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

A kinetic investigation of corrosion of nickel in hydrogen chloride gases containing 0–75% oxygen at 400–700°C was carried out by the thermogravimetric method. There was no great difference in the corrosion behaviour of nickel in the hydrogen chloride gas and its mixtures with oxygen because of exclusive formation of NiCl₂ scale, regardless of the gas compositions. The corrosion behaviour showed the mixed reaction mode; that is, NiCl₂ scale formation according to parabolic kinetics and NiCl₂ scale evaporation according to linear kinetics. With increasing temperature above 500°C, linear kinetics became predominant.     

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.     

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.     

Untersuchungen zum Einfluß von Sulfationen auf die chloridinduzierte lokale Korrosion am Stahl 1.4541 bei Temperaturen bis zu 280°C und gleichzeitiger Werkstoffdehnung

The influence of sulphate ions on stress corrosion cracking for stainless steel AlSl 321 with constant extension rate in aqueous chloride solution at temperatures up to 280°C CERT (Constant extension rate test: ? = 3·10 ⁶ s ¹) was used to study the inhibition effect of sulphate ions on stress corrosion cracking. Smooth tensile round specimens (AlSl 321) have been tested in solutions with sulphate (10 ²m Na₂SO₄) and chloride ions (10^?3m NaCl. 5. 10 ³m NaCl) at 150°C and 280°C. The presence of sulphate in chloride solutions increases the time to fracture and the reduction of area in comparison to pure chloride solution. The reason is the lower concentration of corrosive hydrogen near the fracture surface in comparison with tests in chloride solutions. The stress corrosion cracking is completely inhibited by the ratio of 10:1 for sulphate and chloride ions in the solution. The fracture surface investigated by Scanning Electron Microscopy has shown a cleavage type of fracture in chloride solutions and a ductile fracture in sulphate/chloride mixtures. The diffusivity of corrosive hydrogen is increased at 280°C in comparison to 150°C. Therefore at 280°C the corrosive hydrogen is able to diffuse into the inner part of the specimen and to influence the fracture mode.     

Effect of the cerium (III) chloride heptahydrate on the corrosion inhibition of aluminum alloy

In the present work, the corrosion protection of aluminum alloy AA2024-T3 has been studied in NaCl solution, with and without the addition of cerium (III) chloride heptahydrate. The corrosion inhibitor efficiency after immersion into 10 mM NaCl, with or without 3 mM of CeCl₃·7H₂O at 20°C, 40°C, and 60°C was investigated. The performed quantitative tests include electrochemical techniques, such as the method of quasipotentiostatic polarization (Tafel extrapolation), cyclic polarization, and electrochemical impedance s pectroscopy to determine corrosion rate (v_corr), inhibition efficiency (η %), protective ability (γ), degree of coverage (ϑ), and pitting nucleation resistance. The samples were analyzed with scanning electron microscopy and energy dispersive X-ray analysis to evaluate and characterize the precipitates formed on the surface of aluminum samples and to determine dominant type of corrosion. The formation of Ce³⁺ precipitates occurred on cathodic intermetallic sites and the surface, in general, resulting in improved corrosion resistance. Tested cerium (III) chloride heptahydrate proved to be an effective inorganic corrosion inhibitor for AA2024-T3 in chloride solution, which, by the action of cerium ions, reduced corrosion on the surface of the studied aluminum alloy.     

Crevice corrosion monitoring of titanium and its alloys using microelectrodes

Crevice corrosion of titanium and its alloys in 10% sodium chloride was investigated at 100°C with the aid of microelectrodes. Potential, pH and chloride ion concentration inside the crevice were monitored using an Ag/AgCl electrode, a tungsten microelectrode and a Ag/AgCl chloride ion selective microelectrode, respectively. The pH and Cl^? concentrations within the crevice were calculated from the standard potential‐pH and potential‐log[Cl^?] calibration curves. The effect of Mo on the crevice corrosion of titanium was also studied. The passivation behavior on the titanium and Ti‐15%Mo alloy was studied using electrochemical impedance studies. There was no apparent change in pH and Cl^? ion activity inside the crevice for the alloy at 100°C, whereas a marginal decrease in pH and increase in Cl^? ion concentration were observed for pure titanium. Thus pure titanium is susceptible to crevice corrosion in hot 10% NaCl solutions at 100°C. The chloride ion activity was found to be reduced for the alloy so that the pH inside the crevice increased. The corrosion reaction resistance (R_t) was found to increase with the addition of Mo as an alloying element. It also increases with externally applied anodic potential. Hence, Mo is an effective alloying element, which enhances the crevice corrosion resistance of titanium.     

