Influence on the oxidation kinetics of metals by control of the structure of oxide scales

An explanation of the deviation from the parabolic law is the treatment which considers both shortcircuit and lattice diffusion in the oxide scale. In this study we examine how the oxidation kinetics are influenced by changing the structure of the scale of copper oxide in order to confirm the role of short-circuit diffusion in determining the oxidation rate. In addition we explain the oxidation kinetics of copper and nickel by using a model of the scale structure which includes recrystallization and grain growth. Results are as follows: (1) The nucleation and growth behavior of oxide have a direct effect on the structure and in turn the oxidation kinetics due to short-circuit diffusion. (2) A modified treatment is valid in the region where volume diffusion and short-circuit diffusion play an important role in which it is necessary to consider the scale structure such as the grain size distribution and the boundary width. (3) When recrystallization takes place it is necessary to consider the model of a two-layered scale structure which is different in properties and morphology. (4) In this region the rate curves are S-shaped when oxide recrystallization takes place and exhibit a transition from a parabolic to an nth-power relationship (n>2) when grain growth takes place.This research was performed at the University of Tokyo in partial fulfillment of the requirements for the degree of Doctor of Engineering.     

氢化锆在450~600 ℃下氧化动力学的研究

通过恒温氧化实验研究氢化锆在O2中,450～600℃温度范围内的氧化行为,分析温度和时间对氧化膜生长速度的影响规律。结果表明,氢化锆在O2中450～600℃温度范围内,表面形成氧化膜厚度的平方(D2)与时间(t)的关系曲线呈良好的线性关系,氧化反应动力学符合Wagner理论模型中的抛物线生长规律。氧原子在氧化膜中的扩散过程为氧化反应的控速步骤。扩散系数与温度遵循Arrhenius定律,扩散激活能为18724.5J/mol,据此判断氧原子在氧化膜中的扩散机制以晶界扩散占主导。     

Correlation between the oxidation mechanism of titanium under a pure oxygen atmosphere,morphology of the oxide scale,and diffusional phenomena

The oxidation behavior of titanium was studied over the temperature range of 600 to 800°C in a pure oxygen atmosphere. A parabolic kinetics period is made up of a succession of short parts whose weight gain is nearly constant and whose beginning is characterized by an alteration of the oxidation rate. The kinetics curve is closely correlated with the morphology of the oxide scale which contains several layers separated by short cracks. These cracks decrease the diffusional flows of oxygen and titanium and alter the oxidation rate. A parabolic-linear kinetics transition is attributed to the formation of a continuous crack between the oxide scale and the matrix. The oxide scale then forms a porous barrier of constant thickness which induces a linear rate law due to the steady-state oxygen diffusion. Titanium cannot diffuse across the continuous crack. During the linear kinetics period several layers of constant thickness, separated by a continuous crack, spread out.     

Oxidation kinetics of a Pb-64 at.% in single-phase alloy

The solid-state oxidation kinetics of a Pb-64 at. % In (50 wt. %) single-phase alloy were studied from room temperature to 150°C using an AES (Auger Electron Spectroscopy) depth profiling technique. The general oxidation behavior of this alloy is different from that of a Pb-3 at.% In alloy but similar to that of a Pb-30 at.% In alloy. The oxide formed on this alloy is almost pure In oxide (In₂O₃) with the possible existence of some In suboxide near the oxide/alloy interface. At room temperature, oxidation of the alloy follows a direct logarithmic law, and the results can be described by the model proposed previously by Zhang, Chang, and Marcotte. At temperatures higher than 75° C, rapid oxidation occurred initially followed by a slower parabolic oxidation at longer time. These data were described quantitatively by the model which assumes the existence of short-circuit diffusion in addition to lattice diffusion in the oxide as proposed by Smeltzer, Haering, and Kirkaldy. The effects of alloy composition on the oxidation kinetics of (Pb, In) alloy are also examined by comparing the data for Pb-3, 30, and 64 at. % In alloys.     

General diffusion-kinetic model of metallic oxidation

A new mathematical diffusion-kinetic model of metallic oxidation under isothermal conditions is proposed. This model is used to define the universal kinetic equation to calculate the thickness of porous or dense oxide layer formed at a metal surface as function of oxidation time and several kinetic and equilibrium parameters describing longitudinal and lateral oxidant transfer. A block-slot model is adopted as a physical model of oxide layer. The universal kinetic equation describes various oxidation laws of type h(t) such as linear, parabolic and higher-order than parabolic, transition from one oxidation law to another and acceleration of oxidation, including sudden acceleration.     

新型镍基高温合金的高温氧化行为研究

利用X射线衍射(XRD),扫描电镜(SEM)和能谱(EDS)等方法,研究了GH4700镍基高温合金在空气环境下的高温氧化行为。结果表明:合金在800~900℃下的氧化动力学符合抛物线规律,氧化膜的生长受氧在氧化膜的扩散控制;氧化100 h后形成的氧化膜由3层组成,Nb的存在能有效提高合金的抗氧化性能。     

Kinetics and mechanism of the accelerated oxidation of low carbon scrap steels

Especially with accelerated oxidation, the kinetic curves of steel strips in CO₂-CO gas mixtures at 900° C do not adhere to either the parabolic or the linear growth law. Linear kinetics is essentially obeyed in the oxidation of untreated steel, whereas mixed parabolic or linparabolic laws determine the oxidation of steels treated with oxidation promoters. The observed kinetics are best explained with the Zener diffusion model, which assumes that the activation energy for diffusion is spent in deforming the crystal lattice elastically in the vicinity of the saddle point. The model results in a strong dependence of diffusivity on the melting point and elastic moduli of the diffusion medium (oxide scale). A diffusion coefficient that decreases exponentially with melting point and the Tammann differential relation for oxide growth account adequately for the observed kinetics.     

