The corrosion behaviour of chromium in hydrogen chloride gas and gas mixtures of hydrogen chloride and oxygen at high temperatures

A kinetic investigation of the CrHClO₂ system at 1 atm was carried out varying the oxygen content from 0 to 75 vol% at 400–800°C by the thermogravimetric method in stagnant gases and by measurements of weight loss and weight of sublimates after corrosion tests in flowing gases. In hydrogen chloride gas the corrosion rate is determined by the rates of formation and evaporation of a CrCl₂ scale: the scale was protective, to some extent, up to 600°C, but rapidly evaporated at still higher temperatures. The addition of oxygen led to suppression of corrosion loss up to about 500°C but to catastrophic corrosion at higher temperatures. The scale formed in the gas mixtures consisted mainly of Cr₂O₃ but vigorous vaporization of CrCl₂ and water occurred at the higher temperatures due to oxy-chlorination.     

The corrosion behaviour of iron in hydrogen chloride gas and gas mixtures of hydrogen chloride and oxygen at high temperatures

Catastrophic corrosion of iron by oxychlorination in hydrogen chloride gas containing 0–75 vol. % oxygen at 300–800°C has been investigated mainly by means of measurements of weight loss and the amount of sublimates. In pure hydrogen chloride gas, the corrosion behaviour was determined by the formation and sublimation of ferrous chloride. Addition of oxygen to hydrogen chloride gas greatly accelerated corrosion of iron due to the formation and sublimation of a low melting point volatile ferric chloride by oxychlorination reactions.     

High Temperature Corrosion of the Alloy Ni4Mo in a hydrogen chloride atmosphere

Specimens of the alloy Ni₄Mo were tested in a hydrogen chloride atmosphere at temperatures between 400° – 850° C. The corrosion of the alloy was followed by gravimetric analyses and microstructural examinations. It was found that the layer formed on the specimens due to corrosion is adherent but porous, thus allowing the volatilization of some of the corrosion products. The formation of various kinds of oxides and chlorides was observed. The exact composition of the scale depended on the temperature of exposure to hydrogen chloride and on the amount of oxygen present as an impurity in the test apparatus. The formation of a domain structure in the uncorroded alloy affects the morphology of the scale/alloy interface.     

The Corrosion of metals in an oxidizing-chloridizing environment at high temperature

An investigation has been undertaken into the behaviour of metals which form the basis of high-temperature alloys in an argon ?5.5% oxygen ?0.96% hydrogen chloride ?0.86% sulphur dioxide gas mixture at 900°C. The intention has been to ascertain the reaction products, with particular emphasis on the formation of volatile species which can cause considerable degradation of commercial alloys in this environment. From consideration of the thermodynamics of the gas system, the potentials of the reactive species can be determined and correlated with the possible reaction products. In this gas mixture, the oxides of nickel, iron, cobalt, chromium, molybdenum and tungsten are the stable phases with respect to the corresponding metals. Indeed, on exposure of the metals to the environment, the appropriate oxide scales are developed. However, the reactions are complicated by formation of volatile corrosion products, particularly for nickel, cobalt and molybdenum. Although a Cr₂O₃ scale is established on chromium, there is evidence for penetration of chlorine-containing species to the scale/alloy interface. The oxide scale on tungsten is not very protective and thickens rapidly while that on molybdenum is volatile, resulting in rapid consumption of the specimen.     

