Localised corrosion of highly alloyed stainless steels in an ammonium chloride and diethylamine chloride aqueous solution

This paper studies the pitting corrosion of highly alloyed stainless steels (SS) immersed in an ammonium chloride and diethylamine chloride aqueous solution at temperatures of 25, 40, 60 and 80°C. Four materials were tested: UNS S 31726 SS, UNS S 31254 SS, UNS S 32550 SS and titanium, for comparative purposes. Gravimetric, after immersion up to 103 days, polarisation curves, impedance, SEM, EDX and optical microscopy were the techniques used. UNS S 31726 SS shows the lowest corrosion resistance. UNS S 31254 and UNS S 32550 SSs show similar behaviour. Titanium presents impedance data three orders higher than the other SS materials. The SS materials present a pseudoinductive behaviour on impedance data, associated with an adsorption process of the amine compound which decreases as the temperature increases.     

Effect of chlorination on stainless steels in seawater

The effect of chlorination on the corrosion resistance of different stainless steels in North Sea water has been studied, the sea-water exposures being performed at two Norwegian seawater laboratories. In one laboratory test specimens, simulating various components used in a seawater cooling system, were immersed in the water. In the other laboratory a pipe system containing real components was studied. Seawater temperature, chlorine concentration and chlorination procedure have been varied at both laboratories. The steels investigated include highly alloyed grades like UNS S31254 (AVESTA 254 SMO), UNS S44635 (Avesta Monit) and UNS NO8028 (Sandvik Sanicro 28). The investigation shows that continuously chlorinated seawater is considerably more aggressive than unchlorinated or intermittently chlorinated seawater and that high temperature increases the risks of localized corrosion at the same chlorine concentration. The highest alloyed steel grades were very resistant to crevice corrosion even in continuously chlorinated water but certain kinds of metal-metal crevices have to be avoided. When welded, duplex UNS S31803 was sensitive to pitting corrosion in chlorinated water. Contrary to crevice corrosion, the risk for galvanic corrosion decreases considerably if the seawater is chlorinated.     

Localised effects of macrofouling species on electrochemical corrosion of corrosion resistant alloys

Abstract

Interactions between macrofouling and corrosion have been studied on two duplex stainless steels (UNS S31803 and UNS S32760), an austenitic stainless steel (UNS S31354), a nickel base alloy (UNS N06625), and a cobalt base alloy (UNS R30006) in long term tests conducted in natural sea water off the west coast of Scotland. After an 18 month exposure period, the specimens were heavily fouled primarily with barnacles and mussels and all the materials exhibited crevice corrosion at the specimen/resin interface, although this was less extensive on the nickel base alloy. Localised corrosion was observed under the base of live barnacles on UNS S31603 stainless steel. Direct current electrochemical anodic polarisation tests undertaken after the 18 month exposure period yielded unusually high currents in the range of potentials between the free corrosion value and the breakdown potential. However, long term exposure and associated macrofouling had little effect on the overall breakdown of general surface passivity as indicated by values of the breakdown potential. The higher currents were associated with the appearance, after the anodic polarisation, of black sulphide corrosion products at the specimen/resin crevices, around barnacles, and around mussel byssus threads.     

Study of passive film on stainless steels and high grade nickel base alloy using X-ray photoelectron spectroscopy

Abstract

In the present study an assessment has been made of the air formed passive film and the passive film existing after a short exposure to a synthetic sea water environment on austenitic (UNS S31603), superaustenitic (UNS S31254 and UNS S32654) and superduplex (UNS S32760) stainless steels and a Ni base alloy (UNS N06625) using X-ray photoelectron spectroscopy. Assessment of their corrosion behaviour has been made through use of electrochemical accelerated tests supported by post-test microscopy. The passive film on the Ni base (low Fe) UNS N06625 alloy is remarkably similar to those formed on the high Cr and Mo stainless steels. It has been demonstrated that the Fe/Cr ratio in the passive film is dependent on alloy composition and on the conditions to which the material has been exposed, and a general correlation between passive film constitution and corrosion resistance is evident.     

Theoretical description of the practical possibility of stress corrosion cracking from crevice corrosion sites

Stress corrosion cracking (SCC) from crevice corrosion sites had been found in an experimental work at polarization potential of + 200 mV_SCE. In that work, an occluded U‐bend specimen of Type 316L (UNS S31603) stainless steel was used. The testing was done in sodium chloride (NaCl) solution. Based on that work, the practical possibility of SCC from the occluded U‐bend specimen was described theoretically. It was shown that it would also be possible for SCC to occur in practice (i.e. at practical corrosion potential), but the crevice needs to be tighter. Meanwhile, it would take a longer time for obvious SCC to emerge. For a practical crevice usually formed by placing a crevice former on a large uniform metal surface, the crevice geometry may have little effect on SCC although the crevice can sustain an acidified solution more easily than pitting. The possibility of SCC should mainly depend on the corrosion system itself, i.e. material and environment.     

