Kinetics of Internal Oxidation of Mn-Steel Alloys

Internal oxidation of three Mn-steel alloys with 1.7, 3.5 and 7.0 wt% Mn concentration at 950 °C in a gas mixture composed of nitrogen, hydrogen and water vapor with a dew point of +10°C was evaluated. For these alloys, the kinetics of internal oxidation are diffusion-controlled and obey parabolic growth rate law. The diffusion coefficient of oxygen and manganese determined from the observed internal oxidation kinetics are 3.35 × 10^?7 and 4.14 × 10^?12 cm²/s at 950 °C, respectively. The formed internal oxide precipitates are mainly composed of MnO. The solubility product of MnO in an austenitic iron matrix is estimated to be (7.66 ± 0.18) × 10^?9 mol fraction² at 950 °C. The numerical simulation of concentration depth profiles of precipitated oxygen is in agreement with depth profiles determined with image analysis and X-ray microanalysis. Validity of the numerical simulation in case of the phase transformation was also tested. When a 1.7 wt% Mn-steel alloy is oxidized at 850 °C (instead of 950 °C) with a dew point of +12 °C partial phase transformation from austenite to ferrite takes place due to the Mn depletion. The associated precipitated oxygen concentration depth profile can be predicted accurately with numerical simulation.     

The Effect of Si Additions on the High-Temperature Oxidation of a Ternary Ni–10Cr–4Al Alloy in 1 ATM O2 AT 900–1000 °C

The oxidation of four Ni–10Cr–ySi–4Al alloys has been studied in 1 atm O₂ at 900 and 1000 °C to examine the effects of various Si additions on the behavior of the ternary alloy Ni–10Cr–4Al, which during an initial stage formed external NiO scales associated with an internal oxidation of Cr + Al, later replaced by the growth of a chromia layer at the base of the scale plus an internal oxidation of Al. The addition of 2 at.% Si was able to prevent the oxidation of nickel already from the start of the test, but was insufficient to form external alumina scales at 1000 °C, while at 900 °C alumina formed only over a fraction of the alloy surface. At 1000 °C the addition of 4 at.% Si produced external chromia scales plus a region of internal oxidation of Al and Si, a scaling mode which formed over a fraction of the alloy surface in combination with alumina scales also by oxidation at 900 °C. Conversely, the presence of about 6 at.% Si produced external alumina scales over the whole sample surface at 900 °C, but only over about 60 % of the alloy surface at 1000 °C. The changes in the oxidation modes of the ternary Ni–10Cr–4Al alloy produced by Si additions have been interpreted by extending to these quaternary alloys the mechanism of the third-element effect based on the attainment of the critical volume fraction of internal oxides needed for the transition to the external oxidation of the most-reactive-alloy component, already proposed for ternary alloys.     

Internal Oxidation of Ternary Alloys Forming a High Oxygen Conductive Oxide

Five ternary alloys consisting of a noble base metal (Ni, Co, Fe, Cu) and two reactive metals (Zr + Y, Ce + Gd) being able to form a high oxygen ion conductive oxide were internally oxidized under low oxygen partial pressures. All alloys developed either a continuous yttria-stabilized zirconia phase or a continuous gadolinia-doped ceria phase behind the front of internal oxidation. A Ni–Ce–Gd alloy showed extraordinarily high internal oxidation rates of up to 120 µm²/s at 900 °C. High internal oxidation rates in these ternary alloys were not limited to low concentrations of the reactive metals. The type of the internal oxide phase was found to be more important for the internal oxidation kinetics than the noble base metal.     

The Internal Oxidation of Ternary Alloys. VI: The Transition from Internal to External Oxidation of the Most-Reactive Component under Intermediate Oxidant Pressures

The conditions for the transition from internal to external oxidation of the most-reactive component C of ternary A–B–C alloys are examined, assuming the presence of external scales of the oxide of the component of intermediate reactivity B. For this, approximate expressions for the diffusion coefficient of oxygen and for the concentration of oxygen dissolved in the binary A–B alloy matrix within the zone of internal oxidation as functions of the composition of the metal matrix within the zone of internal oxidation are used. Numerical calculations of the critical content of C needed for this transition are carried out for different combinations of values of the various parameters involved. The results obtained for the ternary alloys are compared with the corresponding data calculated for the binary A–C and B–C alloys under oxygen pressures insufficient to oxidize the most-noble alloy component. This allows to predict the possibility of existence of a third-element effect under intermediate oxidant pressures.     