Effect of Zinc Chloride in Ash in Oxidation Kinetics of Ni-Based and Fe-Based Alloys

Corrosion by molten phases leads to severe corrosion of heat exchangers in waste-to-energy plants. In addition, the presence of heavy metal chlorides in ash deposit increases degradation at low temperature due to the formation of highly corrosive molten phases. In this study, two heat exchanger materials, a low alloy steel (16Mo3) and a nickel based alloy (Inconel 625) were exposed in air to three different synthetic ashes, with various chloride contents, including ZnCl₂ at isothermal temperatures of 450 and 650 °C in a muffle furnace. After the test, thickness and mass losses were evaluated on two separate samples, and metallographic cross sections of the specimens were characterized via SEM/EDX analyses. Both measurement results were in good agreement and showed that the corrosion observed on both materials was higher in the presence of zinc chloride in ash at 450 °C than in ashes without heavy metal chloride at 650 °C.     

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.     

Thermogravimetric Study of Oxidation-Resistant Alloys for High-Temperature Solar Receivers

Three special alloys likely to be suitable for high-temperature solar receivers were studied for their resistance to oxidation up to a temperature of 1050°C in dry atmospheres of CO₂ and air. The alloys were Haynes HR160, Hastelloy X, and Haynes 230, all nickel-based alloys with greater than 20% chromium content. The oxidation rate of specimens cut from sample master alloys was followed by thermogravimetry by continuously monitoring the weight change with a microbalance for a test duration of 10 h. The corrosion resistance was deduced from the total weight increase of the specimens and the morphology of the oxide scale. The surface oxide layer formed (scale) was characterized by scanning electron microscopy and energy dispersive x-ray spectroscopy and in all cases was found to be chromia. Oxidation was analyzed by means of parabolic rate law, albeit in some instances linear breakaway corrosion was also observed. For the temperature range investigated, all alloys corroded more in CO₂ than in air due to the formation of a stronger and more protective oxide scale in the presence of air. At 1000°C, the most resistant alloy to corrosion in CO₂ was Haynes 230. Alloy Haynes HR160 was the most oxidized alloy at 1000°C in both CO₂ and air. Hastelloy X oxidized to a similar extent in CO₂ at both 900°C and 1000°C, but in air, it resisted oxidation better at 1000°C than either at 900°C or 1000°C.     

Effect of Mo on corrosion behavior of Ni20Cr–xMo alloys in air with NaCl–KCl–CaCl2 vapor at 570°C

The effect of Mo on the corrosion behavior of Ni20Cr–xMo alloys in an oxidizing chlorine-containing atmosphere using air mixed with the salt-vapor mixture of NaCl–KCl–CaCl₂ at 570°C was investigated. The results revealed that the corrosion performance of the Ni20Cr alloys in the oxidizing chlorine atmosphere was improved by Mo addition of up to 3 wt%. The Mo-free alloy formed a potassium chromate during corrosion as a result of the reaction between the Cr₂O₃ scale and KCl vapor. The chromate formation increased the chlorine potential at the scale surface and induced the breakdown of the protective Cr₂O₃ scale, resulting in internal chromium chloride precipitates and a Cr-depleted zone. In contrast, the presence of Mo resulted in the formation of a NiO scale, which did not react with the salt vapors and, therefore, prevented the formation of chromates. The beneficial effect of Mo on the high-temperature chlorination of Ni–Cr alloys in salt-vapor-containing atmospheres was ascribed to the suppression of chlorine generation due to NiO scale formation.     

Corrosion behavior of novel Cu–Ni–Al–Si alloy with super-high strength in 3.5% NaCl solution

A novel Cu–6.5Ni–1Al–1Si–0.15Mg–0.15Ce alloy with super-high strength was designed and its corrosion behavior in 3.5% NaCl solution at 25 °C was investigated by the means of SEM observation, TEM observation and XPS analysis. The alloy after solution treatment, 80% cold rolling and aging at 450 °C for 1 h had the best comprehensive properties with hardness of HV 314, electrical conductivity of 19.4% IACS, tensile strength of 1017 MPa, and average annual corrosion rate of 0.028 mm/a. The oxides and chloride products formed at first, followed by the formation of dyroxides products. The alloy showed super-high strength, good electrical conductivity and corrosion resistant because Ni₂Si hindered the precipitation of large NiAl at the grain boundary and the denickelefication of the alloy.     

