Influence of heat flux on localised corrosion of stainless steel under boiling conditions

The article deals with the influence of heat flux on localised forms of corrosion of stainless steels under the conditions of phase transition on a metal surface. The observations focused on the influence of the initiation and propagation of pitting corrosion and stress corrosion cracking. Pitting corrosion was tested in the environment of 0.6% FeCl₃ + 0.3% EDTA + 0.1% HCl, the susceptibility to stress corrosion cracking was verified in 35% MgCl₂. The tests proved a negative influence of heat flux on the initiation and propagation of non‐uniform corrosion.     

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.     

Corrosion Testing of some Austenitic Stainless Steels and of Inconel Alloy at 25°c in Acidic Chloride Solutions

Abstract

The corrosion of austenitic stainless steels types AISI 304, 310 and 316, and of Inconel alloy, was studied at 25°c, in 5% NaCl solution at an initial pH value of 2·5, and in 5% FeCl³ at pH 1·2. The resistance of the alloys in both corrosive environments was in the order: 310 > 316 > 304 > Inconel. Pre-treatment of the specimens with bubbling chlorine gas increased the subsequent corrosion rates of the alloys. Intermittent bubbling of gas mixtures such as Cl₂, N₂, and/or H₂S, increased the corrosion rate of Inconel alloy when Cl₂ was present, but decreased the corrosion rate when H₂ was present. Heat treatment of austenitic stainless steels increased the subsequent corrosion rates, whereas 16% pre-straining of annealed specimens slightly reduced the rates. Addition of trisodium phosphate to the corrosive solution reduced the corrosion rates and pitting tendency for all three types of austenitic stainless steel.     

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.     

Corrosion behavior of martensitic and precipitation hardening stainless steels treated by plasma nitriding

Plasma nitriding is a well established technology to improve wear and corrosion properties of austenitic stainless steels. Nevertheless, in the case of martensitic stainless steels, it continues being a problem mainly from the corrosion resistance viewpoint.In this work, three high chromium stainless steels (M340, N695 and Corrax) were hardened by ion nitriding at low temperature, intending to preserve their corrosion resistance.Corrosion behavior was evaluated by CuSO₄ spot, salt spray fog and potentiodynamic polarization in NaCl solution. Microstructure was analyzed by optical microscopy, SEM (EDS) and glancing angle X-ray diffraction. All the samples showed an acceptable corrosion resistance in experiments with CuSO₄, but in salt spray fog and electrochemical tests, only Corrax showed good behavior. The poor corrosion performance could be explained by chromium carbides formed in thermal treatment stage in martensitic steels and chromium nitrides formed during nitriding, even though the process was carried out at low temperature.     

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.     

The behavior of chromium and molybdenum in the propagation process of localized corrosion of steels

In order to clarify the effect of Cr and Mo on the propagation of localized corrosion of steels, the electrochemical behavior of pure chromium and molybdenum and of some stainless steels was studied under conditions similar to those existing inside occluded corrosion cells of steels. Oxygen-free FeCl₂ and/or CrCl₃ solutions were used for experiments. The surface films formed in these conditions were analyzed by means of AES and XPS. Cr is passive if the pH value >ca. 1.8 and Cr may retard the propagation of localized corrosion of steels in its early stage. The hydrolysis of Cr³⁺ may change the pH to even lower values. At such low pH and high Cl^? concentrations, Cr is active in the potential range of interest for localized corrosion of steels. Mo is passive under these more acidic conditions and the passivity of Mo in this potential range is attributed to the formation of a film of MoO₂ (or hydrated oxide), which is extremely thin but very protective. Mo is thus effective to retard the propagation of localized corrosion of steels in its more advanced stage.     

Pitting corrosion behaviour of austenitic stainless steels with Cu and Sn additions

The influence of Cu and Sn on the pitting corrosion resistance of AISI 304 and 316 stainless steels in chloride-containing media has been investigated. The corrosion behaviour was evaluated by cyclic polarization, potentiostatic CPT measurements and electrochemical impedance spectroscopy in 3.5 wt% NaCl. The corrosion resistance was also studied in FeCl₃ under Standard ASTM G-48. According to the results, Cu addition favours pit nucleation but inhibits its growth, whereas Sn exerts the opposite effect, favouring pit growth and inhibiting its nucleation. Studies by SEM, X-ray mapping and EDS analysis showed Cu-, Cl- and O-rich corrosion products that reduce the extent of corrosion damage.     

