Oxidation rates of niobium and tantalum alloys at low pressures

Niobium and tantalum alloys have excellent properties for use in high-temperature, space-power applications, but must be protected from oxidation that would result from exposure to air in ground-evaluation tests. The oxygenuptake/oxidation rates of three alloys, Nb-1Zr, PWC-11, and ASTAR-811C were measured at oxygen partial pressure of 10^–6 and 10^–7 torr at temperatures up to 1350 K. No visible oxide film was observed, and the oxidation rate was found to be linearly proportional to pressure and exponentially proportional temperature. A thin molybdenum coating on Nb–1Zr was a barrier to lowpressure oxidation at 773 K.     

Active Oxidation of Liquid Silicon: Experimental Investigation of Kinetics

Small scale laboratory experiments on the oxidation of liquid silicon have reproduced important features of the industrial refining of liquid silicon: active oxidation led to the formation of amorphous silica spheres as a reaction product. The boundary condition for active oxidation in terms of maximum oxygen partial pressure in the bulk gas was found to lie between 2·10^?3 and 5·10^?3?atm at T?=?1,500?°C. The active oxidation of liquid silicon had linear kinetics, and the rate was proportional to bulk oxygen partial pressure and the square root of the linear gas flow rate, consistent with viscous flow mass transfer theory. Classical theory for unconstrained flow over a flat plate led to mass transfer rates for SiO_(g) which were 2–3 times slower than observed. However, computational fluid dynamic modeling to take into account the effects of reactor tube walls on flow patterns yielded satisfactory agreement with measured volatilization rates.     

On the influence of sol-gel derived CeO2 coatings on high-temperature oxidation of Co, Ni and Cu

The effects of CeO₂ coatings on high-temperature oxidation of Co, Ni and Cu have been investigated as a function of temperature at oxygen pressures from 1×10⁻⁴ to 1 atm. The oxidation mechanisms for Co and Cu are essentially unaffected by CeO₂ coatings, whereas the oxidation rate of Ni decreases by approximately one order of magnitude. The oxygen pressure dependence does not change markedly with CeO₂ coatings for any of the metals studied. For oxidation of Ni plus CeO₂ coatings, the temperature dependence is less marked at lower temperatures, whereas essentially the same behavior is observed for Co and Cu with and without the coating. Differences in the effects of CeO₂ coatings for the three metal systems have been attributed to the relative influence of grain boundary transport on the overall rates of oxidation.     

The corrosion of chromium and nickel-chromium alloys in oxygen-sulfur-carbon gases at 800°C

The simultaneous oxidation and sulfidation of Cr, Ni-10Cr, Ni-20Cr, and Ni-30Cr was studied at 800°C in three gases falling within the Cr₂O₃ stability field of the Cr-S-O system. The sulfur partial pressure remained constant at 1×10^?6 atm, whereas the oxygen partial pressure varied from 5×10²¹ to 5×10^?20 atm, and the carbon activity varied from 0.108 to 0.416. Reaction kinetics were measured, and the reaction products were characterized by X-ray diffraction, metallography, scanning electron microscopy, and X-ray energy dispersive analysis. Reaction rates decreased with increasing oxygen partial pressure and decreased with increasing chromium content of the alloys. Sulfides always formed along with Cr₂O₃, even though the gases fell within the oxide stability field. No carburization was observed even though carbon activities were sufficiently high to form carbides. The reaction mechanisms are discussed, and the absence of carburization is analyzed on the basis of a three-dimensional stability diagram.     

Influence of hydrostatic pressure on pitting of aluminium in sea water

Abstract

The effect of hydrostatic pressure on the corrosion of aluminium in sea water oj pH 8·2 containing 7ppm dissolved oxygen has been investigated at 20°C. On increasing the pressure from 1 to 300 atm, the corrosion rate increased, an effect attributable to an increase in the rate of the anodic reaction while the cathodic rate remained unchanged. The observed increased susceptibility to pitting corrosion with increasing pressure was found to correlate with the presence of increasing quantities of SO^2?₄ and Cl^? ions in the oxidation layer. The introduction of electron acceptors such as SO^2?₄ and Cl^? into n type compounds such as aluminium oxides increases the density of lattice dejects and promotes breakdown oj the barrier provided by the oxidation layer.     