Corrosion resistance of tantalum base alloys. Elimination of hydrogen embrittlement in tantalum by substitutional alloying

The corrosion behaviour of substitutional Ta–Mo, Ta–W, Ta–Nb, Ta–Hf, Ta–Zr, Ta–Re, Ta–Ni, Ta–V, Ta–W–Mo, Ta–W–Nb, Ta–W–Hf and Ta–W–Re alloys has been investigated in various corrosive media, i.e. (1) concentrated sulfuric acid at 250°C and 200°C, (2) boiling hydrochloric acid of azeotropic composition, (3) concentrated hydrochloric acid at 150°C under pressure, (4) HF-containing solutions and (5)0.5% H₂SO₄ at room temperature (anodisation). In highly corrosive media such as concentrated H₂SO₄ at 250°C and concentrated HCl at 150°C tantalum is hydrogen embrittled, probably by stress induced precipitation of β-hydride. Both corrosion rate and hydrogen embrittlement in concentrated H₂SO₄ at 250°C are strongly influenced by alloying elements. Small alloying additions of either Mo or Re decrease the corrosion rate and the hydrogen embrittlement, while Hf has the opposite effect. Hydrogen embrittlement in concentrated H₂SO₄ at 250°C is completely eliminated by alloying Ta with 1 to 3 at % Mo (0.5 to 1.5 wt % Mo). These results can be explained in terms of the oxygen deficiency of the Ta₂O₅ film and the electronic structure of these alloys.     

Oxidation Kinetics of AISI 441 Ferritic Stainless Steel at High Temperatures in CO2 Atmosphere

Ferritic stainless steels used as interconnectors in SOFC stacks are subjected to air and fuel atmospheres at 800 °C. The use of hydrogen as fuel gas may be substituted by fermentative biogas consisting of mainly CO₂ and CH₄. In this gas mixture, carbon dioxide leads to steel oxidation whereas methane induces carburization. The objective of this study was to investigate the oxidation kinetics of the AISI 441 ferritic stainless steel under pure CO₂ in order to understand oxidation mechanisms. The results show that the kinetic behaviour is linear at low temperatures (800–900 °C) and initially linear then parabolic at higher temperatures (925–1,000 °C). Oxide scale consisted of major Cr₂O₃-rich oxide, topped with MnCr₂O₄ and a dispersion of TiO₂. The chromium-rich oxide was analysed by using the photoelectrochemical method. It exhibits N-type semi-conductor. Oxidation kinetics is modelled by the mixed surface and oxide-diffusion limited steps.     

Microstructural Investigation of the HCl-Induced Corrosion of the Austenitic Alloy 310S (52Fe26Cr19Ni) at 500 °C

This paper investigates the influence of 500 ppm HCl in a 5 %O₂–95 %N₂ atmosphere on the oxidation of the austenitic stainless steel AISI 310S at 500 °C. Laboratory exposures were made for one, 24, 72 and 168 h and the samples were analysed with XRD, SEM/EDX, FIB and TEM/EDX. When exposed in oxygen a thin and protective chromium-rich oxide scale forms. Addition of HCl causes significantly accelerated corrosion. Within the first hour of exposure, accumulations of FeCl₂, CrCl₂ and NiCl₂ forms below the chromium-rich oxide, especially at steel grain boundaries. The chlorine-induced corrosion is suggested to occur through an electrochemical reaction, in which the dissociation of HCl to form chloride ions at the scale surface is coupled to the oxidation of the metal surface beneath the scale by an outwards electronic current and inwards diffusion of chloride ions along oxide grain boundaries.     

Effect of Sulphur on the Oxidation Behaviour of Possible Construction Materials for Heat Exchangers in Oxyfuel Plants in the Temperature Range 550–700 °C

During oxyfuel combustion metallic heat exchangers are subjected to service environments which substantially differ from those prevailing during the conventional air firing process. In the present study the behaviour of three selected construction materials (P92, super S304HCu and alloy 617) during exposure in simulated oxyfuel gas with and without addition of SO₂ at temperatures between 550 and 700 °C has been investigated. The alloy microstructure and the corrosion products formed during exposures up to 1000 h were studied by SEM/EDX and correlated with gravimetric data collected during the discontinuous exposures. It was found that the behaviour of the martensitic steel was hardly affected by the presence of SO₂; however, in the case of the austenitic steel S304HCu the SO₂ suppressed internal oxidation occurring at 650 °C in the SO₂-free gas, thus promoting formation of a protective chromium-rich oxide. In the case of the nickel base alloy 617 the SO₂ addition increased the corrosion rates at 550 and 650 °C due to replacement of the external chromia scale by a multiphase scale with sulphur-containing surface nodules. At 700 °C the alloy formed a chromia base surface scale and SO₂ addition suppressed the formation of volatile Cr species. The results are explained using classical oxidation theory related to conditions for external scale formation in combination with thermodynamic considerations of phase stability as well as relative rates of adsorption of various gas species.     