Intergranular oxidation and internal void formation in Ni-40% Cr alloys

Internal void formation and intergranular oxidation behaviour have been studied during the oxidation of two Ni-40Cr alloys in 1 atm oxygen at 1000° to 1200°C. The development of an external Cr₂O₂ scale causes vacancies to be generated in the alloy at the alloy-scale interface as chromium diffuses into the scale, and others to be generated in the alloy due to the different diffusion rates of chromium towards the interface and of nickel back into the bulk alloy. At 1200°C, internal void formation results from condensation of such vacancies at inclusions in the grains and at the grain boundaries. The intergranular oxidation observed at 1000°C, 1100°C and to a lesser extent. 1200°C results from preferential condensation of vacancies to form voids in the alloy grain boundaries. Significant depletion of chromium in the alloy adjacent to the scale facilitates the supply of oxygen from the scale and its penetration into the alloy grain boundaries to form intergranular oxide. Such intergranular oxide develops deep into the alloy following diffusion of this oxygen through a porous network in the oxide, which arises because of the vacancy condensation, and oxidation of chromium at the tip of the intergranular penetration.     

Long-Term Oxidation of Candidate Cast Iron and Stainless Steel Exhaust System Alloys from 650 to 800 °C in Air with Water Vapor

The oxidation behavior of candidate cast irons and cast stainless steels for diesel exhaust systems was studied for 5,000 h at 650–800 °C in air with 10 % H₂O. At 650 °C, Ni-resist D5S exhibited moderately better oxidation resistance than did the SiMo cast iron. However, the D5S suffered from oxide scale spallation at 700 °C, whereas the oxide scales formed on SiMo cast iron remained relatively adherent from 700 to 800 °C. The oxidation of the cast chromia-forming austenitics trended with the level of Cr and Ni additions, with small mass losses consistent with Cr oxy-hydroxide volatilization for the higher 25Cr/20–35Ni HK and HP type alloys, and transition to rapid Fe-base oxide formation and scale spallation in the lower 19Cr/12Ni CF8C plus alloy. In contrast, small positive mass changes consistent with protective alumina scale formation were observed for the cast AFA alloy under all conditions studied. Implications of these findings for exhaust system components are discussed.     

In Steam Short-Time Oxidation Kinetics of FeCrAl Alloys

In order to investigate the oxidation process of FeCrAl alloy developed by NPIC under simulated LOCA conditions, three experimental groups of alloys were exposed to the steam atmosphere and heated to test temperature (550, 1000, and 1200 °C), respectively, and then maintained at the temperature for 4 hours. The oxidation kinetics of alloys were obtained with a high-precision synchronous thermal analyzer, and the oxide film was investigated by XPS, XRD, and SEM technologies. The results showed that the FeCrAl alloy still retains good oxidation resistance under 1200 °C steam atmosphere. The oxidation process of alloy at 1200 °C can be described into six stages.     

Transition Between Different Oxidation Modes of Binary Fe–Si Alloys at 600–800 °C in Pure O2

The oxidation behavior of three Fe–Si alloys containing approximately 5, 9 and 13 at.% Si has been studied at 600–800 °C under 1 atm O₂. Fe–5Si and Fe–9Si followed multi-stage parabolic kinetics, while Fe–13Si showed more complex kinetics at all temperatures. The increase in Si content resulted in a transition from the internal oxidation of Si beneath an external scale of iron oxides to the exclusive external formation of silica. The critical contents required for the transitions between the various possible oxidation modes of the binary Fe–Si alloys were calculated and compared with the experimental results. A thermodynamic mechanism for the formation of Fe-rich oxide nodules observed in the oxidation of Fe–5Si and Fe–9Si has been proposed.     