Influence of nitrogen and manganese on localized Corrosion behaviour of stainless steels in chloride environments

Electrochemical localized corrosion tests in substitute ocean water at 40°C and 70°C and ASTM G48 tests in 6% FeCl₃ solution were performed on three classes of stainless steels: Ni-austenitic (both traditional and with high nitrogen content ones), high nitrogen Mn-austenitic nickel free and duplex (both traditional and with high nitrogen content ones). The Pitting Resistance Equivalent formula, PRE_Mn = % Cr + 3.3% Mo + 30% N – 1% Mn, proposed to consider the presence of noticeable amount of manganese in some of the new high nitrogen stainless steels yields good linear correlation with experimental results. The existence of a threshold value of PRE_Mn (≥ 45) to attain excellent localized corrosion resistance has been recognized. According to this observation the high nitrogen Ni-austenitic 21Cr24Ni6MoO.24N, 24Crl8Ni4MoO.48N, 24Cr22Ni7MoO.52N and the duplex 25Cr8Ni4MoO.26N “super” stainless steels are immune to localized attack also in the most severe electrochemical test conditions. This superiority is maintained also in ASTM G48 tests. Due to their values of Critical Crevice Temperature (CCT_{ASTM G48} ≥ 35°C) these steels seem suitable for practical service in seawater environments up to about 30 °C.     

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.     

Einfluß der Oberflächenbehandlung nichtrostender Stähle auf deren chemische Beständigkeit insbesondere gegen Spannungsrißkorrosion

Influence of the surface treatment of stainless steels on their chemical resistance, in particular to stress corrosion cracking The stress corrosion resistance of austenitic stainless steels shows a pronounced dependence from the surface treatment. Grinding with a coarse material makes the surface very susceptible to this type of corrosion. The susceptible can be largely removed by subsequent picking, provided the treatment removes a layer about 3 μm in thickness. Grinding affects the structure to a depth of about 200 μm, but particular conditions appear to prevail in the above mentioned thin surface zone, so that in particular transcrystalline stress corrosion may occur. The susceptibility to stress corrosion cracking can be tested with a solution containing (%) 0.06 acetic acid, 1 acetaldehyde and 100 ppm Cl ions (as CuCl₂) when the corrosion susceptibility is to be evaluated in comparative terms. Pitting corrosion by mixed acid, too, can be largely prevented by deep picking of ground material.     

Poly(3‐octylthiophene) thermally treated as coating for corrosion protection of SS304 in sulfuric acid media

Poly(3‐octylthiophene) (P3OT) was synthesized by direct oxidation of the 3‐octylthiophene monomer using ferric chloride (FeCl₃) as an oxidant. Using the drop‐casting technique, P3OT coatings were deposited onto 304 type stainless steel electrodes. For the purpose of determining the effect of thermal annealing on the corrosion protection of stainless steel with P3OT coatings, the coated electrodes were thermally annealed for 30 h at two different temperatures, 55 and 100 °C. The corrosion behavior of P3OT coated stainless steel was investigated in 0.5 M sulfuric acid (H₂SO₄) at room temperature using potentiodynamic polarization curves (PPC), linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS). The results indicated that the thermally treated P3OT coatings improved the corrosion resistance of the stainless steel in 0.5 M H₂SO₄. The best corrosion protection was obtained by the P3OT coating annealed at 100 °C. In order to study the temperature effect on the morphology of the coatings before and after the corrosive environment and compare it with corrosion protection, atomic force microscopy (AFM) and scanning electronic microscopy (SEM) were used.     

Pitting and crevice corrosion behaviour of high alloy stainless steels in chloride‐fluoride solutions

The localised corrosion resistance (pitting and crevice corrosion) of two high alloy stainless steels, namely superduplex (SD) and superaustenitic (SA), has been studied in chloride‐fluoride solutions at pH values ranging from 2 to 6.5. The pitting potential (E_pit) and crevice potential (E_cre) have been calculated for these test media using electrochemical techniques (continuous current). The Critical Pitting Temperature (CPT) and Critical Crevice Temperature (CCT) are in both materials lower then the room temperature. In spite of this fact and due to the high repassivation rate, the resistance of these materials to localised corrosion is high in the tested media. At the highest tested concentration of aggressive anions and pH 6.5 both materials undergo a generalised attack.     

Electrochemical noise studies of the effect of nitrogen on pitting corrosion resistance of high nitrogen austenitic stainless steels

Pitting corrosion studies were carried out on nitrogen containing stainless steels (SS) in 0.01 M FeCl₃ using Electrochemical Noise (EN) technique. Shot-noise parameters like characteristic frequency of corrosion events, f_n and characteristic charge, q and noise resistance (R_N) showed that with increase in nitrogen the tendency to undergo pitting corrosion decreases. A plot of maximum pit depth, Pit_max vs. nitrogen content showed that, Pit_max decreased with increase in nitrogen content and followed a parabolic relationship. A new parameter, charge ratio was defined; it was observed that charge ratio values decreased with increase in nitrogen content.     