A general model for the repassivation potential as a function of multiple aqueous species. 2. Effect of oxyanions on localized corrosion of Fe–Ni–Cr–Mo–W–N alloys

A recently developed model for predicting the repassivation potential has been applied to stainless steels and nickel-base alloys in aqueous environments containing chlorides and various inhibiting anions. The model accounts for the effects of solution chemistry and temperature on the repassivation of localized corrosion by considering competitive dissolution, adsorption, and oxide formation processes at the interface between the metal and the occluded site solution. An extensive database of repassivation potentials has been established for six alloys (UNS 31603, N06600, N06690, S31254, S32205, and UNS S41425) in contact with solutions that combine chlorides with hydroxides, molybdates, vanadates, sulfates, nitrates, and nitrites at various concentrations and temperatures. Also, repassivation potentials are reported for four alloys (UNS N08367, N08800, N06625, and N10276) in chloride solutions. The database has been used to establish the parameters of the model and verify its accuracy. The model quantitatively predicts the transition between concentrations at which localized corrosion is possible and those at which inhibition is expected. It is capable of predicting the repassivation potential over wide ranges of experimental conditions using parameters that can be generated from a limited number of experimental data. The parameters of the model have been generalized as a function of alloy composition, thus making it possible to predict the repassivation potential for alloys that have not been experimentally investigated.     

Pitting and crevice corrosion of superaustenitic stainless steels

Superaustenites are mainly used in offshore applications, oil production and chemical industry. Most important types of localised corrosion of these steels are pitting and crevice corrosion. Investigated materials were N08028, S31254 and three modified alloys. Chromium content of investigated alloys varied between 20 and 27%, molybdenum between 3.2 and 6.0%, nitrogen between 0.1 and 0.36% and copper between 0 and 1.1%. For means of comparison stainless steel AISI 316L has been included in the study. Pitting and crevice corrosion of these highly corrosion resistant steels has been investigated by use of standardized tests. Critical pitting temperature and critical crevice temperatures were determined according to ASTM G 48, Methods C and D, respectively. Electrochemical measurements for determination of pitting potentials were done according to ASTM G 61 as well as for determination of critical pitting temperatures according to ASTM G 150. Results are presented as function of MARC (Measure of alloying for resistance to corrosion) defined by Speidel since linear correlation coefficients were higher when compared to conventional PREN. Results obtained by different testing methods must not be compared directly. Every test however is sensitive to microstructural defects like precipitations and segregations that decrease corrosion resistance. The higher alloyed a material is, the higher is its tendency to form microstructural defects, and the more difficult is it to reach its theoretical corrosion resistance at given chemical composition.     

Effect of oxygen and biofilms on crevice corrosion of UNS S31803 and UNS N08825 in natural seawater

The effect of oxygen and biofilms on crevice corrosion of UNS S31803 and UNS N08825 in seawater was studied. Passivity breakdown occurred through crevice corrosion in UNS N08825 and through transpassive dissolution in UNS S31803 although both alloys displayed crevice corrosion under potentiodynamic conditions. The most severe crevice corrosion occurred in the absence of oxygen and the presence of a biofilm. Microbial adhesion as investigated by fluorescence microscopy occurred mainly outside the crevice and DNA sequencing revealed a shift in biofilm composition as a function of substratum surface and oxygen pressure.     

Study of the pitting corrosion of superduplex stainless steel and X-65 carbon steel during erosion–corrosion by cyclic polarisation technique

Erosion-enhanced corrosion behaviour of X-65 carbon steel and UNS S32750 superduplex stainless steel was investigated by electrochemical cyclic polarisation. The tests were performed using a jet slurry device coupled with a potentio-galvanostat at various jet velocities of 4, 6.5 and 9?m?s^?1 and impingement angles of 30 and 90? in a 3.5?wt-% NaCl water containing 6?wt-% silica sand particles. The results showed that increasing the jet velocity and impingement angle increased the corrosion rate of both alloys. Negative hysteresis and greater E_rp than OCP were observed for superduplex stainless steel in all erosion–corrosion conditions that indicated the pitting resistance of the alloy. However, the low resistance of carbon steel against pitting during erosion–corrosion was demonstrated by positive hysteresis in the cyclic polarisation curves as well as SEM images of the eroded surfaces.     

