced or completely prevented by increasing the Mo-content of the steels.     

Elektrochemische Untersuchung der Lochkorrosion chemisch beständiger Stähle

Electrochemical investigation into the pitting corrosion of corrosion resistant steels In view of the fact that the characteristics termed pitting potential depend from the measuring methods and nonstationary defects and hysteresis phenomena produced thereby these condition have been investigated on three different systems. In sulphate inhibited chloride solution an actual hysteresis is found with two critical boundary potentials for pit formation and pit passivation. The first of these potentials may be found either by potentiocinetic or by potentiostatic methods, the second only galvanostatically. In the case of 35% Cr steel no hysteresis is found; in this case there is no connection between pitting potential and the current and potential variations found during the investigation. With this material pitting corrosion may occur below the pitting potential while the pit passivation potential is a function of the properties of the measuring circuit. The pitting behaviour of austenitic CrNi steels containing various amounts of molybdenum may be characterized potentiostatically or potentiocinetically, but at low voltage feed rates only.     

Localized corrosion properties of low interstitial ferritic,high purity austenitic and high chromium duplex stainless steels

Within the framework of a research aimed at characterizing the behaviour of new materials to pitting and crevice corrosion, an investigation has been made, using electrochemical techniques, of the following materials: ELI ferritic stainless steels (18 Cr-2 Mo-Ti; 21 Cr-3 Mo-Ti; 26 Cr-1 Mo); high chromium duplex stainless steel (Z 5 CNDU 21-08) and high chromium-nickel austenitic stainless steel (Z 2 CNDU 25-20); commercial austenitic stainless steels (AISI 304 L and 316 L) and laboratory heats of austenitic stainless steels with low contents of interstitials (LTM/18 Cr- 12 Ni, LTM/16 Cr- 14 Ni-2 Mo). It was possible to graduate a scale of resistance to pitting and crevice corrosion in neutral chloride solutions at 40 C; in particular the two experimental austenitic stainless steels LTM/18 Cr- 12 Ni and LTM/16 Cr- 14 Ni-2 Mo are at the same level as the AISI 316 L and 18 Cr-2 Mo-Ti, respectively. An occluded cell was developed and used for determining the critical potential for crevice corrosion (E_{localized corrosion}). For the steels under investigation E_{localized corrosion} is less noble than E_pitting especially for ELI ferritic 18 Cr-2 Mo-Ti and 21 Cr–3 Mo-Ti.     

Elektrochemisches Verhalten und Deckschichtbildung hochlegierter Manganstähle

Electrochemical behaviour and scaling of high alloy manganese steels Passivating surface layers are considered to be one of the indispensable requirements for stress corrosion cracking of metallic materials. It is shown by potentiostatic and potentiokinetic current density-potential curves that the steel X 40 MnCrN 19 in neutral aqueous chloride solutions has a passive potential region. The passivation behaviour Of precipitation hardened samples is in agreement with the chromium depletion theory. The effect of alloying on the passivation behaviour of low carbon Mn steels is studied in 3 % NaCl solution at 20 and 100 °C Increasing proportions ε-martensite reduce the passivation of susceptibility. Increasing the Mn content has the same effect. The vital factor concerning passivation behaviour, however, is chromium content. Increasing the temperature of the corrodent results in an increased tendency to form scales of steels containing less than 8 % Cr. Long-term corrosion tests have shown, that increasing the Cr content produces a continuous transition from general localized and even pitting Corrosion. Tests made without applied current in aerated solutions have shown, that the variation in time of corrosion potentials depends from the tendency to be passivated of the materials and from the oxygen content of the solutions. In oxygen containing solutions passivable steels exhibit a pronounced corrosion in the pitting region, because with such alloys anodic dissolution current densities equal to those of the limiting diffusion current of oxygen reduction are obtained only at potentials above the pitting potential.     

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.     

