Diffusion of18O in massive Cr2O3 and in Cr2O3 scales at 900°C and its relation to the oxidation kinetics of chromia forming alloys

The lattice and grain-boundary diffusion coefficients of¹⁸O atP _{O 2}=0.1 atm and at 900°C were determined in massive Cr₂O₃ and in Cr₂O₃ scales which were grown on a Ni–30Cr alloy. The diffusion profiles were established by SIMS and analyzed considering two domains in the case of polycrystalline Cr₂O₃ (massive or scales), the first one relative to apparent diffusion and the second to grain-boundary diffusion. A ridge model is proposed for Cr₂O₃ scales to modify thef value, fraction of sites associated with the grain boundary. With such a model,f is equal to 0.0006 and 0.0005 for the scales formed during 15 hr and 165 hr, respectively. The oxygen-lattice diffusion coefficients determined in Cr₂O₃ scales are in very good agreement with those in massive Cr₂O₃. With some assumptions, our diffusion data lead to a calculated parabolic oxidation constant equal to the experimental one. Scale growth occurs by countercurrent diffusion of oxygen and chromium, mainly by grain-boundary diffusion.     

Chromium transport through Cr2O3 scales I. On lattice diffusion of chromium

Cr specimens preoxidized at 1100–1300°C to give Cr₂O₃ scales with varying thicknesses and microstructures have been treated at temperature in high vacuum. During the high vacuum treatment the specimens lose weight due to outward Cr transport through the Cr₂O₃ scales. The initial rate of weight loss gradually diminishes, but eventually the weight loss reaches a linear rate. Concurrently the Cr₂O₃ scale exhibits grain growth and densifies. It is concluded that the mode of outward chromium transport gradually changes during the high vacuum treatment: from lattice and grain-boundary diffusion and possibly vapor transport along microcracks during the initial stage to lattice diffusion only for the densified scales. It is concluded that chromium diffuses by an interstitial type mechanism. Self-diffusion coefficients of Cr in Cr₂O₃ at the Cr-Cr₂O₃ phase boundary have been calculated from the linear rates of chromium transport for different defect structure situations.     

High-temperature corrosion of Cr2O3-forming alloys in CO-CO2-N2 atmospheres

The corrosion of Fe–28Cr, Ni–28Cr, Co–28Cr, and pure chromium in a number of gas atmospheres made up of CO–CO₂(–N₂) was studied at 900°C. In addition, chromium was reacted with H₂–H₂O–N₂, and Fe–28Cr was reacted with pure oxygen at 1 atm. Exposure of pure chromium to H₂–H₂O–N₂ produced a single-phase of Cr₂O₃. In a CO–CO₂ mixture, a sublayer consisting of Cr₂O₃ and Cr₇C₃ was formed underneath an external Cr₂O₃ layer. Adding nitrogen to the CO–CO₂ mixture resulted in the formation of an additional single-phase layer of Cr₂N next to the metal substrate. Oxidizing the binary alloys in CO–CO₂–N₂ resulted in a single Cr₂O₃ scale on Fe–28Cr and Ni–28Cr, while oxide precipitation occurred below the outer-oxide scale on Co–28Cr, which is ascribed to the slow alloy interdiffusion and possibily high oxygen solubility of Co–Cr alloys. Oxide growth followed the parabolic law, and the rate constant was virtually independent of oxygen partial pressure for Fe–28Cr, but varied between the different materials, decreasing in the order chromium >Fe–28Cr>Ni(Co)–28Cr. The formation of an inner corrosion zone on chromium caused a reduction in external-oxide growth rate. Permeation of carbon and nitrogen through Cr₂O₃ is thought to be due to molecular diffusion, and it is concluded that the nature of the atmosphere affects the permeability of the oxide.     