The influence of an intermediate annealing treatment on the oxidation of copper and nickel

A study has been made of the effects of an intermediate, isothermal annealing treatment in argon on the oxidation kinetics of copper and nickel in 1 atm oxygen at 800 and 1100°C, respectively, using a semiautomatic microbalance. Changes in scale morphology and composition have been investigated using various physical techniques. The outer CuO layer formed on copper during oxidation dissociates very rapidly on annealing to give CU₂O and oxygen since the partial pressure of oxygen in the gas is below the dissociation pressure of CuO but above that of Cu₂O at 800°C. The CuO layer is quickly re-formed on reoxidation in oxygen. There are relatively few other changes in the oxide morphologies of either metal during annealing, although the small grains present in the scale adjacent to the metal after oxidation are able to grow. During reoxidation both metals show a reduction in oxidation rate constant because of the decrease in total cation vacancy concentration in the scale and the reduced cation vacancy gradient across the scale brought about by the reduction in oxygen partial pressure at the oxide-gas interface during annealing. The reoxidation rate constants following annealing approach those recorded prior to annealing as the equilibrium cation vacancy levels in the scales are reestablished in the oxidizing environment. Rosenberg's method for analysis of the kinetics of reoxidation has enabled the equilibrium concentrations and diffusion coefficients of cation vacancies in CU₂O and NiO during oxidation in 1 atm oxygen at the appropriate temperatures to be estimated approximately. These show reasonable agreement with literature values.     

A comparison of the effects of small additions of various second elements on the oxidation of nickel at 1200°C

The oxidation behaviour of Ni-4.2% Mo, Ni-4.0% W, Ni-2.5% Al, Ni-4.2% V and Ni-5.0% Cr (all wt. %) at 1200 °C in flowing oxygen at 1 atm. pressure has been studied using various techniques. In particular, the solubility of the second element in NiO, its distribution across the NiO scale and the effects of these on the oxidation rates and scale morphologies have been examined. The oxidation rates of all the alloys are greater than that of nickel, although for Ni-4.2% Mo, where incorporation of internal oxide into the scale does not occur and molybdenum does not dope the oxide, the small increase in weight gain during oxidation Compared with that for nickel is due to internal oxide formation only. As the internal oxide particles pileup at the alloy/oxide interface, they exert a blocking effect to outward diffusion of Ni²⁺ ions, especially in the later stages of oxidation. Ni-4.0% W behaves similarly, although a few internal oxide particles are incorporated into the scale and a small amount of doping of the oxide ensures that it thickens at a slightly faster rate than the scale on nickel and for Ni-4.2% Mo. The oxidation rates of the other alloys are significantly faster than that of nickel and increase in the order Ni-2.5% Al, Ni-4.2% V, Ni-5.0% Cr. These increased rates are largely caused by increases in the total cation vacancy concentrations in the scales, although internal oxide formation can make a significant contribution to the oxidation kinetics. The influence on the oxidation behaviour of a number of factors, namely doping of the scale, internal oxidation, dissociation of NiO and transport of gaseous oxygen within the scale, blocking effects in the oxide and at the alloy/oxide interface, and grain growth of the oxide, are considered in detail.     

The oxidation and hot corrosion behavior of tungsten-fiber reinforced composites

The oxidation and hot corrosion behavior of a tungsten-fiber, reinforced Ni~ 20Cr alloy has been examined under the following exposure conditions: (a) pure oxygen at 1 atm pressure; (b) sulfidation in H₂–10 %H₂S; (c) presulfidation in H₂–10 %H₂S followed by oxidation in oxygen; and (d) oxidation in 1 atm oxygen after precoating with approximately 1 mg/cm² of Na₂SO₄. Rapid oxidation of the tungsten fibers causes considerable distortion of the matrix and catastrophic degradation of the matrix follows. Inter diffusion between the matrix and the fibers is also important. During sulfidation, only the matrix forms sulfides, the fibers remaining unaffected. Consequently, presulfidation, although having a dramatic effect on the oxidation of the matrix does not have a damaging effect on the fibres. Equally, the presence of sodium sulfate is not critical, although severe oxidation of the exposed tungsten fibers is still observed.     