Electrochemical synthesis of ferritic stainless steels alloyed with 1 wt-%Ti,V and Nb in sulphuric acid solution

Abstract

Corrosion behaviours of stainless steel alloys containing corrosion resistant elements were investigated. Ferritic stainless steel electrodes were synthesised by the application of a scan rate of 1 mV s^–1. Stainless steels were unalloyed and alloyed with approximate 1 wt-% Ti, V and Nb elements. The samples were obtained from casting and forging. The steels were exposed to different heat treatments. Heat treatment was not applied to the first group of samples. The second and the third group of samples were rapidly cooled after annealing at 1100°C for 30 and 180 min respectively. The corrosion performances of ferritic stainless steels were investigated in 0·1 M H₂SO₄ solution, by use of electrochemical impedance spectroscopy. Scanning electron microscopy (SEM) investigations were performed. Scanning electron microscopy micrographs showed generalised pitting on the surface. Corrosion resistance was calculated by Stearn-Geary equation. It was determined that titanium has the best effect on the corrosion resistance of ferritic stainless steels homogenised for 180 min.     

Neue Erkenntnisse auf dem Gebiet der ferritischen rostfreien Stähle

Recent developments in ferritic stainless steels The pitting resistance of ferritic stainless steels in HCl is visibly improved by Mo, in particular in the case of vacuum-melted material. In this context the ratio Cr:Mo = 25:2 is superior ta Cr:Mo = 17:3; addition of Mo prevents, beyond that, crevice corrosion. Ti increases resistance in the Strauß test but not in the Huey test, while Nb turns out to have a positive effect in either test. Steels containing Cr: Mo = 17:l are certainly still susceptible to pitting, but no longer to stress corrosion cracking in boiling MgCl₂, solution; stress corrosion cracking is not observed in 55% boiling Ca(NO₃)₂, and 25% boiling NaOH, but after annealing at 980 °C intercrystalline corrosion takes place. The test duration required for establishing cracking susceptibility is considerably shorter with ferritic than with austenitic steels (100 and 1000 to 2000 hours respectively).     

Erosion and Corrosion Behavior of Laser Cladded Stainless Steels with Tungsten Carbide

Laser cladding of tungsten carbide (WC) on stainless steels 13Cr-4Ni and AISI 304 substrates has been performed using high power diode laser. The cladded stainless steels were characterized for microstructural changes, hardness, solid particle erosion resistance and corrosion behavior. Resistance of the clad to solid particle erosion was evaluated using alumina particles according to ASTM G76 and corrosion behavior was studied by employing the anodic polarization and open circuit potential measurement in 3.5% NaCl solution and tap water. The hardness of laser cladded AISI 304 and 13Cr-4Ni stainless steel was increased up to 815 and 725Hv_100?g, respectively. The erosion resistance of the modified surface was improved significantly such that the erosion rate of cladded AISI 304 (at 114?W/mm²) was observed ~0.74?mg/cm²/h as compared to ~1.16 and 0.97?mg/cm²/h for untreated AISI 304 and 13Cr-4Ni, respectively. Laser cladding of both the stainless steels, however, reduced the corrosion resistance in both NaCl and tap water.     

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.     

Influence of Cu and Sn content in the corrosion of AISI 304 and 316 stainless steels in H2SO4

This paper addresses the influence of Cu and Sn addition on the corrosion resistance of AISI 304 and 316 stainless steels in 30 wt% H₂SO₄ at 25 and 50 °C. The corrosion process was evaluated by gravimetric tests, DC measurements and electrochemical impedance spectroscopy (EIS). The corrosion products were analysed by SEM, X-ray mapping and XPS before and after accelerated tests. The behaviour of both AISI 304 and 316 stainless steels in sulphuric acid solution was greatly improved by increasing Cu concentration and the synergic effect of Cu and Sn. Addition of Sn increased corrosion resistance, but less than addition of copper.     

Effect of Mo and Mn additions on the corrosion behaviour of AISI 304 and 316 stainless steels in H2SO4

The work addresses the influence of Mn and Mo additions on corrosion resistance of AISI 304 and 316 stainless steels in 30 wt.% H₂SO₄ at 25 and 50 °C. Corrosion mechanism was determined by gravimetric tests, DC polarization measurements and electrochemical impedance spectroscopy (EIS). The morphology and nature of the reaction products formed on the material surface were analysed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Reduction of temperature from 50 to 25 °C drastically decreased the corrosion rate of AISI 304 and 316 stainless steels in sulphuric acid solution. Mn additions did not affect significantly the general corrosion resistance due to its low ability to form insoluble compounds in acid medium. Meanwhile, the formation of molybdenum insoluble oxides enhanced the corrosion performance.