Sulfidation kinetics and scale structures of chromium at temperatures of 973–1173 K and 104–10−6 Pa sulfur pressures

The sulfidation behavior of chromium was investigated over a temperature range of 973–1173 K in H₂S-H₂ gas mixtures of 10⁴–10^–6 Pa sulfur partial pressures using thermogravimetry, X-ray diffractometry, optical and scanning electron microscopy, and electron-probe microanalysis. Sulfidation kinetics are rapid for short periods and obey a linear rate law at low sulfur pressures, whereas at high sulfur pressures sulfidation tends to be parabolic. The surface morphologies can be divided into four types: at high sulfur pressures a petal-like crystal of Cr₂S₃(rho. and tri.) (type 1), at intermediate sulfur pressures a twinlike structure of Cr₃S₄ (type 2), at low sulfur pressures a flat surface with numerous hexagonal pits of Cr_1–xS (type 3), and a fine twinlike structure of ordered Cr_1–xS (type 4). At 973 K, the sulfur pressure ranges are type 1 at > 10^–4, type 2 at , and type 3 at . The critical sulfur pressure where type 2 was formed, 10^–5 Pa at 973 K, shifts toward higherressures at higher temperatures and becomes 10^–3 Pa at 1073 K and 10^–1 Pa at 1173K. Type 4 is observed at 1173K and 10^–6 Pa sulfur pressure. Thesulfide scale is composed of two distinct layers: an external layer, which is dense with a fine columnar structure, and an inner layer, which is porous with a layered structure of sulfides and voids. The external scale is composed offour layers at high sulfur pressures: at the scale-gas interface Cr₂S₃(rho.), next Cr₂S₃(tri.), third Cr₃S₄, and innermost Cr_1–xS. With decreasing sulfur pressures,the number of layers in the external scale was reduced. Pt markers were positioned between the external and inner scales.Emeritus Professor.     

The air oxidation of an austenitic Fe-Mn-Cr stainless steel for fusion-reactor applications

The oxidation in air of an austenitic Fe-Mn-Cr steel containing 17.8 Mn, 9.5 Cr, 1.0 Ni, 0.27 C, and 0.03 N was studied over the range 700–1000°C. Oxidation of surface-abraded samples at low temperatures, 700–750°C, resulted in only Mn ₂O₃ containing dissolved chromium, except at corners, where large nodules containing spinel and manganowustite formed. The Mn₂O₃ layer grew into the substrate forming a globular-type film. This growth mode was the result of slow interdiffusion in the alloy after the cold-worked surface layer had been recrystallized and/or consumed, as evidenced by the formation of a ferrite layer subjacent to the scale and by the instability of the planar interface. No internal oxidation was observed beneath the Mn₂O₃ film at either 700 or 750°C. Samples oxidized in thehigh-temperature region, 800–1000°C, exhibited vastly different behavior, forming thick stratified scales at long times (24 hr), the scales consisting of a very thin outer layer of Mn₂O₃ (with appreciable iron in solution), Fe-Mn spinel beneath the outer layer, and a thick inner layer of manganowustite and a chromium-containing spinel. No chromium was found in the outer two layers. A thin layer of nearly pure Fe₂O₃ formed between Mn₂O₃ and the outer spinel. Quasiparabolic kinetics were observed. The high-temperature rates were about 10³ to 10⁴ times greater than at low temperatures at the transition temperature. The rapid rates at high temperatures were attributed to manganowustite growth. However, oxidation of an electropolished sample at 750°C, from which the superficial cold-worked layer had been removed, formed scales similar to those observed at high temperatures at comparable rates. A difference by a factor of over 10⁴ existed between the oxidation rate of the electropolished sample and the surface-abraded sample at 750°C. The much slower oxidation rate of the latter is attributed to greatly enchanced manganese diffusion through the high dislocation-density, cold-worked layer. Short-time tests at 800°C revealed an incubation period during which a thin protective layer of Mn²O₃ formed. The incubation period corresponded to the recrystallization time of the cold-worked layer. Subsequently, nodular growth occurred which was associated with internal oxidation. The nodules, consisting of spinel and manganowustite, eventually linked up to form a thick, stratified scale. Comparison of the scale structures with calculated phase diagrams of composition versus oxygen activity (at constant temperature), showed that the protective films formed at low temperatures were due to kinetics factors, involving enhanced manganese diffusion through the cold-worked layer, rather than to thermodynamics. A model for the breakdown of protective films is proposed which involves internal oxidation.     