Effect of Heat Input on the Microstructure and Properties of Dissimilar Weld Joint Between Incoloy 28 and Superaustenitic Stainless Steel

Abstract This work focuses on studying the effect of welding heat input within the range from 1 to 5 kJ/mm on the microstructure and the corresponding mechanical and corrosion properties of dissimilar joint between superaustenitic stainless steel （UNS S31254） and Incoloy 28 （UNS N08028）. The two materials were butt-welded with ER NiCrMo3. The metallurgical changes associated with welding of SASS and Incoloy 28 were studied using optical microscope, SEM, and EDX. The mechanical and corrosion properties were investigated using tensile test, Vickers hardness test, and pitting and crevice corrosion tests. The weld metal microstructure showed precipitates with needle-like shape at 3 and 5 kJ/mm. Also, the microstructure showed unmixed zone （UMZ） at the fusion line of both SASS and Incoloy 28 sides at all the investigated heat inputs. The Mo microsegregation within UMZ at Incoloy 28 side increased as the heat input increased from 1 to 5 k J/ram but that in SASS increased with increasing heat input from 1 to 3 kJ/mm and then decreased with increasing from 3 to 5 kJ/mm. The ultimate tensile strengths for all specimens at all the investigated heat inputs are acceptable. The average hardness noticeably changed in weld metal as the heat input increased from 1 to 5 kJ/mm. Other zones such as HAZ or UMZ did not demonstrate marked changes in the average hardness. The pitting and crevice corrosion rates of the weld joint were found significant at l and 3 kJ/mm but insignificant at 5 kJ/mm according to ASTM G48.     

Microbially influenced corrosion on stainless steels in waste water treatment plants: Part 1

Abstract

Field tests on stainless steels have been carried out at five waste water treatment plants for one year. Three grades of stainless steel, i.e. AISI 304 (UNS S30400), AISI 316 (UNS S31600), and duplex 2205 (UNS S31803) were tested in the final settling tank in the plants. The time dependence of the open circuit potential (OCP) was measured for all coupons. Ennoblement of the OCP, similar to that reported from investigations in sea water, was found in one of the plants. Waters from three of the exposure sites, containing dispersed deposits from exposed coupons, were chemically analysed. Pitting corrosion was observed after the field test on steel grade AISI 304 in three of the five plants, and on AISI 316 in one plant. No corrosion was found on 2205 in any of the plants. Laboratory measurements of the OCP were carried out for the AISI 304, AISI 316, and duplex 2205 steels in water collected from one of the plants. Cathodic polarisation curves were recorded in waste water from the same plant. T he cathodic reaction rate increased at the highest OCP. Simulation of the ennoblement was carried out by potentiostatic polarisation in a 600 ppm chloride solution. The current response indicated corrosion of welded AISI 304 material and of AISI 304 and AISI 316 steels in crevice assemblies after a long induction time. Part 2 of this study presents the results of further testing and a risk assessment design.     

Effect of temperature on the corrosion resistance and pitting behaviour of Alloy 31 in LiBr solutions

The corrosion resistance and pitting behaviour of Alloy 31, a high-alloyed austenitic stainless steel (UNS N08031), is studied in two heavy brine LiBr solutions (850 g/l) with and without corrosion inhibitor (lithium chromate) at different temperatures (25 °C, 50 °C, 75 °C and 100 °C) using electrochemical techniques. Cyclic potentiodynamic curves indicate that UNS N08031 is less pitting corrosion resistant and it reduces its repassivation properties as temperature increases. Comparison between the results obtained in LiBr solutions with and without inhibitor suggested a decrease in the inhibitor efficiency of lithium chromate at high temperatures.     

Conditions for stress corrosion cracking to occur from crevice corrosion sites and related electrochemical features

The occurrence of stress corrosion cracking (SCC) from crevice corrosion sites was studied using a kind of occluded U‐bend specimen of Type 316L (UNS S31603) stainless steel. It was done in 0.5 M NaCl solution at room temperature and 50°C. The galvanostatic and potentiostatic polarization methods were adopted. It was found that a tight crevice and high polarization current were the necessary conditions for SCC to occur relative rapidly from crevice corrosion sites. Meanwhile, if there was obvious SCC developing from a crevice corrosion site, the IR drop (or solution resistance) in the crevice path would increase. The increase of IR was attributed to the corrosion product deposition and/or hydrogen bubbles evolved from the cracks. On the other hand, the usually high aspect ratio of stress corrosion cracks, i.e. the inhibited dissolution on the crack walls, might be explained as due to the existence of high IR drops in them.     