Corrosion of iron–aluminium alloys in gaseous atmosphere containing hydrogen chloride and hydrogen sulphide at 600 and 700°C

Abstract

The corrosion of two binary iron–aluminium alloys was compared in gaseous CO₂–H₂–HCl–H₂S and CO₂–H₂ mixtures at 600 and 700°C. In each environment, the Fe–14Al alloy resisted corrosion due to the formation of a protective alumina scale. The Fe–4Al alloy corroded more rapidly in the CO₂–H₂–HCl–H₂S atmosphere than in the CO₂–H₂ atmosphere at both temperatures. The corrosion products comprised thick outer layers of iron oxide, porous inner layers of mixed iron–aluminium oxide and internal precipitates of aluminium oxide. Sulphur was detected near the scale/alloy interface and the increase in corrosion rate was attributed to the presence of chlorine and sulphur.     

Autoklaven-Untersuchungen der Spannungsrißkorrosion von Fe-Cr-Ni-Legierungen in NaCl/Co2/H2S-Medien

Autoclave investigation of stress corrosion cracking behaviour of Fe-Cr-Ni alloys in NaCl/CO₂/H₂S-environment In oil and gas production, the corrosion problems increase as the depth of the reservoirs increases. The oil and gas products contain chloride-rich waters and mixtures of H₂S and CO₂ at high pressures and temperatures. Materials that can be used under these conditions are only high strength high alloy steels and nickel base alloys. These materials must be assessed for corrosion resistance under these conditions. The environment contain chloride ions and hydrogen sulphide, which are known to be critical components for SCC. With the aid of autoclave experiments, the fields of corrosion resistance for the materials no. 1.4462, 1.4563 and 2.4618 were determined as a function of temperature and hydrogen sulphide pressure. The base environment was a 5 Molar sodium chloride solution at 20 bar carbon dioxide. While the corrosion resistance of the duplex steel, material no. 1.4462, decreases markedly as the strength of the material and the hydrogen sulphide pressure increase, the two austenitic materials are completely resistant up to 300 °C and hydrogen sulphide pressure of 15 bar. Only at 300 °C and high partial pressures of hydrogen sulphide the material no. 1.4563 did fail, when stressed to stress levels higher than the YS. The crack path was predominantly transgranular with minute fractions of intergranular cracking. The microstructure appears to have no effect. All results indicate that a mixed mechanism of hydrogen- and chloride induced SCC is operting, while a corrosion enhancement due to interaction of both critical components takes place.     

High-temperature corrosion behaviors of typical nickel alloy coatings in a simulated boiler coal ash/gas environment in the Zhundong region

The high-temperature corrosion behaviors of five nickel alloy coatings used in coal-fired boilers in the Zhundong region (Xinjiang province) were investigated in simulated coal ash and coal-combusted flue gas environment at 650°C for 250 and 500 hr. The samples were analyzed by weight gain experiment, X-ray diffraction test, and scanning electron microscopy technique with energy-dispersive spectroscopy. The results indicated that the corrosion level is in the order of NiCrMo13 ≈ Hastelloy C-276 (276) > NiCrBSi > Inconel 718 (718) > 45CT. The compositions of the corrosion scale in five nickel alloy coatings mainly consist of NiO, Ni₃S₂, and Cr₂O₃. The enrichment of Cr in the corrosion scale in 45CT, 718, and NiCrBSi coatings inhibits the formation of oxide and sulfide on the coating surface. The presence of W and Mo in nickel alloy coatings accelerates the formation of corrosion products, thus weakening the corrosion resistance of NiCrMo13 and 276 in simulated coal ash and coal-combusted flue gas environment.     

