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.     

Kühlwasserseitige Korrosionsbeständigkeit von metallischen Werkstoffen zur Handhabung von Schwefelsäure

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

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.     

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

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

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.     

An investigation on the effect of bleaching environment on pitting corrosion and transpassive dissolution of 316 stainless steel

Pitting corrosion and transpassive dissolution of 316 stainless steel in a solution containing five percent of commercial bleaching liquid was investigated by employing potentiodynamic polarization method and recording corrosion potential during immersion. Today commercial bleaching liquids are widely used as a cleaner additive. Therefore those house appliances made from stainless steels are in contact with aqueous solution containing bleaching liquid. This may cause severe localized corrosion and transpassive dissolution. In order to investigate the possibility of tranpassive dissolution of stainless steel by bleaching liquid, potentiodynamic polarization and recording the variation of corrosion potential of specimens were carried out in 0.2 M Na₂SO₄ solution containing 5%wt. commercial bleaching liquid. A 500 mV drop in transpassive potential and also instantaneously ennobled corrosion potential revealed the possibility of transpassive dissolution due to the oxidizing effect of the species such as free chlorine and its derivatives in bleaching liquid. Evaluation of the occurrence of localized corrosion at the presence of Cl^? and bleaching liquid was investigated by similar electrochemical experiments in 0.2 M Na₂SO₄ + 0.4 M NaCl containing 5%wt. bleaching solution. Initiation of stable pitting at potentials lower than the transpassive potential as well as a sharp increase of the corrosion potential in this environment demonstrates the possibility of pitting corrosion.     

Zur Korrosionsprüfung von Schweißverbindungen hochlegierter CrNiMo-Stähle und NiCrMo-Legierungen

On the corrosion testing of weldments of high alloyed CrNiMo-stainless steels and NiCrMo-alloys Weluments of high-alloyed CrNiMo stainless steels and Nicro alloys can he more susceptible to localized corrosion than the solution annealed basic material owing to segregations and precipitations in the heat affected zone, the high temperature zone and/or in the weld. To investigate these differences the FeCl₃-test (10% FeCl₃ · 6aq), the test “green death” (11.5% H₂SO₄, 1.2% HCl, 1% CuCl₂, 1% FeCl₃) as well as chronopotentiostatic tests in artificial sea water or in 3% NaCl-solution are used. In particular for testing the highest alloyed materials a CaCl₂ test was developed (4.5M CaCl₂, chronopotentiostatic test in duration of 8 to 10 hours at + 200 mV (SCE)), which can be carried out to a temperature of 115°C at atmospheric pressure. The aggressivity increases in the range FeCl₃-test, “green death”-test, CaCl₂-test. Matching and graduated over-alloyed weldments (TIG, heat input of 7 and 15.5 kJ/cm) of materials 1.4529, 1.4562, 2.4856, 2.4819 (german materials No.) are comparingly examined in various tests, of materials 1.4406, 1.4539, 1.4439 and 1.4563 (german materials No.) only matching weldments in the FeCl₃-test. In strongly oxidizing media only a highly over-alloyed performed weldment (filler material 2.4607, german material No.) produces the best corrosion behaviour, measured as the critical temperatures of localized corrosion. Measurements of critical current densities of passivation can be used for investigations of corrosion behaviour of weldments, too. Critical current densities of passivation are showing a tendency to inverse proportion to the critical temperatures of localized corrosion. Suitable electrolytes are among others 0.2M H₂SO₄ + 1M NaCl + 10^?3% KSCN, N₂-bubbled, 25 to 60°C and xM H₂SO₄ + 4M NaCl + 10^?3% KSCN (x = 0.05 to 1), 25°C, in contact with air. An influence of heat input at the welding is indicated in the test of localized corrosion, but it is only small. It is sometimes more clearly shown at measurements of passivation.     

Elektrochemische Untersuchungen zur Hochtemperaturkorrosion von Chrom-Nickel-Stählen in Alkalisulfatschmelzen bei 700°C

Electrochemical investigations into the high temperature corrosion of chromium nickel steels in alkali sulfate melts at 700°C Specimens from austenitic stainless steels, with and without susceptibility against intergranular corrosion attack, decarburized and carburized, and stabilized with Ti or Nb, have been corroded in eutectic mixture of alkali sulphates at 700°C at constant potentials. Furthermore additions of 10% NaCl and 1% SO₃ have been investigated. Any selective corrosion of both carbides and Cr depleted zones did not take place. With decreasing potentials there was a preferred attack at grain boundaries – especially in the case of NaCl additions. At very negative potentials an “active” corrosion state exists without formation of protective oxide layers with the consequence of fissured surfaces and internal oxidation. The effect is supported by NaCl addition and by Ni as alloying element.     

