Internal Oxidation of Fe–Mn–Cr Steels,Simulations and Experiments

A multi-element and multi-phase internal oxidation model that couples thermodynamics with kinetics is developed to predict the internal oxidation behaviour of Fe–Mn–Cr steels as a function of annealing time and oxygen partial pressure. To validate the simulation results, selected Fe–Mn–Cr steels were annealed at 950 °C for 1–16 h in a gas mixture of Ar with 5 vol% H₂ and dew points of ? 30, ? 10 and 10 °C. The measured kinetics of internal oxidation as well as the concentration depth profiles of internal oxides in the annealed Fe–Mn–Cr steels are in agreement with the predictions. Internal MnO and MnCr₂O₄ are formed during annealing, and both two oxides have a relatively low solubility product. Local thermodynamic equilibrium is established in the internal oxidation zone of Fe–Mn–Cr steels during annealing and the internal oxidation kinetics are solely controlled by diffusion of oxygen. The internal oxidation of Fe–Mn–Cr steels follows the parabolic rate law. The parabolic rate constant increases with annealing dew point, but decreases with the concentration of the alloying elements.     

The internal oxidation of two-phase binary alloys beneath an external scale of the less-stable oxide

The internal oxidation of two phase binary A-B alloys by a single oxidant at high temperatures, under partial pressures sufficient to also form external scales of the less-stable oxide, is examined by means of quantitative models and compared with the corresponding behavior of single-phase alloys. It is shown that, depending on various factors, particularly on the solubility and diffusivity of the most-reactive component B in the most-noble component A, this process may or may not involve a diffusion process of the alloy components, leading to different scale morphologies. It is also concluded that even when the solubility and diffusivity of B in A are sufficiently high, so that the internal oxidation of the common type occurs, the restriction to the diffusion of B in the alloy due to its limited solubility affects the kinetics of internal oxidation, producing an increase of the rate of internal oxidation and of the critical concentration of B in the alloy required for the transition to the external oxidation of B with respect to single-phase alloys under the same values of all the relevant parameters. The lower the solubility of B in A, the larger these effects.     

Factors affecting the oxidation behaviour of thin Fe‐Cr‐Al foils. Part II: The effect of alloying elements: Overdoping

The oxidation behaviour of iron‐chromium‐aluminium alloys containing 7 mass‐% aluminium, additions of silicon and reactive elements (Hf, Y, Ti, Ce, La, Zr) was investigated at temperatures ranging between 900 and 1300°C. It was found that a significant increase in the oxidation rate and in the depth of internal oxidation (so‐called “overdoping”) occurs above a critical concentration of reactive elements. The critical upper limit of each reactive elements depends on the aluminium concentration, on the kind of the respective reactive element and on the type and amount of other reactive elements. Alloys containing yttrium are only subject to internal oxidation at yttrium concentrations of 0.08 mass‐% and more. The susceptibility to “overdoping” is significantly increased by additions of zirconium and titanium to yttrium‐containing alloys. Additions of hafnium, on the other hand, decrease the oxidation rate and the susceptibility to overdoping.     

Numerical Analysis of Internal Oxidation and Nitridation by the Cellular Automata Approach

In this study, the phenomena of internal oxidation and nitridation are modeled numerically by means of the cellular automata approach. As an example, TiN formation in Ni-base alloys was simulated by treating nitrogen diffusion and precipitation separately and simultaneously. It was shown that the concentration profiles of nitrogen diffusion are consistent with the analytical solution. The progress of internal nitridation follows a parabolic rate law in agreement with Wagner’s theory of internal oxidation and experimental results. Furthermore, the cellular automata approach is capable to predict the transition from internal precipitation to superficial scale formation and to implement the process of nucleation and growth of nitride and oxide precipitates.     

INTERNAL OXIDATION BEHAVIOR OF Pd-40Ag-1M(M=Zr,Y)ALLOYS

The internal oxidation behavior of Pd-40Ag-1M(M=Zr,Y)alloy wires has been studied inair at 800—1200℃.The relationship between the internal oxidation depth ξ and the reactiontime t can be expressed as ξ= Kt~n,where n=0.5—0.75.The higher the temperature,thelarger the value of n is.The active elements Zr and Y show different internal oxidationcharacters.For the alloys eontaining Zr,the oxidation rate along the grain boundaries isabout twice as high as that in grains,and“lateral oxidation”exists along the grainboundaries.For the alloys containing Y,the oxidation rates in grains and along the grainboundaries are roughly the same,and there is no“lateral oxidation”along the grain bounda-ries.The activation energies of both alloys are in the range of 120—150kJ/mol.Some prop-erties for oxidized alloys were studied.The mechanisms of the internal oxidation were dis-cussed.     