Influence of gas phase composition on the kinetics of chloride melt induced corrosion of pure iron (EU‐project OPTICORR)

Heat exchanger tubes in waste‐fired boilers are usually attacked by aggressive gases like oxygen, HCl and water vapour as well as by solid and molten salts. Especially if the salt deposit is molten, these compounds cause acceleration of the corrosion process. This study focuses on kinetic investigations on the influence of gas phase composition (O₂, HCl and H₂O) on the chloride melt induced corrosion of Fe. Thermogravimetric (TG) tests were conducted on Fe covered by a 50 mol.% KCl/50 mol.% ZnCl₂‐salt mixture at T = 320°C, first in an Ar ‐ O₂ ‐ atmosphere. In these experiments the amounts of salt deposit (15 and 30 mg/cm²) and oxygen (4–16 vol.%) were varied to investigate their influences on corrosion kinetics. The TG curves show three kinetic stages, i.e. an incubation phase, a linear stage and a logarithmic/parabolic stage [1]. Further it could be shown that the duration of the incubation phase and the slope of the linear stage depend on the amount of the salt deposit as well as on the oxygen partial pressure (p(O₂)). The incubation time increases with increasing amount of salt deposit and decreases with increasing p(O₂). Experiments that were carried out in an Ar – O₂ – HCl atmosphere (500–2000 vppm HCl, 4–16 vol.% O₂) yield enhanced mass gain in comparison to TG tests without HCl. In atmospheres containing at least 1000 vppm HCl corrosion starts immediately without going through an incubation phase following a linear rate law. In the next stage the TG curve follows a rate law that is either parabolic or logarithmic. At higher amounts of HCl (2000 vppm, 8 vol.% O₂) the TG curve shows a relative mass loss after about 55 h of corrosion indicating an evaporation of iron chloride. This phenomenon was also observed at 1000 vppm HCl and 16 vol.% O₂ but not in the other experiments presented in this study. Experiments carried out in Ar – O₂ – H₂O are discussed also. In general the TG curves show lower mass gains after some hours of corrosion in comparison to TG tests without H₂O but at the beginning a shortened incubation phase is evident.     

Investigation of the surface properties of heat treated electroless Ni–P coating

Electroless nickel phosphorus (Ni–P) coatings were synthesised from an acid chloride electrolyte. The synthesised coatings were heat treated at different temperatures, and the surfaces of the heat treated coating were characterised using scanning electron microscopy and X-ray diffraction. Adhesion, wettability, hardness and corrosion behaviour of the coatings were measured. The surface morphology showed the formation of a nano crystalline nickel matrix under heat treated condition. X-ray diffraction analysis of the heat treated samples revealed the recrystallisation of nickel and formation of Ni₃P phase in the coatings. The wettabilty study showed that the as-deposited Ni–P coating is hydrophobic and wettability increases to a maximum of 70.8° contact angle for heat treated temperature of 400°C due to nano crystalline formation. The Rockwell C adhesion test revealed the presence of micro cracks with increase in heat treatment temperature, however the failure is within the acceptability limit. The micro hardness of the Ni–P coating increased with increase in heat treatment temperature. Corrosion potential of the Ni–P coating shifted to a positive potential under heat treated conditions owing to oxidation and precipitation of Ni₃P phase. Decreased corrosion rate and corrosion current density (7.37–0.21?µA?cm^?2) is attributed to heat treatment at 400°C.     