Spannungsrißkorrosion von hochlegierten Manganstählen in wäßrigen Chloridlösungen

Stress corrosion cracking of high alloy manganese steels in aqueous chlorides In tensile tests made without applied current in aerated solutions a stabilization of the austenitic structure by increasing Mn and N contents yields increased times to failure. The potential-time-to-failure curves determined by potentiostatic tensile tests reveal a compley joint action of constitution and passivation behaviour of the steels. The intercrystalline stress corrosion cracking of the steel X 40 MnCr 19 with chromium carbide precipitations at the grain boundaries can be attributed to an electrochemical differentiation of the chromium-depleted grain boundary region. Steels of this type are characterized by a pronounced sensitivity to intercrystalline stress corrosion cracking the precipitation annealed state, and by a certain sensitivity to transcrystalline corrosion cracking after solution annealing. Low carbon Mn steels containing up to 4 % Cr are susceptible to transcrystalline stress corrosion cracking irrespective of the heat treatment. As to the temperature dependence of times-to-failure, constitution and layer formation have different effects. Increasing the Cr content to 8 % gives rise to a transition from stress corrosion cracking to pitting type corrosion. In terms of electron optics, an increased chromium content gives rise to a changed dislocation pattern, so that there may be an effect of the type of gliding processes on stress corrosion, The increased stress corrosion resistance of MnCr steels containing at least 8% Cr may be due to the lower height Of the gliding step and to an increasing tendency to repassivation of damaged surface layers.     

节镍型不锈钢的耐腐蚀性能比较

通过3.5%NaCl溶液中动电位极化曲线测定和中性盐雾试验,对200系列奥氏体不锈钢和400系列铁素体不锈钢两类节镍型不锈钢与304不锈钢的耐腐蚀性能进行了对比研究。结果显示,400系列铁素体不锈钢的耐点蚀性能优于200系列奥氏体不锈钢,两种节镍型不锈钢的耐点蚀性能均不如304不锈钢好;200系列奥氏体不锈钢的耐均匀腐蚀性能最差,443不锈钢耐均匀腐蚀性能与304不锈钢相当,439不锈钢比304不锈钢耐均匀腐蚀性能稍差。201、202、304、439和443不锈钢在3.5%NaCl溶液中的点蚀电位分别为(vs.SCE)-32 mV、-22 mV、312mV、165 mV和227 mV,腐蚀速率分别为0.0071 mm/a、0.0062 mm/a、0.0026 mm/a、0.0038 mm/a和0.0024mm/a。     

Oberflächenbehandlung als Korrosionsschutzmaßnahme von nichtrostenden Stählen

Surface treatment as corrosion protection measure of stainless steels The pickling behaviour of several stainless austenitic steels and of one steel with ferritic/austenitic grain structure were investigated in pickling solutions of different compositions based on hydrofluoric acid. Because of uncertainties in practical applications, the influence of temperature, time and acid content on the mass loss is of high interest. In another series of experiments, aqueous solutions of citric acid were tested for their suitability as pickling chemicals for the materials X 6 CrNiTi 18 10 (AISI 321) and X 6 CrNiMoTi 17 12 2 (AISI 316 Ti). Finally, the pickling procedures based on nitric acid/hydrofluoric acid mixtures were compared with mechanical cleansing methods and with pickling procedures based on aqueous citric acid solutions as well, to elucidate their influence on the corrosion resistance of the treated materials. The valuation followed a pitting corrosion test in sodium chloride solutions of different concentrations after Herbsleb and Schwenk. Pickling with hydrofluoric acid solutions is superior to other cleansing procedures, if corrosive environments are present. The ecologically beneficial citric acid solutions are only able to remove the annealing colours from stainless steels.     

Korrosion nichtrostender austenitischer Stähle in (kondensierender) chloridhaltiger Salpetersäure

Corrosion of austenitic stainless steels in (condensing) nitric acid containing chlorides The corrosion parameters involved in the behaviour of austenitic stainless steels and nickelbase alloys in chloride containing nitric acid are being stated. Investigation of the corrosion resistance of the austenitic stainless steel 1.4306, ESR grade for application in nitric acid, in nitric acid condensates containing small amounts of chlorides. The condensates were formed from boiling nitric acids of molarities 6 to 10 containing 15 to 45 mg chlorides/1. The calculated corrosion rates of < 1 μm/y can be considered rather small. Especially in cases of insufficient wetting of the heat exchanger surfaces, however, local roughening and pitting corrosion is to be expected, mostly under rust-colored, chloride-containing deposits. The intensity of pitting corrosion increases with increasing chloride contents of the nitric acid solutions that evaporate. The sealing surfaces consisting of steel 1.4306 and PTFE did not exhibit any crevice corrosion. Nitric acid grade ESR-1.4306 definitely does not suffice requirements as described in this paper. It is suggested to use stainless steels which exhibit an improved resistance against chlorides and, at the same time, a high resistance against nitric acid attack. The following steel grades may be considered: X 1 CrNi 25 21 (Mat. No. 1.4335), X 2 CrNiMoN 25 22 2 (Mat. No. 1.4466) and/or X 1 NiCrMoCuN 31 27 4 (Mat. No. 1.4563).     