The Internal Oxidation of Ternary Alloys. III: The Coupled Internal Oxidation of the Two Most-Reactive Components under High Oxidant Pressures

The kinetics of the simultaneous internal oxidation of the two most-reactive components B and C in ternary A–B–C alloys, where A is the most-noble and C the most-reactive component, in the presence of an external layer of the A oxide, AO, (high oxidant pressures) are examined assuming the existence of either a single or a double front of internal oxidation. For a single front a unique solution is obtained for the parabolic rate constant of internal oxidation under assigned values of all the parameters involved. When the front is double, a finite range of solutions is allowed with an upper limit equal to the single-front solution and a lower limit equal to the rate constant for the growth of external AO scales. In the case of a single front of internal oxidation, an increase of the rate constant for the growth of the external scales produces an increase of the rate constant for the internal oxidation but a decrease of the degrees of enrichment of the components being oxidized internally within the region of internal oxidation. The behavior in the case of a double front is more complex because it depends also on the actual value of the ratio between the rate constants of internal oxidation for the two fronts.     

Cu-Al合金内氧化的热力学分析——Ⅱ热力学函数的应用

这是(Cu-Al合金内氧化的热力学分析》一文的第Ⅱ部分。对Cu-Al合金内氧化的热力学条件进行了分析，绘制了内氧化的热力学条件区位图。结果表明：区位图中择优氧化区位很大，范围由上、下限氧分压确定，其中：lgPo2max=(-17611／T) 12．91，lgPo2min=(-55830／T)-(4／3)lg[％Al] 19．95，但实际的内氧化区位是靠近上限Po2的一个很小区域；溶度积Ksp和残余Al浓度都是极小量，内氧化可进行得很彻底；内氧化控制中温度和氧分压的调节必须同步：理想的内氧化工艺条件应是：采用1223K左右的高温，介质中的氧分压力求接近或等于上限Po2;为了避免氧化，降温过程宜采用通H2急冷的方法。     

Oxidation of two-phase Co-54.86 wt.% Cu alloy at 700–1000°C

The oxidation in 1 atm of pure oxygen of a binary two-phase Co-Cu alloy has been studied as a simple example of the oxidation behavior of a multiphase alloy. The two-phase alloy oxidizes according to a parabolic rate law to a good approximation throughout the entire exposure period over the temperature range 700–1000°C with an oxidation rate constant greater than that for pure cobalt in the whole temperature range, and greater than that for pure copper at 900–1000°C, but lower below 900°C. The scale presents essentially the same type of layered structure at all the temperatures investigated, with an outer region composed of copper oxides, while cobalt is preferentially accumulated in the inner region of the scale, mainly in the form of CoO. A subscale formed by internal oxidation of the particles of the Co-rich phase is also present. The observed increase of the oxidation rate of the alloy in comparison with pure cobalt is attributed mainly to the presence of a high concentration of copper dissolved in CoO in the form of monovalent ions, which produces a significant modification of the concentration of defects of cobalt oxide with a consequent increase of the oxidation rate constant of the alloy if a suitable model for the defect structure of pure CoO is considered, which takes into account also the presence of a small concentration of interstitial metal ions.     

Cu-Al合金内氧化的热力学分析——Ⅰ热力学函数

对Cu-Al合金内氧化的热力学条件进行了分析，绘制了内氧化的热力学条件区位图。结果表明：区位图中择优氧化区位很大，范围由上、下限氧分压确定，其中：lgPO2(max)=(-1761l／T) 12．91,lgPO2(min)=(-55830／T)-(4／3)Ig[％Al] 19．95，但实际的内氧化区位是靠近上限PO2，的1个很小区域；溶度积Ksp和残余Al浓度都是极小量，内氧化可进行得很彻底；内氧化控制中温度和氧分压的调节必须同步；理想的内氧化工艺条件应是：采用1223K左右的高温，介质中的氧分压力求接近或等于上限PO2；为了避免氧化，降温过程宜采用通H2急冷的方法。     

Comparison of the effects of small additions of silicon or aluminum on the oxidation of iron-chromium alloys

A study has been undertaken of the oxidation behavior of Fe-26 wt.% Cr-1 wt.% Al and Fe-26 wt.% Cr-1 wt.% Si at 800° and 1000°C in oxygen, in order to determine the usefulness of the two tertiary elements in facilitating the development of the Cr₂O₃ external scale. The research has also permitted a comparison of the modes of internal oxidation of these elements, with a view to ascertaining the ease of establishment of the tertiary element oxides as healing layers at the scale/alloy interface. It has been shown that aluminum is the more effective addition in this respect, due to formation of a higher population density of internal oxide nuclei in the early stages. However, in the 1% Al alloy, the precipitates penetrate inward, to considerable depths, as continuous platelets, making development of a complete healing layer difficult. In practice, a higher aluminum concentration is necessary for the closely spaced precipitates to coalesce to form the healing layer, but the process then occurs rapidly. The initial internal oxide nuclei in the 1% Si alloy have a much smaller population density and are restricted to a location very close to the surface. Thus, a healing layer can be established, but the large interparticle spacing makes this a very slow process. Even at a higher silicon concentration, it takes a significant period to be completed. The effects are discussed and accounted for, particularly in terms of the relative stabilities of the various oxides.     