Depolarised gas anodes for aluminium electrowinning

Consumable carbon anodes are used in the electrowinning of aluminium by the Hall-Heroult process.Emissions of CO2 may be eliminated by introducing an inert oxygen evolving anode,which however will require a higher anode potential.An alternative approach is to use a natural gas or hydrogen gas anode to reduce the CO2 emissions and lower the anode potential.Preliminary laboratory experiments were carried out in an alternative molten salt electrolyte consisting of CaCl2-CaO-NaCl at 680 °C.Porous anodes of platinum and tin oxide were tested during electrolysis at constant current.The behaviour of inert anode candidate materials such as tin oxide and nickel ferrite were also studied.     

The oxidation of nickel-chromium alloys in atmospheres containing sulphur dioxide

The simultaneous attack of oxygen and sulphur on a range of NiCr alloys containing 2–30%Cr has been investigated between 500 and 790°C in Ar-10% SO₂ atmospheres. Reaction kinetics were followed using an automatic recording balance and scale structures were examined by metallography, scanning electron microscopy and microprobe analysis.Compared with pure Ni, the addition of up to 5%Cr at 500°C, or 15%Cr at 700°C, has little effect on kinetics. At higher Cr levels (8–10% at 550°C or 15–20% at 700°C) initial protective behaviour is followed by a period of rapid attack. Even with Cr contents as high as 30% the protection shown is not as good as in the absence of sulphur from the atmosphere. The failure to form protective oxides is thought to be due primarily to the penetration of initially formed Cr₂O₃ scales by sulphur, possibly by solution and diffusion, leading to the formation of duplex (oxide + sulphide) scales which grow rapidly by nickel ion migration.     

The corrosion of steel and aluminium in calcium chloride/ammonia,magnesium chloride/methylamine and magnesium chloride/methylamine/decane

The corrosion of St 37, StE 36, Al 99,5 and Al-Mg 3 in the chemical pairs of substances calcium chloride/ammonia, magnesium chloride/methylamine and magnesium chloride/methylamine/decane was investigated. The corrosion tests were performed in autoclaves at room temperature to 180 °C. The nominal duration of the experiments was 1000 hours. Rod shaped fatigue specimens with polished surfaces served as test specimens; these were fatigue tested after the corrosion treatments. All materials tested were compatible with calcium chloride/ammonia under the experimental conditions employed. Steel and aluminium showed similar behaviour against magnesium chloride/methylamine and magnesiumchloride/methylamine/decane, respectively. At room temperature and 70°C to 80°C the corrosion of steel and aluminium was low (wall losses in the order of 1 m?m/a). Corrosion increased with increasing temperature. The activation energy for the reaction, which determined the rate of weight loss in magnesium chloride/methylamine/decane, was AE_st = 0, 60 ± 0,18 eV for steel, and AE_Al = 1, 07 ± 0,07 eV for aluminium. A corrosion treatment on aluminum fatigue specimens after 1000-1500 hours at 110 °C caused a notable decrease in fatigue strength; no such behaviour was noted for steel, even when corroded at 170 °C.     

Corrosion behaviour of the new gas turbine alloy 2100 GT in hot gases and combustion products