Effect of Y2O3 dispersoids in 80Ni-20Cr alloy on the early stages of oxidation at low-oxygen potential

Specimens of a 80Ni-20Cr type alloy, with and without Y₂O₃ dispersoid particles, were oxidized at 1000°C in H₂/H₂O mixtures where the partial pressure of oxygen (P _{O 2}) was varied between 10₃ and 10₂₄ atm. Oxide particles nucleated homogeneously on both alloys, and preferential nucleation on dispersoid particles at the surface was not observed. Continuous Cr₂O₃ films formed slightly faster at aP _{O 2} of 10^–21 atm on the alloy containing the dispersoid, but the difference was negligible at higher pressures. Oxidation atP _{O 2}=10^-19 and 10^–21 atm involved both the formation of Cr₂O₃ and the evaporation of chromium. Thin films of -Al₂O₃ were observed on both alloys after oxidation atP _{O 2}.     

Sulfidation Behavior of Inconel 738 Superalloy at 500–900°C

The high-temperature sulfidation behavior of the cast nickel-base superalloy Inconel 738 (IN-738) was studied over the temperature range 500–900°C in pure sulfur vapor over the range 10²–10⁴ Pa. The sulfidation kinetics followed the parabolic rate law in all cases. The sulfidation rates increased with increasing temperature and sulfur pressure. The scales formed were bilayered and temperature-dependent. At T700°C, the outer scale consisted of mostly NiS (with dissolved Co) and minor (CoS₂ and NiCo₂S₄, while the inner layer was a heterophasic mixture of NiS, NiCo₂S₄, and minor amounts of Al₂S₃ and chromium sulfide (Cr₂S₃/Cr₃S₄). At T750°C, the outer scale consisted of mostly Ni₃S₂ (with dissolved Co) and minor amounts of Co₃S₄ and Cr₂S₃/Cr₃S₄, while the inner layer was a complex, heterophasic mixture of Ni₃S₂, Cr₂S₃/Cr₃S₄, CoCr₂S₄, and minor Al₂S₃. Platinum markers were found to be located at the interface between the inner and outer scales, suggesting that the outer scale grew by the outward transport of cations and the inner scale grew by the inward transport of sulfur. The formation of Al₂S₃ and Cr₂S₃/Cr₃S₄ partly blocked the transport of cations through the inner scale and consequently reduced the sulfidation rates as compared to pure nickel.     

The effect of particle size of alumina dispersions on the oxidation resistance of Ni-Cr alloys

The oxidation behavior of Ni-Cr alloys with various chromium concentrations and particle sizes of a dispersion of 10 vol.% Al₂O₃ was observed in 1 atm of oxygen at 1000°C. This study was intended to determine the critical chromium concentration to form a protective Cr₂O₃ oxide layer for different Al₂O₃ particle sizes. The oxidation rate of Ni-Cr alloys containing 10 vol.% Al₂O₃ followed a parabolic rate law and a Cr₂O₃ protective layer continuously formed when the oxidation rate decreased rapidly. Times to form a continuous and protective Cr₂O₃ layer during the initial oxidation shortened as the size of the dispersion decreased. The critical chromium concentration to form a protective Cr₂O₃ layer in the oxide scale was 69 wt.% and was related strongly to the particle size of the Al₂O₃ dispersion.     