Corrosion of HR3C heat exchanger alloy in a biomass fired PF utility boiler

Detailed microscopic examinations have been conducted on two, temperature‐regulated probes (commercial HR3C heat exchanger alloy) after being exposed to biomass flue gas inside a PF boiler for 3770 h at 600°C and 650°C respectively. Corrosion of the tube proceeds via scale formation and internal element depletion. Three characteristic types of internal corrosion have been identified depending on their position relative to the flue gas passage and deposit/flue gas chemistry. Severe, mainly internal corrosion occurs at down‐stream locations where higher potassium chloride content exists within the deposit. Corrosion mechanisms corresponding to each type of internal corrosion have been proposed based on further laboratory tests and thermodynamic analysis. The increased temperature (650°C) causes slightly higher material wastage for the alloy.     

KCl-Induced Corrosion of a 304-type Austenitic Stainless Steel in O2 and in O2 + H2O Environment: The Influence of Temperature

The oxidation of the 304-type (Fe18Cr10Ni) austenitic stainless steel was investigated in the temperature range 400–600 °C in 5% O₂ and 5% O₂ + 40% H₂O. Exposure time was up to 1 week. Prior to exposure, the polished samples were coated with 0.1 mg/cm² KCl. Uncoated samples were also exposed and used as references. The oxidized samples were analyzed by gravimetry and by ESEM/EDX, XRD, IC and AES. The results show that KCl is strongly corrosive. Corrosion is initiated by the reaction of KCl with the chromia-containing oxide that normally forms a protective layer on the alloy. This reaction produces potassium chromate particles, leaving a chromium-depleted oxide on the alloy surface. At 500 and 600 °C this results in rapid oxidation, resulting in the formation of a thick scale consisting of a mixture of hematite, spinel oxide ((Fe,Cr,Ni)₃O₄) and K₂CrO₄. The thick scale is poorly protective and permeable to e.g. chloride ions. The KCl-induced corrosion of alloy 304L in dry O₂ and in an O₂ + H₂O mixture increases strongly with temperature in the range 400–600 °C. The strong temperature dependence is explained partly by the temperature dependence of the chromate-formation reaction and partly by the ability of the chromium-depleted oxide to protect the alloy at low temperature. At 400 °C, the oxide was still protective after 168 h.     

The contribution of hydrogen to the corrosion of 2024 aluminium alloy exposed to thermal and environmental cycling in chloride media

This work is focused on the role of hydrogen in corrosion damage induced by the cyclic exposure of 2024 aluminium alloy to chloride media with air emersion periods at room and/or negative temperatures. Various analysis and microscopic observation techniques were applied at intergranular corrosion defects. A mechanism involving the contribution of hydrogen to the degradation of the alloy mechanical properties is presented. Several consecutive stress states appear during cycling, resulting from volume expansion of the electrolyte trapped in the intergranular defects during emersion phases at −20 °C. These stress states lead to hydrogen diffusion, transport and trapping.     

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.     

Influence of the Oxygen Partial Pressure on the High Temperature Corrosion of 38Ni–34Fe–25Cr Alloy in Presence of NaCl Deposit

In biomass gasification processes, some molten salts formed during the process can promite high temperature corrosion. In this study the chromia-forming austenitic alloy Haynes^® HR-120 was oxidized with a deposit of sodium chloride for 96 h at 825 and 900 °C. Two different atmospheres were selected; one with a high oxygen partial pressure (Ar/O₂ 90/10 %vol.) and one, named syngas, with a low oxygen partial pressure (CO/H₂/CO₂ 45/45/10 %vol.). While at 900 °C the behaviour of the alloy in presence of sodium chloride was catastrophic in high oxidizing conditions, the impact of sodium chloride was insignificant in the syngas atmosphere. When exposed to the Ar/O₂ mixture, the catastrophic oxidation was attributed to the setting up of an active oxidation. At 900 °C under the syngas atmosphere, the protective behaviour of the alloy seems linked to the association of a faster evaporation of the salt and a very low oxygen partial pressure. At 825 °C a catastrophic behaviour is observed under the syngas atmosphere as the NaCl evaporation rate is much slower.     

Hot Corrosion Behavior of a Ni3Al-Based IC21 Alloy in a Molten Salt Environment

Ni₃Al-based alloys have become important candidates for hot components in turbine engines, owing to their low densities and outstanding mechanical properties in service environments. The hot corrosion behavior of a Ni₃Al-based IC21 alloy in a molten salt environment of 75 wt% Na₂SO₄ and 25 wt% NaCl at 900 °C was studied, via oxidation kinetics analyses, scanning electron microscope observations and energy dispersive as well as diffraction analyses by X-ray. A multilayer corrosion oxide scale and dendritic morphology internal corrosion zone formed after hot corrosion, and inter-phase selective corrosion phenomena were also observed. Salt fluxing and oxidation-sulfidation processes were inferred to be the essential hot corrosion mechanisms of the alloy. Moreover, additions of Cr and Y proved to be beneficial to the hot corrosion resistance of the IC21 alloy, while the Mo content should be strictly controlled.     