Enhanced Oxygen Diffusion Along Internal Oxide–Metal Matrix Interfaces in Ni–Al Alloys During Internal Oxidation

A study of the internal oxidation of dilute Ni–Al alloys in an NiO/Ni Rhines pack was performed at 800, 1000, and 1100°C. Considerable deviations from the classical internal oxidation model have been observed. The rate of internal oxidation depends not only on the concentration of the alloying element but also on its nature, which contributes to determining the size, shape, orientation and distribution of the internal oxide precipitates. For instance, the precipitates in the Ni–Al alloys are continuous rods, arranged in a cone-shaped configuration that extends from the surface to the internal oxide front. The observed depths of internal oxidation for the various concentrations of aluminum are discussed and related to the morphologies of the internal oxide precipitates. The apparent N^(s) _oD_o values determined from internal oxide penetrations increase with increasing solute content in the alloy. It is postulated that diffusivity of oxygen is enhanced along the internal oxide–metal matrix interface compared with that in the metal matrix.     

The Internal Oxidation of Ternary Alloys. IV: The Internal Oxidation of the Most-Reactive Component Beneath External Scales of the Component Having Intermediate Reactivity

The kinetics of internal oxidation of the most-reactive component C of ternary A–B–C alloys in the presence of external scales of the oxide of the component of intermediate reactivity B, BO, are examined using convenient approximations. The precipitation of the most-stable oxide leaves behind a matrix composed of a mixture of the two most-noble components, A and B, whose composition changes with depth due to the consumption of B to form the external scale. For the calculation of the parabolic rate constant use is made of approximate expressions for the concentration of oxygen dissolved in the binary A–B metal matrix within the zone of internal oxidation and for the diffusion coefficient of oxygen as functions of the alloy composition. Numerical calculations of the parabolic rate constant of internal oxidation 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 the same conditions.     

On the mechanism of Ag exudation during internal oxidation

Internal oxidation experiments under different oxidation conditions focusing on the characteristics of noble metal exudation are presented together with finite element method (FEM) simulation calculations of the build-up of internal stresses. In a high-temperature bending test with a fully oxidized Ag–SnO₂–In₂O₃ sample stress states that were comparable with those occurring during internal oxidation were generated, but exudation of Ag was not observed. From further targeted internal oxidation experiments in combination with FEM simulation calculations of internal stress distributions it can be concluded that internal stresses play a minor role in the occurrence of noble metal exudation. It is suggested that exudation occurs due to a gradient in the chemical potential of the noble metal. The potential gradient is a consequence of the concentration gradient of inward diffusing oxygen. The influence of the oxygen-induced driving force on the development of microstructure considering internal and external noble metal layers is discussed.     

Transition from internal to external oxidation for binary alloys in the presence of an outer scale

The critical concentration required for the transition from internal to external oxidation of the most reactive component B of a binary A-B alloy for the case of simultaneous formation of an outer AO scale is calculated by extending Wagner's original analysis, which excluded the presence of an AO oxide. It is shown that the formation of an outer AO scale tends to produce an increase in the critical concentration of B, essentially as a result of a decrease of the enrichment of B in the internal oxidized region. Examples of the calculation of some parameters are presented to examine the effect of the different factors on the properties of internal oxidation and on its transition to the formation of an external scale of the oxide of the less noble component.     

Kinetic equation based on non-steady-state diffusion of oxygen in solid copper

The kinetics of internal oxidation of dilute Cu-Al alloys, containing 0. 447 5%- 2. 214%Al (mole fraction) was investigated over the temperature range of 1 023 - 1 273 K and the depth of internal oxidation was measured by microscopy. Based on non-steady-state diffusion, a rate equation is derived to describe the kinetics of internal oxidation of plate: X=k√t, where X is the oxidation depth, t is the oxidation time. For the internal oxidation of Cu-Al alloys employed in the synthesis of alumina dispersion strengthened copper, the permeability of oxygen in solid copper is obtained from the internal oxidation measurements. Investigation shows that the depth of the internal oxidation is a parabolic function of time, the typical shape of the front of internal oxidation is of planar morphology,and there is no evidence for preferential diffusion along grain boundaries.     