The corrosion behavior of Fe-Al alloys in H2/H2S/H2O atmospheres at 700–900°C

The corrosion behavior of five Fe-Al binary alloys containing up to 40 at. % Al was studied over the temperature range of 700–900°C in a H₂/H₂S/H₂O mixture with varying sulfur partial pressures of 10^–7–10^–5 atm. and oxygen partial pressures of 10^–24–10^–2° atm. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants decreased with increasing Al content. The scales formed on Fe-5 and –10 at.% Al were duplex, consisting of an outer layer of iron sulfide (FeS or Fe_1–xS) and an inner complex scale of FeAl₂S₄ and FeS. Alloys having intermediate Al contents (Fe-18 and –28 at.% Al) formed scales that consisted of mostly iron sulfide and Al₂O₃ as well as minor a amount of FeAl₂S₄. The amount of Al₂O₃ increased with increasing Al content. The Fe 40 at.% Al formed only Al₂O₃ at 700°C, while most Al₂O₃ and some FeS were detected at T800°C. The formation of Al₂O₃ was responsible for the reduction of the corrosion rates.     

Effects of sulfur pressure on the sulfidation behavior of 310 stainless steel

High-temperature sulfidation behavior of 310 stainless steel was studied over the temperature range of 700–900°C above a pure sulfur pool with the sulfurvapor range of 10^–4–10^–1 atm. The corrosion kinetics followed the parabolic rate law in all cases. The corrosion rates increased with increasing temperature and sulfur pressure. The scales formed on 310 stainless steel were complex and multilayered. The outer scale consisted of iron sulfide (with dissolved Cr), (Fe, Ni)₉S₈ and chromium sulfides (Cr₂S₃ and Cr₃S₄ with dissolved Fe), while the inner layer was a heterophasic mixture of Cr₂S₃, Cr₃S₄, NiCr₂S₄, and Fe₁–_xS. Platinum markers were found to be located at the interface between the inner and outer scales, suggesting that the outer scale grew by the outward transport of cations (Fe, Ni, and Cr), and the inner scale grew by the inward transport of sulfur. The formation of Cr₂S₃, Cr₃S₄, and NiCr₂S₄ partly blocked the transport of iron through the inner scale, resulting in a reduction of the corrosion rates as compared with the results in the literature.     

The corrosion of Fe-Mo alloys in H2/H2O/H2S atmospheres

The corrosion of Fe-Mo alloys containing up to 40 wt.% Mo was studied over the temperature range 600–980C in a H₂/H₂O/H₂S mixture having a sulfur pressure of 10^–5 atm. and an oxygen pressure of 10^–20 atm. at 850C. All alloys were two-phase, consisting of an Fe-rich solid solution and an intermetallic compound, Fe₃Mo₂. The scales formed on Fe-Mo alloys were bilayered, consisting of an outer layer of iron sulfide (FeS) and of a complex inner layer whose composition and microstructure were a function of the reaction temperature and of the Mo content of the alloys. No oxides formed under any conditions. The corrosion kinetics followed the parabolic rate law at all temperatures. The addition of Mo caused only a slight decrease of the corrosion rate. Platinum markers were always located at the interface between the inner and outer scales, indicating that outer scale growth was primarily due to outward diffusion of iron, while the inner scale growth had a contribution from inward diffusion of sulfur.     

Sulfidation behavior of Fe-25Cr-20Ni-1.5Al2O3 in simulated coal combustion/gasification environments

The effect of minor addition of -Al₂O₃ dispersoids on the sulfidation behavior of Fe-25Cr-20Ni was investigated over a range of pO₂, 1.13×10^–20 to 1.18×10 ****^–22 atm. at constant pS₂=1.22×10^–8 atm. Fe-25Cr-20Ni and Fe-25Cr-20Ni 1.5 Al₂O₃ with and without preformed oxide scales were exposed to bioxidant gas mixtures H₂/H₂O/H₂S/Ar at 700° C. Both isothermal and cyclic exposures were included. Scales were characterized by a combination of several surface analytical tools. A remarkable improvement in sulfidation resistance is observed in Fe-25Cr-20Ni-1.5Al₂O₃ under the conditions investigated here. This is attributed to the ability of the alloy to form and maintain a predominantly Cr₂O₃ scale with reduced Fe-diffusion and content. Possible scientific reasons for such improvement are discussed. The base alloy, Fe-25Cr-20Ni, fails to develop and retain such a Cr₂O₃ scale and undergoes sulfidation within a few minutes of exposure. The scale breakdown process by sulfidation is explained qualitatively. Experimental evidence suggests that sulfur in the environment enhances Fe-diffusion and content in the scale.     