The mechanism of oxidation of dilute NiAl alloys at 800–1200°C

The oxidation behaviour of dilute NiAl alloys at 800–1200°C in flowing oxygen at 1 atm pressure has been studied using kinetic measurements, optical and scanning electron microscopy and electron probe micro-analysis. The oxidation rates of Ni0.5 to 4%Al alloys are greater than the corresponding values for nickel at 1000 and 1200°C, but less at 800°C. The increased rates at the higher temperatures are largely due to increases in the total cation vacancy concentration in the scale, although internal oxide formation can make a significant contribution to the oxidation rate. The decreased rates at 800°C are almost certainly due to a build-up of Al₂O₃ particles at the oxide/alloy interface. The roles played in the oxidation processes by doping, internal oxidation, blocking effects in the oxide, dissociation of NiO and gaseous transport of oxygen within the scale are considered in detail and related to the oxidation rates of the various alloys.     

The Effect of Water Vapor on the Transition from Internal to External Oxidation of Austenitic Steels at 1,073 K

The effect of water vapor on the transition from internal to external oxidation of austenitic alloys has been conducted at 1,073 K under the equilibrium oxygen partial pressure for the coexistence of Fe and FeO. Critical Cr concentrations in the Fe–Cr–30Ni (at.%) austenitic alloys were determined to be 30 at.% in dry atmosphere and 37 at.% in humid atmosphere. Thus, water vapor significantly affected the transition from internal to external oxidation of austenitic alloys. Two oxides of Cr₂O₃ and FeCr₂O₄ precipitated in the Fe–5Cr–30Ni (at.%) alloy and solid state reaction for the formation of FeCr₂O₄ may be influenced by water vapor. Oxygen permeability, which was estimated by considering the effective stoichiometric ratio, was also enhanced by water vapor.     

The Internal Oxidation of Ternary Alloys. V: The Transition from Internal to External Oxidation of the Most-Reactive Component under Low Oxidant Pressures

This paper examines the conditions for the transition from internal to external oxidation of the most-reactive component C of ternary A–B–C alloys by a single oxidant under gas-phase oxidant activities below the stability of the oxide of the two most-reactive components using Wagners criterion. For this, approximate relations between the solubility and diffusivity of oxygen and the composition of the binary A–B alloy matrix in the zone of internal oxidation, already developed previously, are used. The critical C content needed for the transition in ternary alloys is calculated as a function of the many parameters involved. At variance with the behavior of binary alloys, for ternary alloys this critical C content depends also on the ratio between the concentrations of A and B in the bulk alloy. The results calculated for ternary alloys are compared with those obtained for binary A–C and B–C alloys under the same values of all the relevant parameters. Finally, complete oxidation maps for ternary alloys under low oxidant pressures,including the condition for the stability of external scales of the C oxide, are also presented.     

On the Pre-oxidation Treatments of Four Commercial Ni-Based Superalloys in Air and in Ar–H<Subscript>2</Subscript>O at 950 °C

The short-term oxidation behaviour of RA 602CA, Inconel 693, Manaurite 40XO and Sumitomo 696, which are four alloys recommended for hydrocarbon processing, was studied both in air and in Ar–H₂O to determine the conditions of pre-oxidation treatments. Regardless of the considered material, the oxidation rate at 950 °C was systematically higher in Ar–H₂O than in dry air. Surface examination of the Al-containing alloys indicated that they were not uniformly oxidized all over the surface. All Al-containing alloys (from 1.6 to 3.2% wt) formed an external protective alumina scale and behaved as alumina-forming alloys in dry air at 950 °C. In contrast, these alloys developed a rate-controlling chromia scale and severe internal oxidation in a H₂O-containing atmosphere. Compared with their oxidation behaviour in air + H₂O, the phenomenon was significantly enhanced in the atmosphere that coupled water vapour with a low oxygen pressure. Consequently, the Al-containing alloys should not be pre-oxidized in a water vapour atmosphere prior to long exposure to a corrosive atmosphere. In contrast, the chromia-forming Al-free 696 alloy exhibited identical oxidation behaviour in both atmospheres, demonstrating that the degradation of this alloy was not significantly affected by water vapour.     