The Corrosion of Co-15 wt.% Y at 600-800°C in Sulfidizing-Oxidizing Atmospheres

The corrosion of Co-15 wt.% Y has been studiedat 600-800°C inH₂-H₂S-CO₂ mixturesproviding a sulfur pressure of 10^-8 atm at600-800°C and of 10^-7 atm at 800°Cand an oxygen pressure of 10^-24 atm at 600°C and of10^-20 atm at 700-800°C. The corrosionrates in such sulfidizing-oxidizing atmospheres werecompared with those of pure cobalt and yttrium. Theaddition of yttrium to cobalt is only slightly beneficial, sincefor a yttrium content of 15 wt.% the corrosion rate isreduced quite significantly with respect to pure cobaltat 800°C under 10^-7 atm S₂,only to a limited extent at 600°C, and even slightlyincreased at 700°C. Moreover, the alloy corrodesconsiderably more rapidly than pure yttrium at800°C, when the latter behaves protectively. At 600 and 700°C, yttrium exhibitedbreakaway behavior, while the alloy corroded morerapidly than yttrium at short times, but more slowly atlong times. Under all conditions, except at 800°Cunder 10^-8 atm S₂, the alloy formsan external layer of cobalt sulfide overlying anintermediate region of very complex compositioncontaining a mixture of the compounds of the two metalsand an innermost region of internal attack containing compoundsof yttrium with both oxygen and sulfur. Thus, cobalt canstill diffuse through the intermediate region to formthe outer cobalt-sulfide layer at nonnegligible rates. The scaling behavior of the Co-15% Yalloy is discussed by taking into account the limitedsolubility of yttrium in cobalt as well as the presenceof an intermetallic Co-Y compound in thealloy.     

The oxidation behavior of dilute Ni-V alloys at 1200°C

The oxidation behavior of nickel and dilute Ni-V alloys has been studied in flowing oxygen at 1 atm pressure, using various kinetic and electron-optical techniques. The oxidation rate rises progressively as the alloy vanadium content is increased from 0 to 0.8% and then to 1.7%. However, further additions to 4.2% cause only a slight further increase. These increases in oxidation rate are largely controlled by the extent of doping of the NiO, particularly for the two more dilute alloys, although internal oxidation, spinel blocking effects in the oxide, and dissociation of the NiO affect the weight gains to some extent, particularly for the case of the Ni-4.2% V alloy.     

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.     

Prediction of the chromium oxide oxidation rate from the equilibrium constants and the mass transfer coefficients at high temperatures

Previously published experimental data on the oxidation/volatilization of chromium oxide covering a wide range of oxygen pressure (10^–6 to 1 atm) and temperature (900 to 1385°C) were used to predict its oxidation rate from the equilibrium constants and the mass transfer coefficients using the kinetic model originally developed by Bartlett. The experimental data available were found to be either surface-reaction-controlled or volatile-product-controlled which are the limiting cases of the model. The availability of the dimensionless fluid correlations and the force constants for the diffusing species enabled the prediction of the mass transfer rate for the various sample shapes and hydrodynamic conditions. The good agreement between the experimental and predicted oxidation rates covered four orders of magnitude range.Prepared for the U.S. Department of Energy under contract No. W-7405-Eng-82.     

Vacuum oxidation of freshly deposited iron nanofilms

The interaction between freshly deposited iron films and oxygen at different evacuation degrees (from 10^?5 to 760 mmHg) and room temperature is studied with the use of gravimetry (weighing with quartz nanobalance) and atomic force microscopy. According to data of atomic force microscopy, upon deposition of the metal on a glass substrate and during its subsequent oxidation, a metal-oxide composite film composed of metal-oxide nanoparticles with sizes of 20–30 nm where a metal core is covered with an oxide shell is formed. The reaction between freshly deposited iron and oxygen is shown to proceed quickly already at a pressure of 10^?5 mmHg. An increase in the pressure is found to result in an increase in the bulk oxidation degree of the film. The growth kinetics of the film is two-stage. The initial oxidation stage can approximately be described with a linear-logarithmic dependence. The thinner the deposited iron nanolayer, the higher the bulk oxidation degree. The large value of the rate of initial oxidation of freshly deposited layer at a pressure of 10^?5 mmHg, can be related to redox processes at the magnetite-hematite interfaces of multilayer nanoparticles that constitute the deposited nanocomposite layer. Upon passivation of the layer, the inherent nanoporosity makes the metal-oxide nanocomposite an adsorbent that can accumulate and store the adsorbed components of the environment (air).     

On the High-Temperature Oxidation of Cu-Rich Cu-Ni Alloys

Cu-2 wt.%Ni and Cu-5wt.%Ni were oxidized at 800to 1050°C and oxygen pressures from from 5 ×10^-4 to 1 atm. The oxidation, as measured bythermogravimetry, was approximately parabolic. The oxidescales could be divided in two main regions: An outerregion consisting of copper oxides and an inner porousregion, which consists of Cu₂O with dispersedNiO particles. NiO particles exists as internal-oxide particles. The interface between the two layersreflects the original surface, which shows that theouter part grows by outward Cu diffusion via vacancies.The inner part grows by outward diffusion of copper and inward transport of gaseous oxygen by thedissociative-transport mechanism. The amount ofporosity, the relative thickness of the inner layercompared to the total thickness of the scale, and theoxidation rate as a function of Ni content was dependenton the reaction conditions.     