Sulfidation properties of Cr23C6 at 1073 K in H2S-H2 atmospheres of 103.5−10−6 Pa sulfur pressure

The sulfidation behavior of chromium carbide, Cr₂₃C₆, was investigated in H₂S-H₂ gas mixtures over a sulfur partial pressure range of 10^3.5–10^–6 Pa at 1073 K using thermogravimetry, optical and scanning electron microscopy, X-ray diffraction analysis, and electron-probe microanalysis. The kinetics were rapid for short time periods and followed a linear rate law at low sulfur pressures, whereas sulfidation tends to obey a parabolic rate law at high pressures. Sulfidation rates decreased with increasing carbon content in the carbide. Surface morphologies could be divided into three groups: (I) at high sulfur pressures, petal-like. crystals (Cr₂S₃); (II) at intermediate pressures, a twinlike structure (Cr₃S₄); (III) and at low pressures, a flat surface with numerous hexagonal pits (Cr_1–xS). The scale consisted of two distinct layers: an external scale with a single or multilayer structure and an inner scale with a mixture of Cr_1–xS, Cr₃C₂, and Cr₇C₃. These higher carbides, Cr₃C₂ and Cr₇C₃, may be formed by the sulfidation-carburization of Cr₂₃C₆. Pt-marker experiments indicated that the external scale grew by chromium diffusion and that sulfur migration played an important role in the growth of the inner scale.     

High-Temperature Oxidation Behavior of Ti2AlC in Air

The isothermal oxidation behavior of bulk Ti₂AlC in air has been investigated in temperature range 1000–1300°C for exposure time up to 20 hr by TGA, XRD, and SEM/EDS. The results demonstrated that Ti₂AlC had excellent oxidation resistance. The oxidation of Ti₂AlC obeyed a cubic law with cubic rate constants, k_c, increasing from 2.38×10^-12 to 2.13×10^-10 kg³/m⁶/sec as the temperature increased from 1000 to 1300°C. As revealed by X-ray diffraction (XRD) and SEM/EDS results, scales consisting of a continuous inner -Al₂O₃ layer and a discontinuous outer TiO₂ (rutile) layer formed on the Ti₂AlC substrate. A possible mechanism for the selective oxidation of Al to form protective alumina is proposed in comparison with the oxidation of Ti–Al alloys. In addition, the scales had good adhesion to the Ti₂AlC substrate during thermal cycling.     

Oxidation Mechanism of Ni—20Cr Foils and Its Relation to the Oxide-Scale Microstructure

The oxidation behavior of Ni—20Cr foils of 100- and 200-m thickness wasstudied in air between 500 and 900°C. Simultaneously, the morphology,microstructure, and composition of the oxide layers were determined byscanning and transmission electron microscopies. Depending on thetemperature, the oxide layer differed significantly. The scale formedat all temperatures was complex, with an outer NiO layer having columnargrains, and an inner layer of equiaxedNiCr₂O₄+NiO+Cr₂O₃ grains. At low temperatures (500 and 600°C),the chromium content was insufficient to form a continuousCr₂O₃ layer, while such a continuous layer formed at theinner interface at oxidation temperatures of 700 to 900°C. At 600°C,internal oxidation of chromium occurred in the substrate. The oxidationmechanism is described taking into account these morphologies and theoxidation kinetics. The observation of no significant differences betweenthe oxidation behavior of thin strips and thick materials is related to thelimited exposure times of the study.     