Korrosionsbeständigkeit von Installationsteilen aus nichtrostenden austenitischen Chrom-Nickel-Stählen bei erhöhter Temperatur

Corrosion resistance of installation elements of stainless austenitic chromium-nickel steels at high temperatures The test results presented prove the statements made in DIN 50 929 Part 2. In accordance with DIN 50 930 Part 4, the corrosion probability for stainless steels increases when chloride containing water evaporates on warm material surfaces, whereby chloride ions concentrate. Under these conditions, ferritic chromium steels and austenitic chromium-nickel steels can suffer pitting corrosion, austenitic chromium-nickel steels also stress corrosion cracking. In the latter case, the corrosion cracks start from pits. The molybdenum-containing material no. 1.4571 withstands pitting and stress corrosion cracking in wet, chloride-containing environments at 90°C over some weeks. With increasing exposure time and at temperatures above 45°C, however, corrosion damage cannot be excluded. Then, according to DIN 50 929 Part 2, coating of the external surfaces of installation components, e.g., tubes, is required. The coating must be thick, free from pores and holidays, and resistant to heat and aging.     

Einfluß von Passivierungs- und Kohlenstoffschichten auf austenitischen CrNiMo-Stählen auf die Beständigkeit gegen Lochfraß und Spannungsrißkorrosion

Effects of passivation and carbon films on austenitic CrNiMo steels on their piting and stress corrosion resistance The influence of passive film and combinations of a passivation and a carbon layer on the resistance to pitting and SCC of austenitic CrNiMo steels has been investigated in physiological sodium chloride solution (Tyrode solution) at pH 6.9 to 7.4 at 37 ± 1°C. The passive film was obtained after electrolytic polishing in H₃PO₄ + H₂SO₄ + C₆H₅NHCOCH₃ + oxalic acid + corrosion inhibitor CS by treatment with 40% nitric acid the carbon film was obtained by CVD. Impurities in the steel (non-metallic inclusions) and the different metallic phases were investigated and the chemical composition of the passive film was determined by quantitative analysis. The resistance to pitting of the steel with and without passive film was determined potentiodynamically in Tyrode's solution at 37 ± 1°C. The resistance to SCC was determined in Tyrode's solution at 37 ± 1°C, in neutral glycerole and in boiling magnesium chloride solution at 154 ± 1°C and evaluated in terms of K_σ and K_τ. The corrosion damage was investigated by optical and scanning electron microscopy. The investigations have revealed that the different surface conditions considerably improve the pitting and SCC resistance of the steels in the media used in this work, so that they make possible the use of these materials as surgical implants.     

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.     

Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle (Teil II)

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels (Part II) Austenitic stainless steel (18% Cr, 12% Ni, Mo gradation between 0,06 to 3,6%) had been solution nitrided. By step‐by‐step removing, the samples could be prepared with various surface contents of nitrogen from 0.04 to 0.42%. In two test series the influence of nitrogen had been determined. The susceptibility against pitting corrosion of these samples had been tested by the chronopotentiostatical method. For the investigated steel composition and the used corrosion system there is no infuence of molybdenum on the effectiveness of nitrogen. The effectiveness of nitrogen can be described by the factor 25 in the PRE. By the investigation of the surfaces with the XPS analysis, it could be shown that the passivation and the pit nucleation is influenced by nitrogen. In these ranges NO_x, NH_x, and NH_z‐spectra have been detected. Bound Mo was found in steels containing molybdenum. It is assumed that the repassivation mechanisms of N and Mo work independently of each other. With the results efforts are supported to improve the pitting corrosion resistance also at molybdenum poor steels by surface nitriding or nitrogen alloying. The achieved results justify the assumption that the observed positive effect of the nitrogen may be extented to even higher nitrogen contents. A prerequisite for this is avoiding secondary phases in the matrix. The adverse influence of small particles is known well.     