Cu—Al合金内氧化工艺及动力的研究

对 Cu- Al合金的内氧化工艺及其动力学进行了系统研究。结果表明 :本实验条件下以 12 2 3K,0 .5 h内氧化工艺所得材料的性能最佳 ,其显微组织特征是 Cu基体上均匀弥散分布着纳米级 γ- Al2 O3粒子。理想条件的内氧化初期和实际条件下的内氧化动力学曲线服从抛物线规律。温度、时间、Cu- Al合金粉颗粒半径和 Al浓度是实际内氧化控制的 4要素 ,它们间的函数关系近似满足下式 :t=6 .79R2 CBexp(2 32 5 1/T)。实际内氧化时间不宜过长 ,内氧化温度应该 :112 3K相似文献   

Internal oxidation of Ag-in alloys: Stress relief and the influence of imposed strain

The kinetics of internal oxidation of silver-indium alloys containing 3.5, 5.9, and 9.8 at.% In in air at temperatures 773 to 973 K were established by TGA with no load applied to the specimens. Silver nodules free of oxide particles were observed to form at the surface during internal oxidation. The volume of these silver nodules was comparable to the total volume increase caused by internal oxidation. The alloys were also creep tested during oxidation in air at creep rates varying from 10^–7 to 5×10^–5 s^–1 at 773, 873, and 973 K. The parabolic rate constants k_p for the internal oxidation of the solute were determined from the measured widths of the internal oxidation zones. A small increase in k_p was observed with increased strain rate. The large volume change associated with internal oxide formation resulted in a stress gradient between the stress-free surface and the internal oxidation front which is under a high compressive stress. Stress relief occurred by transport of silver to the surface. A Nabarro-Herring creep type mechanism based on lattice diffusion of Ag cannot account for the high rate of silver transport to the surface. Pipe-diffusion controlled creep is proposed as the mechanism of stress accommodation by silver diffusion.     

The scaling behavior of a monophase Cu-3.36 wt.% Co Alloy at 700–1000°C

The oxidation of a dilute copper-cobalt alloy at high temperatures has been studied to examine the effect of the cobalt addition on the different aspects of copper oxidation. The alloy oxidizes parabolically with a rate constant generally smaller than that of pure copper but approaching it at higher temperatures. The scale is essentially composed of copper oxides (CuO is observed only at 700°C) containing a small concentration of dissolved cobalt and particles of CoO in the inner region of the scale while internal oxidation is observed at all temperatures. The oxidation behavior of the alloy is examined with reference to the known factors affecting the corrosion of binary alloys. A theoretical calculation of the parabolic rate constant for pure copper and for the alloy with cobalt is also presented. Possible reasons for the observed deviation from the effect of doping as predicted on the basis of a simple model for the defect structure of Cu₂O are pointed out.     

An Improved Treatment of the Kinetics of Coupled Internal Oxidation by a Single Oxidant of the Two Most-Reactive Components of Ternary Alloys and of the Conditions for the Transition to Their External Oxidation

An improved treatment of the kinetics of coupled internal oxidation of the two most-reactive components of ternary alloys by a single oxidant, involving the presence of two different fronts of internal oxidation, as well as of the critical contents of these two components needed to avoid this oxidation mode, is developed both for the case of the absence and of the presence of external scales of the oxide of the most-noble component. These analyses are compared with the approximate solutions presented earlier based on the assumption of a simultaneous precipitation of the two oxides at the same front of internal oxidation. The most-important parameter to establish the magnitude of deviation of the double-front solution from that calculated under the assumption of a single front is the solubility product of the oxide of intermediate thermodynamic stability. Only when this parameter is relatively large the kinetics for the double-front solution differ significantly from the simpler case of single front. In the presence of external scales another important factor is the magnitude of the respective parabolic rate constant. An increase of this constant tends to reduce the differences between the single and double-front solutions under the same values of all the remaining relevant parameters. The same approach is adopted to calculate the critical contents of the two most reactive components required to avoid this form of internal oxidation. In this case, the assumption of the existence of a single front of internal oxidation represents an even better approximation than for the calculation of the kinetic parameters of internal oxidation.     

Ce对Fe-Cr合金高温氧化行为的影响

Fe-15Cr 和 Fe-30Cr 合金在1000至1200℃空气中氧化时,表面富铁氧化伤的发展导致保护性Cr_2O_3层衰退,氧化速率增大。添加 Ce 可延迟衰退过程的发生,从而大幅度减低氧化速率。随氧化温度和合金成份变化,Cr_2O_3层衰退的开始时间和发展特征随之改变,Ce 对氧化行为的影响因而呈现出规律性的变化。研究发现,合金中 Cr 的内氧化使 Cr_2O_3层形成小舌包卷合金并使其氧化成富铁氧化物。这是Cr_2O_3层衰退的原因之一。含 Ce 合金中 Ce 的优先内氧化则降低自氧化层进入合金的氧浓度,抑制Cr 的内氧化。氧浓度降低还能促进 Si 的内氧化物在氧化层/合金界面集聚。