Influence of different heat treatments on corrosion resistance of martensitic stainless steels

The changes in microstructure, caused by different heat treatments, have considerable influence on the corrosion resistance of stainless steels. The heat treatment causes an alteration of carbide contained in steels. Changes in the constant B for these steels, (B = Rp · i_COR) have been observed in quenched, tempered and annealed conditions. Pitting corrosion resistance of martensitic stainless steels in quenched and tempered conditions in 0.1M H₂SO₄ by adding Cl^? ions has been investigated.     

Lochkorrosion stickstofflegierter austenitischer CrNiMnMoN-Stähle in 3%iger NaCl-Lösung

Pitting corrosion of nitrogen alloyed austenitic CrNiMnMoN steels in 3% NaCl solution Nitrogen containing austenitic CrNiMnMoN steels investigated electrochemically in chloride containing aqueous solutions exhibit pitting corrosion susceptibility which may be attributed to the materials conditions after solution annealing and work hardening. The range of passivity of high chromium steels goes up to a potential of E ≈? 1300 mV_{H H}, but beyond the limiting potential E_L for stable pitting there may be pitting phenomena on the rolled surfaces of the specimens. At potentials between E ≈? 300 mV_H and E_N various current density peaks appear and indicate the range of repassivable pitting in terms of pit formation on the cutting edges of the specimens. After cold rolling of the sheet the current density is increased in the entire potential range, since the pit density cutting edges and rolled surfaces increases as deformation is increased. Such cold working, however, does not result in a shift of the limiting potential E_L for stable pitting. Investigations concerning the place of formation of the pits indicate that nuclei are preferentially formed at the sites of sulfide inclusions the different shapes of which produce pits of corresponding appearance on the different faces of the specimen. The growth of the pit is influenced by the depth of the pores resulting from the dissolution of the inclusion, and by lattice defects in the metal.     

Der Einfluß des Molybdängehaltes auf die Korrosion austenitischer Cr-Ni-Stähle im Aktivzustand

The influence of the molybdenum content on the corrosion rate of austenitic Cr-Ni steels in the active condition The corrosion rate of steels X 5 CrNi 189, X 5 CrNoMo 18 10, X 5 CrNiMo 18 12 and X 5 CrNiMo 17 13 has been investigated under potentiostatic conditions in the active zone in 2 n H₂SO₄ flushed with nitrogen and sulphur dioxide. The active rest potential of the steels is in the vicinity of the active-passive transition, and the corrosion rate increase at cathodic polarisation. With increasing Mo content, the corrosion rate is reduced in the active condition, but the passivation potential and the corrosion rate in the passive condition are not influenced. In the acid flushed with SO₂, the corrosion rate is increased in the active range, and the latter is extended in the direction of the electronegative potentials. With these steels, even a pre-activation of the specimens has an influence on the test results. In the active-passive transition zone, the steels in the test solution containing SO₂ are partially passive and subject to local corrosion attacks.     

Stress—corrosion cracking of austenitic stainless steel in hydrochloric acid media at room temperature

Stress—corrosion cracking of solution quenched, type 304, stainless steel can occur at room temperature in HCl solutions ranging between 5·10^?1M and 1M HCl. The cracking observed in HCl solutions is similar to that previously observed in H₂SO₄ + NaCl and HClO₄ + NaCl solutions. Cracking occurs at ? 0·200 V (NHE), in the active potential region, it is under cathodic control, and it develops in conditions under which the corrosion rate of the external surface area is more or less constant and independent of the HCl concentration, in the range 10^?1 M?1 M HCl. At higher HCl concentrations, corrosion rates increase and uneven, general corrosion occurs instead of cracking. The development of pitting and stress—corrosion cracking under active conditions precludes the conclusion that active—passive cells always play a role in localized corrosion and, in particular, in stress—corrosion cracking. Under these conditions, it has been shown that sensitized and non-sensitized specimens behave similarly (giving rise in both cases to transgranular cracking); active—passive cells, due to chromium depletion at the grain boundaries, are not involved. Active—passive corrosion mechanisms can however arise at more noble potentials (0·100?0·200 V NHE), as in the case of HClH₂O₂ solutions of specific concentration, producing intergranular corrosion of the stainless steel in the sensitized condition.     