改性纳米SiC粉体强化铸造奥氏体不锈钢耐点蚀性能的研究

在生产条件下采用冲入法制备了改性纳米SiC粉体强化奥氏体不锈钢试样,用化学浸泡和电化学检测两种方法研究了纳米SiC粉体对不锈钢耐点蚀性能的影响。结果表明,经改性纳米SiC粉体强化处理后的不锈钢组织明显细化,成分偏析引起的铁素体析出减少;当纳米SiC粉体加入量为0.1 mass%时,不锈钢的点蚀速率降低了 16%,电极电位提高了3倍。能谱分析表明,经强化处理,不锈钢中的Cr成分偏析减轻,有效改善了晶界等易发生点蚀部位的贫Cr现象。     

Improvement of the Corrosion Resistance of High Alloyed Austenitic Cr-Ni-Mo Stainless Steels by Solution Nitriding

Characteristic features of austenitic steel grades combine a good corrosion resistance with a low hardness, wear resistance and scratch resistance. An interesting possibility for improving the wear behaviour of these steels without loss of their corrosion resistance lies in enriching the near surface region with nitrogen. The process of a solution nitriding allows the rise of the solution of nitrogen in the solid phase. On this state nitrogen increases the corrosion resistance and the tribilogical load-bearing capacity. The aim of the study was, to investigate the improvement of the pitting corrosion behaviour by solution nitriding. A special topic was to observe the effect of nitrogen by different molybdenum content. So austenitic stainless steels (18% Cr, 12% Ni, Mo gradation between 0.06 to 3.6%) had been solution nitrided. The samples could be prepared with various surface content of nitrogen from 0.04 to 0.45% with a step-by-step grinding. The susceptibility against pitting corrosion of these samples had been tested by determination of the stable pitting potential in 0.5M and 1M NaCl at 25℃. For the investigated steel composition and the used corrosion system there is no influence of molybdenum on the effectiveness of nitrogen. The influence of nitrogen to all of the determined parameters can be described well by PRE = Cr 3.3 * Mo 25 *N. XPS analysis of the sample surfaces support the results of the pitting corrosion tests.Additionally surface investigations with an acid elektolyte (0.1M HCl 0.4M NaCl) were performed. In this case the passivation effective nitrogen content increases markedly with rising molybdenum concentration of the steel.Obviously an interaction of Mo and N is connected with a strongly acid electrolyte.     

Microstructure and pitting corrosion of similar and dissimilar stainless steel welds

Abstract

Pitting Corrosion behaviour of similar and dissimilar metal welds of three classes of stainless steels, namely, austenitic stainless steel (AISI 304), ferritic stainless steel (AISI 430) and duplex stainless steel (AISI 2205), has been studied. Three regions of the weldment, i.e. fusion zone, heat affected zone and unaffected parent metal, were subjected to corrosion studies. Electron beam and friction welds have been compared. Optical, scanning electron microscopy and electron probe analysis were carried out to determine the mechanism of corrosion behaviour. Dissimilar metal electron beam welds of austenitic–ferritic (A–F), ferritic–duplex (F–D) and austenitic–duplex stainless steel (A–D) welds contained coarse grains which are predominantly equiaxed on austenitic and duplex stainless steel side while they were columnar on the ferritic stainless steel side. Microstructural features in the central region of dissimilar stainless steel friction welds exhibit fine equiaxed grains due to dynamic recrystallisation as a result of thermomechanical working during welding and is confined to ferritic stainless steel side in the case of A–F, D–F welds and duplex stainless steel side in the case of D–A welds. Beside this region bent and elongated grains were observed on ferritic stainless steel side in the case of A–F, D–F welds and duplex stainless steel side in the case of D–A welds. Interdiffusion of elements was significant in electron beam welding and insignificant in friction welds. Pitting corrosion has been observed to be predominantly confined to heat affected zone (HAZ) close to fusion boundary of ferritic stainless steel interface of A–F electron beam and D–F electron beam and friction weldments. The pitting resistance of stainless steel electron beam weldments was found to be lower than that of parent metal as a result of segregation and partitioning of alloying elements. In general, friction weldments exhibited better pitting corrosion resistance due to lower incidence of carbides in the microstructure.     

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.     

Beitrag zur Methodik der Messung von Lochfraßpotentialen an austenitischen Chrom-Nickel-Stählen

Contribution to the methodology of pitting corrosion potential measurement on austenitic chromium nickel steels Reproducible values of the pitting potential and the incubation period are obtained only when definite techniques are applied to the specimen preparation. When the specimens are to be masked for the purpose of suspension they must be passivated without this mask because otherwise there would occur some type of crevice corrosion in the boundary zone between mask and open specimen surface. The corrosion potential in this is more negative (by 150 mV for a steel AISI 316) the the pitting potential as such. Preferential dissolution occurs in this zone when the pitting potential is attained. When, on the other hand, the passivation is effected without the mask, uniform pitting is achieved across the whole free surface and the pitting potential may be measured without difficulty. This potential turns out to be independent from the duration of passivation, while the incubation period distinctly increases with passivation time.