Über die transpassive Auflösung von Nickel-Basis-Legierungen und Edelstählen in sauerstoff- und chloridhaltigem Hochtemperatur-Wasser

Transpassive dissolution of nickel-base alloys and stainless steels in oxygen and chloride containing high-temperature water The corrosion behaviour of different nickel base alloys and stainless steels (2.4605 [alloy 59; NiCr23Mol6Al], 2.4633 [alloy 602 CA; NiCr25FeAlY], 2.4819 [alloy C-276; NiMol6Crl5W], 2.4856 [alloy 625; NiCr22Mo9Nb], 2.4606 [alloy 686; NiCr20Mu16], 2.4646 [alloy 214; NiCrl6AlFe] and 1.4401 [UNS S 31600; X5CrNiMol7122]) was investigated in oxygen and chloride containing high-temperature water (temperatures up to 600°C; pressures up to 38 MPa; oxygen concentration 0.48 mol/kg; chloride concentrations up to 0. 1 mol/kg). All alloys show a similar corrosion behaviour, depending on temperature. At temperatures below about 150°C, only slight intergranular corrosion was observed. At higher temperatures (between about 150 and 300°C) pitting was detected. Most of the original surface in this temperature range remained unattacked. At higher temperatures, morphology of pitting changed towards shallow pitting and the whole surface is penetrated. The high general corrosion observed in these areas can be attributed to transpassive dissolution of the alloys' protecting chromium oxide layers with following dissolution of the alloy. At supercritical temperatures, corrosion decreased drastically, and only transpassive intergranular corrosion was detected. The observed decrease of ion-induced corrosion phenomena can he attributed to the change of physical and chemical properties of water (solubility of ions). Corrosion in neutral and alkaline solution was significantly less. Both pitting and transpassive dissolution shifted towards higher temperatures or were not detected respectively.     

Corrosion of aluminium,stainless steels and AISI 680 nickel alloy in nitrogen‐based fuels

Nitrogen‐based compounds can potentially be used as alternative non‐carbon or low‐carbon fuels. Nevertheless, the corrosion of construction materials at high temperatures and pressures in the presence of such fuel has not been reported yet. This work is focused on the corrosion of AISI Al 6061, 1005 carbon steel (CS), 304, 316L, 310 austenitic stainless steels (SS) and 680 nickel alloy in highly concentrated water solution of ammonium nitrate and urea (ANU). The corrosion at 50 °C and ambient pressure and at 350 °C and 20 bar was investigated to simulate storage and working conditions. Sodium chloride was added to the fuel (0–5 wt%) to simulate industrial fertilizers and accelerated corrosion environment. Heavy corrosion of CS was observed in ANU solution at 50 °C, while Al 6061, 304 and 316L SS showed high resistance both to uniform and pitting corrosion in ANU containing 1% of sodium chloride. Addition of 5% sodium chloride caused pitting of Al 6061 but had no influence on the corrosion of SS. Tests in ANU at 350 °C and 20 bar showed pitting on SS 304 and 316L and 680 nickel alloy. The highest corrosion resistance was found for SS 310 due to formation of stable oxide film on its surface.     

Effects of Platinum on the Hot Corrosion Behavior of Hf-Modified �á�-Ni3Al?+?��-Ni-Based Alloys

The establishment of a protective ??-Al₂O₃ scale is critical for providing high temperature protection from oxidation and hot corrosion, thereby improving lifetimes of advanced gas turbine engine components. Recent work by our group has shown that a wide range of Pt + Hf-modified ?á?-Ni₃Al + ??-Ni alloy compositions form a very adherent and slow-growing Al₂O₃ scale and exhibit excellent oxidation resistance. The main thrust of the present study was to understand the effects of Pt addition on the Type I (900 °C) and Type II (705 °C) hot corrosion (HC) behavior of model Hf-modified ?á? + ?? alloy compositions. The salt used to bring about hot corrosion was Na₂SO₄. It was found that the Type I HC resistance of ?á? + ?? alloys improved with up to about 10 at.% Pt addition, but then decreased significantly with increasing Pt content up to 30 at.% (the maximum level studied); however, under Type II HC conditions the resistance of ?á? + ?? alloys progressively improved with increasing Pt content up to 30 at.%. The effect of pre-oxidation on hot corrosion resistance was also examined, and the results indicated that pre-oxidation generally improved Type II HC resistance for the test duration studied.