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.     

Lochkorrosion an Nichtrostenden Stählen

Pitting corrosion of stainless steels Stainless steels can get pitting corrosion in halide containing solution, which make them a big risk in industrial production. Many investigations were made in the past in order to understand processes involved in pitting corrosion, pit initiation and pit growth. Results about the influence of alloying elements, their contents, the state of the structure, the condition of the surface, the content of chloride, the temperatures, the pH-value, the velocity of flow and of the oxidizer on the chloride induced pitting corrosion of passive stainless steels are presented. Electrochemical measurements and the application of surface analytical methods (SEM, SAM, XPS) with high lateral resolution are carried out. A part of the samples received a diffusion annealing in order to obtain reproducible results. Pitting Resistance Equivalents (PRE) – Pitting Index – with different multipliers are given and discussed critical. An electrochemical method for selecting materials without susceptibility to pitting corrosion are also presented.     

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.     

Untersuchungen über den Einfluß von Schwefelwasserstoff und Schwefeldioxyd auf die Korrosion chemisch beständiger Chrom-Nickel-Stähle in schwefelsaurer Natriumsulfatlösung

Investigations into the influence of hydrogen sulphur dioxide on the corrosion of chemically resistant chrome nickel steels in a sulphuric acid chrome nickel steels in a sulphuric acid solution of sodium sulphate By measuring the current/potential curves and determining the weight losses, the influence of H₂S and SO₂ on the corrosion of an 18/8 Cr? NI steel and of an 18/8 Cr? Ni stell with 2pCMo and 2.8pC Cu in sodium sulphate solution has been investigated. H₂S and SO₂ have the effect of shifting the rest potential towards the electronegative side, compared with a solution flushed with nitrogen, enlarging the potential range of active dissolution, and greatly increasing the dissolution, and greatly increasing the corrosion rate in the active zone. From the results of the measurements, it may be concluded that the metal dissolution is catalyzed by hydrogen sulphide ions and probably by reduction products of the sulphur dioxide. This catalyzing effect is not confined to the zone of activation overpotential but also occurs in the zone of the active plateau, the shape of which is largely determined by the migration phenomena. SO₂also has the effect of increasing the dissolution rate in the passive condition.     

Surface analytical and electrochemical study on the role of adsorbed chloride ions in corrosion of stainless steels

The pitting potential E_pit of 18/8 CrNi stainless steels with different sulfur content (0.003, 0.017 and 0.29%) has been determined from potentiodynamic polarization curves in deaerated neutral solutions (0.1 M NaCl and 1 M Na₂SO₄ + 0.1 M NaCl) with nominally identical chloride content. E_pit decreased with increasing sulfur content of the alloy and was about 0.2 V more negative in pure 0.1 M NaCl solution. The chemical composition of the passive film and the adsorbed chloride content have been determined by XPS surface analysis on mechanically polished samples passivated for one hour at potentials below the pitting potential. XPS results show that the surface films are composed in all cases of mixed iron‐chromium oxi‐hydroxides with a higher chromium content than the bulk composition. The average passive film composition (ca. 40% chromium oxi‐hydroxide) and the film thickness (2.3 ± 0.2 nm) were similar for all 18/8 CrNi steels regardless the different sulfur content. The amount of chlorides in the passive film is about twice as high on steels exposed to pure 0.1 N NaCl solution compared to the mixed 1 M Na₂SO₄ + 0.1 M NaCl solution. Thus the lower pitting potential measured in pure 0.1 N NaCl solution correlates with the higher amount of chloride ions on the passive film surface.     

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.     

Pitting of austenitic stainless steel clad metals

Austenitic stainless steel welds with different ferrite contents (4 and 12 FN) were obtained by the Submerged Arc Welding (SAW) strip cladding process, and some clads were remelted by TIG. The welds were post weld heat treated (PWHT) at 600, 800, 1000°C for 1 h. Pitting potentials were measured in 1 N H₂SO₄ + 0.5 N NaCl. Etching at the pitting potentials was carried out in the same solution in order to locate the pit sites; pitting studies were also conducted in 10% FeCl₃ solution. The results showed that an increase in ferrite content decreases pitting resistance. PWHT at 800°C decreases pitting resistance, too, whereas PWHT at 1000°C results in increased pitting resistance at austenite/ferrite interfaces. TIG samples showed less pits than their SAW counterparts.     

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.