Application of the Rosenburg kinetic method for determination of the parabolic rate constants for metal oxidation

The Rosenburg continuous kinetic method is proposed for the determination of the parabolic rate constants of metal oxidation as a function of temperature and oxidant pressure. Using this method, it is possible to make numerous measurements in a continuous manner on a single metal sample left in situ in the furnace, thus eliminating systematic errors due to differences between samples. Moreover, using this method it is possible to determine directly from a given kinetic curve such important parameters as the coefficients of chemical diffusion and self-diffusion of the more mobile species in the studied compound and the total equilibrium defect concentration. The latter parameter has been inaccessible up to now by the experimental method. The limits of applicability of this method are given in the paper. As an example of this method, the kinetics of cobalt oxidation are investigated in the range of temperature 1000–1250°C and oxygen pressure 10^–3–1 atm; the results compare favorably with those obtained by other authors. The method is, however, applicable to certain other systems, namely, metal oxides and sulfides.     

Oxidation of tantalum in oxygen-nitrogen and oxygen-inert gas mixtures

The oxidation of tantalum in oxygen-nitrogen and oxygen-inert gas mixtures at925°C has been studied. The oxygen pressure was close to 0.5 atm in all experiments, and partial pressures of the second component of from 0 to 180 Torr were employed. Spherical specimens were used to provide quantitatively significant kinetic data. A model has been proposed which suggests that the oxygen pressure at the reaction interface close to the metal surface is lower than the external pressure because of the finite permeability of the porous outer oxide layer, and that the inert gas effectively reduces the permeability. The model gives good quantitative agreement with the experimental results.     

High-Temperature Oxidation of Ni–20 wt.% Cu from 700 to 1100°C

Ni–20 wt.% Cu was oxidized in different oxygen pressures from 1×10^–5 to 1 atm at 700–1100°C. The oxidation consisted of an initial transient period in which a composite scale of NiO and Cu oxides formed, and a subsequent quasi steady-state regime during which parabolic growth of NiO determined the overall oxidation rate. Based on the oxide composition and the oxygen- pressure dependence of the parabolic rate constant, it is concluded that outward transport of Ni via vacancies determines the growth rate of the oxide during the steady-state period, either in the grain boundaries or in the lattice. The influence of Cu dissolved in NiO on the oxidation rate and the oxygen-pressure dependence of the parabolic rate constants is discussed.     

Study of the oxidation kinetics of vanadium carbide

The oxidation of an oxycarbide of vanadium, VO_0.6C_0.7, and of a vanadium carbide, VC_0.98, was studied athermally up to temperatures of 800° C and isothermally between 400 and 580° C at oxygen pressures ranging from 10^–2 to 1 atm. The oxycarbide followed the parabolic rate law below 450° C with V₂O₅ forming as the only reaction product. The activation energy was 49 kcal/mole. VC_0.98 did not form an oxide in this temperature range, but rather dissolved oxygen, the activation energy being 26.6 kcal/mole. No oxygen pressure dependence on the kinetics was found for either sample in this temperature range. Both samples followed the cubic rate law during oxidation in the range of 500–580° C during which V₂O₅ formed. There was a P^1/3 dependence and the activation energy was the same for both materials, 51 kcal/mole. The cubic rate law and the positive pressure dependency (rather than an anticipated negative dependency) were attributed to an electric field associated with oxygen ions chemisorbed on a thin layer of V₂O₅.     

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.     

The Oxidation of Two Fe-Y Alloys Under Low Oxygen Pressures at 600-800°C

The corrosion of pure yttrium and of two Fe-basealloys containing approximately 15 and 30 wt.% Y wasstudied at 600-800°C in H₂-CO₂mixtures providing an equilibrium oxygen pressure of10^-24 atm at 600°C and 10^-20 atm at 700 and800°C. The corrosion of yttrium under these lowoxygen pressures resulted in the growth ofY₂O₃ scales and presented twoapproximately parabolic stages at 800°C, while at 600-700°C it was faster andnonprotective. The corrosion of the two alloys followedapproximately the parabolic rate law, except for Fe-15Yat 600°C which oxidized nearly linearly. At 600 and700°C, when the gas-phase oxygen pressure was in thefield of stability of iron oxide, the alloys formed alsoa thin external Fe₃O₄ layer, whileat 800°C, when the oxygen pressure was below thestability of FeO, a thin outermost layer of pure iron wasobserved to form. Under all conditions a region ofinternal oxidation formed in the alloy, in which theyttrium-rich phases were transformed into a mixture ofiron metal and oxides, which included double Fe-Yoxides as well as Y₂O₃. Themicrostructure of the internal-oxidation region followedclosely that of the original alloys, which moreover didnot undergo any yttrium depletion. These results are examinedby taking into account the low solubility of yttrium iniron and the presence of intermetallic compounds in thealloys.