High-temperature corrosion of dilute chromium-lanthanum alloys

The kinetics of oxidation in air of chromium-lanthanum alloys have been investigated in the temperature range 1100–1400°C. The positive effect of lanthanum on the heat resistance of chromium was established and is explained as a result of the formation of a barrier oxide film consisting of Cr₂O₃ and LaCrO₃. The dispersed particles of lanthanum chromite distributed on grain boundaries form diffusion barriers that change the oxidation law from parabolic to logarithmic. An empirical equation which quantitatively describes masstransport processes with decreasing effective diffusion area and simultaneous sublimation of scales is proposed.     

Mechanism of Chromium Oxidation in SO2 at 3 × 104 Pa and 105 Pa

The kinetics, phase composition, and morphology of scales growing on chromium in SO₂ atmospheres were studied over the temperature range 1073–1273 K and SO₂pressures of 3×10⁴ Pa and 10⁵ Pa. It was found that the scales consist mainly of Cr₂O₃, with only small amounts of sulfur (probably CrS) detected next to the metallic substrate. Oxidation proceeds according to the linear rate law at 10⁵ Pa SO₂ whereas at 1173 and 1273 K at 3×10⁴ Pa SO₂ the parabolic rate law is followed. The transport phenomena were studied by means of radiotracer techniques as well as marker techniques. The oxide–sulfide scales grew mainly by outward diffusion of metal; however, inward transport of S₂ or SO₂ molecules was also observed. The mechanisms of sulfide and oxide formation are discussed on the basis of the experimental results.     

The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal

The oxidation behavior at 900°C of pure Cr and Cr implanted with 2×10¹⁶ Y ions/cm² was studied. The kinetics of oxidation were measured thermogravimetrically and manometrically. The mechanisms of oxide growth were studied using¹⁸O-tracer oxidation experiments, and the composition and microstructure of the oxide scales were characterized by TEM and STEM. Segregation of Y cations at Cr₂O₃ grain boundaries was found to be the critical factor governing changes in the oxidation behavior of Cr upon the addition of Y. In the absence of Y, pure Cr oxidized by the outward diffusion of cations via grain boundaries in the Cr₂O₃ scale. When Y was present at high concentration in the scale, as when Cr implanted with 2×10¹⁰ Y ions/cm² was oxidized, anion diffusion predominated. It is concluded that strain-induced segregation of Y at grain boundaries in the oxide reduced the cation flux along the grain boundaries. The rate of oxidation was reduced because the grain-boundary diffusivity of cations became lower than the grain-boundary diffusivity of the anions, which then controlled the rate of oxidation. Changes in the relative rates of Cr³⁺ and O^2– transport, as well as a solute-drag effect exerted by Y on the oxide grain boundaries, resulted in changes in the microstructure of the oxide.     

Kinetics and mechanisms of the oxidation of cobalt at 600–800°C

Two-phase layered scales comprising CoO and Co ₃O₄ formed on cobalt during oxidation at 600°, 700°, and 800°C and at oxygen partial pressures in the range 0.001–1 atm. The kinetics, which were obtained by thermogravimetric analysis, obeyed a parabolic rate law after an initial, non-parabolic stage of oxidation. The monoxide consisted of relatively large grains (10 ) and the spinel comprised small grains (3 ) for all conditions of oxidation. Grain boundary diffusion of cations played a significant role in the growth of the spinel layer. Thermogravimetric data and the steady-state ratio of the oxide layer thicknesses were employed to calculate the rates of thickening of the individual oxide layers and the rate of oxidation of CoO to Co₃O₄.     

Effect of theθ-α-Al2O3 transformation on the oxidation behavior ofβ-NiAl + Zr

Isothermal oxidation of NiAl + Zr has been performed over the temperature range of 800–1200°C and studied by TGA, XRD, and SEM. A discontinuous decrease in growth rate of two orders of magnitude was observed at 1000° C due to the formation of -Al₂O₃ from -Al₂O₃. This transformation also resulted in a dramatic change in the surface morphology of the scales, as a whisker topography was changed into a weblike network of oxide ridges and radial transformation cracks. It is believed that the ridges are evidence for a shortcircuit outward aluminum diffusion growth mechanism that has been documented in a number of¹⁸O tracer studies.