Corrosion of Binary Fe–Si Alloys in Reducing Oxidizing and Sulfidizing–Oxidizing Atmospheres at 700 °C

The corrosion behavior of three Fe–Si alloys containing approximately 5, 9 and 13 at.% Si was studied at 700 °C in an H₂–CO₂ gas mixture providing 10^?20 atm O₂ as well as in an H₂–H₂S–CO₂ gas mixture providing the same oxygen pressure coupled to an S₂ pressure of 10^?8 atm. All the alloys followed complex kinetics which were mostly linear for Fe–5Si, but showed one or two parabolic stages for the other two alloys. Simple oxidation produced essentially two-layered scales in which Si was confined to the alloy consumption zone in the form of silicon oxide and iron-silicon double oxide. Corrosion in the oxidizing–sulfidizing gas mixture produced scales composed of a thick external zone of pure FeS followed by an internal region containing complex mixtures of FeS with Si and Fe oxides. Internal oxidation of silicon was only observed for the oxidation of Fe–5Si in both environments. The extent of corrosion decreased in both gas mixtures with an increase in the Si content of the alloys. Finally, the addition of sulfur produced a significant increase of the overall mass gains for each alloy.     

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.     

The transition phenomenon. a hypothesis concerning the behaviour of Zr and its alloy during corrosion in steam

The validity of a proposed transition theory was investigated by exposing a variety of Zr-alloys to 500°C superheated steam. The transition theory is based on oxidation of intermetallic particles in the oxide at specific oxygen partial pressures. The experiment showed that the theory was valid for those alloys possessing intermetallic particles in the oxide. Those alloys with no particles were dominated by hydrogen absorption and an apparent hydride instability at the metal/oxide interface.     

Prediction of Oxide Phases Formed upon Internal Oxidation of Advanced High-Strength Steels

The effect of Cr on the oxidation of Fe–Mn-based steels during isothermal annealing at different dew points was investigated. The Fe–Mn–Cr–(Si) phase diagrams for oxidizing environments were computed to predict the oxide phases. Various Fe–Mn steels with different concentrations of Cr and Si were annealed at 950 °C in a gas mixture of Ar or N₂ with 5 vol% H₂ and dew points ranging from ? 45 to 10 °C. The identified oxide species after annealing match with those predicted based on the phase diagrams. (Mn,Fe)O is the only oxide phase formed during annealing of Fe–Mn binary steel alloys. Adding Cr leads to the formation of (Mn,Cr,Fe)₃O₄ spinel. The dissociation oxygen partial pressure of (Mn,Cr,Fe)₃O₄ in the Fe–Mn–Cr steels is lower than that of (Mn,Fe)O. The Si in the steels results in the formation (Mn,Fe)₂SiO₄, and increasing the Si concentration suppresses the formation of (Mn,Cr,Fe)₃O₄ and (Mn,Fe)O during annealing.     

Effect of Dilute Tellurium and Selenium Additions on the High-Temperature Oxidation Resistance of Copper Alloys

The high-temperature oxidation resistance of Cu–Te–Se alloys and Cu–Se alloys at 300, 400, 500 and 600 °C was studied by measuring weight gain per unit area after fixed oxidation times. The morphologies of the oxide scales formed were observed using a scanning electron microscope, with the distribution of element detected by an energy-dispersive spectrometer, and the phases identified using X-ray diffraction. The focus of this study was to understand the effects of tellurium (Te) and selenium (Se) additions on the high-temperature oxidation resistance of copper alloys. At the dilute levels studied (≤0.5 wt% total), these elements underwent internal oxidation. Meanwhile, new phases formed, which made oxidation films more compact and increased the adherence between the oxide film and the alloy matrix, as well as prevented oxygen diffusing in the copper alloy matrix, so the oxidation resistance of copper alloys was improved.     