Not only excellent high temperature mechanical properties are needed to establish a new gas turbine alloy, but also a very good oxidation behaviour, together with good resistance to so‐called “hot corrosion”. This paper describes experimental studies on the corrosion behaviour in hot gases and combustion products of a new Ni‐Cr‐Ta alloy 2100 GT in comparison to the commercially established alloys 230, C‐263 and 617. Alloy 2100 GT is a newly developed cobalt, tungsten and molybdenum free Ni‐base superalloy of Krupp VDM. It contains as major alloying elements 25 wt.‐% chromium, 8 wt.‐% tantalum, 2.4–3 wt.‐% aluminium and 0.2–0.3 wt.‐% carbon. High temperature strength is achieved by the addition of tantalum, resulting in significantly increased solid solution strengthening, carbide hardening due to the formation of primary precipitated tantalum carbides, and γ′‐precipitation hardening by aluminium and tantalum. The isothermal oxidation tests showed that the parabolic rate constant of alloy 2100 GT is similar to that of alumina‐forming alloys. This is achieved by the remarkably high aluminium content for a wrought alloy. Additions of yttrium improve the spalling resistance under thermal cycling by the formation of very thin and tightly adherent oxide layers. No deleterious effect caused by the addition of tantalum could be found. In the cyclic oxidation tests performed at temperatures between 700°C and 1200°C alloy 2100 GT showed the lowest mass change of all the alloys investigated. Na₂SO₄ has been found to be a dominant component of alkali salt deposits on gas turbine components at elevated temperatures. Combustion gases contain SO₂ because of the impure nature of the fuel. To investigate the hot corrosion behaviour of alloy 2100 GT, tests were performed with salt deposits containing 0.1 mol Na₂SO₄ and a test gas comprising air and 0.1% SO₂. Test temperatures were 600°C, 700°C, 850°C and 950°C. Alloy 2100 GT exhibited the best performance at all test temperatures. It was the only alloy which did not suffer any fluxing of the oxide layer and only slight internal sulphidation was observed.     

Hot corrosion behaviour of Nimonic-105 in NaCl and Na2SO4

The hot corrosion behaviour of Nimonic-105 alloy was investigated in the presence of NaCl and Na₂SO₄ by employing the crucible test. The experiments were carried out in the temperature range 700°–800°C for periods of 2 to 20 hours. The end reaction products were characterised by the XRD, XRF, SEM, EPMA and chemical analysis techniques. Weight loss plots obtained in pure salts followed a linear rate law. However, the weight loss results obtained in salt mixtures indicated two zones of severe corrosion. The first zone occured in the presence of low concentrations of NaCl (1–5%) when the salt mixture was maintained in the solid + liquid (S + L) state and the other in the molten state, containing higher concentrations of NaCl (15–30%). Blisters and cracks were observed on the immersed surface of the corroded sample in the first zone and on the exposed top surface in the second zone. Both zones were occurred in the temperature range 700°–800°C, i.e., above the eutectic temperature (635°C) of the corrodent mixture and around the m.p. of NaCl (800°C). The heavy corrosion in the second zone was associated predominantly with voluminous formation of nickel coated Ni₃S₂ globules, and Na₂MoO₄. Denudation of alloying elements was observed due to preferential removal by the corrodents. The degradation of the alloy in the presence of corrodents is discussed.     

The corrosion of pure niobium in oxidizing,sulfidizing, and oxidizing-sulfidizing gas mixtures at 600–800°C

The corrosion of pure niobium has been studied at 600–800°C in various environments as part of a study of the corrosion resistance of its alloys with iron, cobalt, and nickel to atmospheres of low-oxygen and/or high-sulfur activities. The results have shown that not only the sulfidation but also the corrosion in mixed atmospheres and particularly the oxidation under low oxygen pressures of pure niobium are quite slow, with kinetics rather similar in the three types of gas mixtures used. The good corrosion resistance of niobium to attack by oxygen under low pressures is quite interesting because this element is corroded very rapidly by oxygen under high oxygen pressures, due to the formation of the nonprotective highest oxide Nb₂O₅ as a main corrosion product.     

Corrosion of mild steel under heat transfer in high temperature aerated sodium chloride solutions

It is suggested that acidity may be generated at high temperatures by a mechanism analogous to the pitting/crevice corrosion which occurs at room temperature in oxygenated chloride solutions. The corrosion rate of mild steel was monitored in oxygenated and de-oxygenated 100 p.p.m. sodium chloride solutions at temperatures between 200° and 350°C at heat fluxes of 110–260 kW/m². Corrosion rates were measured by determining the hydrogen generated.In de-oxygenated solutions, corrosion rates were low and a thin magnetite film was found on both heated and unheated surfaces. In oxygenated solutions, severe corrosion occurred at heated surfaces forming a thick laminated oxide scale.