Localised corrosion behaviour of alloys 33 and 24 in simulated flue gas desulphurisation environment

Abstract

Potentiodynamic anodic polarisation measurements have been carried out on type 316L stainless steel (as a reference material) and on alloys 33 and 24 in a simulated flue gas desulphurisation environment in order to assess the localised corrosion resistance. The results showed that the pitting corrosion resistance was higher in the case of alloys 33 and 24 than in the reference material owing to the higher contents of nitrogen, chromium, and molybdenum. An accelerated leaching study conducted on the alloys 33 and 24 showed only minor tendencies for the leaching of metal ions at various impressed potentials. Observations by SEM confirmed the lower tendency towards pitting of the alloys 33 and 24.     

The effect of an impinging liquid‐solid jet on the electrochemical corrosion of stainless steels

Stainless steels rely on their passive film for corrosion protection in saline environments and localised disruption of the passive film can lead to high local rates of material loss. Materials which exhibit passivity in static conditions are often susceptible to erosion‐corrosion under severe hydrodynamic regimes. In this paper the corrosion behaviour of two superaustenitic (UNS S31254 and UNS S32654) and one superduplex (UNS S32750) stainless steels was examined in static conditions at a range of temperatures from 18°C to 70°C and during exposure to an impinging saline jet containing varying concentrations of solid particles. In static conditions the materials exhibit decreasing resistance to passivity breakdown as the temperature is increased and a critical breakdown temperature for UNS S31254 and UNS S32750 was identified. Under liquid‐solid impingement the materials exhibit an active regime near to the free corrosion potential followed by a stabilised current regime as more positive potentials. The complex electrochemical response is dependent on the material grade and the solid particle concentration. Also in the paper assessment of the „recovery”︁ of the stainless steels after exposure to slurry impingement is addressed.     

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

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

In situ investigation of crevice corrosion on UNS S32101 duplex stainless steel in sodium chloride solution

The crevice corrosion of UNS S32101 in neutral 0.1 M NaCl solutions at room temperature was investigated directly by a facile method. Experimental results showed that both delayed and immediate crevice corrosion can be initiated. Morphology study indicated that the heaviest corrosion attack happened just below the passive/active boundary on the crevice wall. The relocation of the active dissolution regions during crevice corrosion was observed and explained by established theory. The mechanisms of the delayed and immediate types of crevice corrosion on UNS S32101 duplex stainless steel were discussed.     

Effect of aqueous LiBr solutions on the corrosion resistance and galvanic corrosion of an austenitic stainless steel in its welded and non-welded condition

The corrosion resistance and galvanic behaviour of a highly alloyed austenitic stainless steel (UNS N08031) and a nickel-base alloy (UNS N06059) in its welded (GTAW) and non-welded condition were analysed in LiBr solutions by means of electrochemical measurements. Samples microstructure was studied by SEM and EDX analysis. The alloys considered showed passive behaviour and they were able to repassivate after the breakdown of the passive film. The pitting resistance of the materials increased as the LiBr concentration decreased. With regard to galvanic corrosion, the welded metal was always the anodic element of the UNS N08031-welded metal pair.     

Influence of microstructure on the corrosion resistance of hyperduplex stainless steel

Hyperduplex UNS S32707 is a newly developed austenitic–ferritic stainless steel. The steel contains about 27%Cr, 7%Ni, 4.5%Mo, and 0.4%N, which results in a pitting resistance equivalent factor (PRE) equal to 49. In this study, the pitting corrosion resistance of this new grade of stainless steel was investigated by varying the microstructure using different thermal processes. The critical pitting temperature measurement and cyclic polarization tests confirm the high corrosion resistance of the hyperduplex steel in the solution treated condition. However, deleterious phases form easily during thermal processing and cause a drastic decrease in the corrosion resistance.     

Role of surface finishing on pitting corrosion of a duplex stainless steel in seawater

Localized corrosion of duplex UNS S32550 stainless steel in seawater was investigated in the laboratory and in field trials for several surface finish conditions: polished, ground, and sandblasted. Electrochemical data obtained by polarization curves showed that the smoother, polished surface had better characteristics (higher pitting and protection potentials) than the ground or sandblasted surfaces. However, despite its high degree of roughness, the sandblasted surface was the most resistant in field conditions, exhibiting the lowest number of sites attacked. Internal compressive stresses created by sandblasting seem also to have an “unsensitizing” effect on sensitized zones that exist in cast steel (due to repairs of mold defects), reducing its susceptibility to microbiologically influenced corrosion (MIC). Such stresses are not generated in polished or ground surfaces, and localized MIC attack can occur.