Stability of External α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Scales on Alloy 602 CA at 1100–1200 °C

An external ultrathin α-Al₂O₃ scale grown on the Ni-base alloy 602 CA during air oxidation at 800 °C was characterized by means of high-resolution TEM/EDX and electron diffraction. Alloy samples pre-oxidized at 800 °C were subsequently exposed at 1100, 1150 and 1200 °C for up to 100 h. Whereas the external alumina remained stable at 1100 °C, with the increasing exposure temperature, the pre-grown alumina scale tended to break down resulting in an external chromia scale accompanied by internal alumina precipitation. The transition from external to internal Al oxidation was investigated using SEM/EDX/EBSD. The critical Al depletion at the scale-alloy interface during the post-exposure at 1100–1200 °C was modeled using the CALPHAD-based thermodynamic-kinetic approach.     

Oxidation Behavior of Tribaloy T-800 Alloy at 800 and 1,000 °C

The oxidation behavior of Co-based Tribaloy T-800 alloy has been studied isothermally in air at 800 and 1,000 °C, respectively. The results showed that the oxidation mechanism was dependent on the exposure temperature. The oxidation of the alloy followed subparabolic oxidation kinetics at 800 °C. The oxide scale at this temperature exhibited a multi-layered structure including an outer layer of Co oxide, a layer composed of complex oxide and spinel, a nonuniform Mo-rich oxide layer, an intermediate mixed oxides layer and an internal attacked layer with different protrusions into Laves phase. During 1,000 °C exposure, it followed linear kinetics. The oxidation rendered a relatively uniform external Cr-rich oxide layer coupled with a thin layer of spinel on the top surface and voids at local scale/alloy interface and intergranular region together with internal Si oxide at 1,000 °C.     

Investigation on the oxidation behaviour of gamma titanium aluminides coated with thermal barrier coatings

In the present study, the applicability of thermal barrier coatings (TBCs) on γ‐TiAl alloys was investigated. Two alloys with the chemical compositions of Ti‐45Al‐8Nb‐0.2B‐0.15C and Ti‐45Al‐1Cr‐6Nb‐0.4W‐0.2B‐0.5C‐0.2Si were used. Before TBC deposition, the specimens were pre‐oxidised in laboratory air or low partial pressure oxygen atmosphere. Yttria partially stabilised zirconia top coats were then deposited using electron‐beam physical vapour deposition (EB‐PVD). The oxidation behaviour of the γ‐TiAl specimens with TBC was studied by cyclic oxidation testing in air at 850 and 900 °C. Post‐oxidation analysis of the coating systems was performed using scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (EDS). No spallation of the TBC was observed for pre‐oxidised specimens of both alloys when exposed to air at 850 °C for 1100 cycles of 1 h dwell time at high temperature. SEM micrographs of the thermally grown oxide scale revealed outer mixed TiO₂/Al₂O₃ protrusions with a columnar structure. The protrusions contained small particles of zirconia and a low amount of about 0.5 at% zirconium was measured by EDS analysis throughout this outer oxide mixture. The TBCs exhibited excellent adherence on the oxide scale. Intercolumnar gaps and pores in the root area of the TBC were filled with titania and alumina. Below the outer columnar oxide scale, a broad porous zone of predominant titania was observed. The transition region between the oxide scale and substrate consisted of a discontinuous nitride layer intermixed with alumina particles and intermetallic phases rich in niobium formed at the nitride layer/substrate interface. When thermally cycled at 900 °C, the oxide scales on the alloy Ti‐45Al‐8Nb‐0.2B‐0.15C pre‐oxidised in low partial pressure oxygen spalled off after 540 cycles. For the sample with TBC, spallation was observed after 810 cycles. Failure occurred in the thermally grown oxide near the oxide/nitride layer interface. Microstructural examinations revealed again oxide scales with columnar structure beneath the zirconia top coat and good adherence of the TBC on the thermally grown oxides formed at 900 °C.