High-temperature oxidation of zirconium-hydride powders

The oxidation kinetics of zirconium-hydride powders were studied in the temperature range of 298–1378 in air at atmospheric pressure. TG, DTA, DSC, x-ray analysis, and scanning electron microscopy were used. The results obtained are in accordance with the proposed pseudo-parabolic model of zirconium-hydride oxidation. This model includes the initial linear mode of oxide growth with oxygen diffusion through a non-solid film of ZrO₂ of variable depth and a stationary diffusion process followed by oxide sintering. It has been established that the activation energy of the limiting stage of oxidation (238.3 kJ/mol) coincides with the activation energy of oxygen self-diffusion in monocline ZrO₂.     

The growth and structure of oxide films on Fe. II. Oxidation of polycrystalline Fe at 240–320°C

The influence of surface pretreatment and metal orientation on the oxidation of coarse-grained polycrystalline Fe has been studied at 240 to 320°C in 5×10^–3 Torr O₂ using electron diffraction, electron microscopy, and Mössbauer spectroscopy to complement kinetic data. Consistent with previous studies on Fe single crystals, differences in oxidation kinetics for surfaces covered with an electropolish film from those with a similar thickness prior oxide formed by dry oxidation at room temperature are interpreted in terms of differing densities of leakage paths in the oxide layers. The more complex kinetics for electropolished polycrystalline Fe are a result of the leakage path density, the degree of oxide separation, and the extent of -Fe₂O₃ formation varying with substrate orientation. Where adherent Fe₃O₄ layers are formed on polycrystalline and single-crystal Fe surfaces, the parabolic rate constants give an activation energy which is consistent with a previous value of 32 kcal · mole^–1, suggesting that at these low temperatures the transport mechanism for magnetite growth is cation diffusion via easy diffusion paths in the oxide.     

Corrosion of 9Cr Steel in CO2 at Intermediate Temperature III: Modelling and Simulation of Void-induced Duplex Oxide Growth

9Cr–1Mo steel forms in CO₂ at 550?°C a duplex oxide layer containing an outer magnetite scale and an inner Fe–Cr rich spinel scale. The inner spinel oxide layer is formed according to a void-induced oxidation mechanism. The kinetics of the total oxide growth is simulated from the proposed oxidation model. It is found that the rate limiting step of the total oxide growth is iron diffusion through high diffusion paths such as oxide grain boundaries in the inner Fe–Cr rich spinel oxide layer. In the proposed oxidation model, a network of nanometric high diffusion paths through the oxide layer allows the very fast supply of CO₂ inside pores formed at the oxide/metal interface. Its existence is demonstrated to be physically realistic and allows explaining several observed physical features evolving in the oxide layer with time.     

Oxidation and embrittlement of Ti-6Al-2Sn-4Zr-2Mo alloy

Ti-6Al-2Sn-4Zr-2Mo titanium alloy is a candidate material for multiwall thermal protection system concepts for advanced space transportation system vehicles. The total oxidation kinetics for this alloy, exposed to laboratory air in the 593–760°C range, were monitored by thermogravimetric analysis. The oxide thickness was measured by microscopy and the substrate contamination was estimated from microhardness measurements. Tensile elongation was determined for selected foil specimens after exposure to simulated space shuttle reentry conditions. The variation of total weight gain with time was found to have two distinct parabolic stages separated by a transient region. This transient was due to a process which involved an increase in the parabolic growth rate constant for the oxide and a simultaneous increase in oxygen solubility at the oxide metal interface. The time dependent increase in oxygen solubility at the interface was from about 7 at. % in stage 1 to about 18 at. % in stage 2. The diffusion coefficient for oxygen in the alloy was determined as a function of temperature using the difference between the total weight gain in stage 1 and the corresponding weight gain due to oxide growth. A model for the total oxidation kinetics, accounting for the two individual components namely oxide growth and solid solution formation, is proposed. The activation energy for the diffusion of oxygen in the alpha-solid solution is shown to be roughly equal to the activation energy for the degradation of tensile elongation for the alloy in the foil gage condition.     

Kinetics of the oxidation of ilmenite

The oxidation of ilmenite (FeTiO₃) in air and dry oxygen was investigated over the temperature interval 600 to 970°C. Dense platelets of ilmenite crystals as well as powder samples of ilmenite were oxidized. The weight data were recorded employing a thermobalance. The oxidation kinetics of ilmenite platelets were parabolic except for the initial stages during which logarithmic kinetics were observed. For powder samples the logarithmic rate law was followed primarily. The logarithmic rate law was attributed to free penetration of oxygen through cracks and short-circuit paths. The activation energies associated with the logarithmic rate law were nearly one-half of those obtained from parabolic oxidation. The growth morphology of the products of oxidation of ilmenite was observed with a scanning electron microscope. The effect of growth morphology on the kinetics is discussed, and a probable reaction mechanism is suggested for the oxidation of ilmenite.     

Correlations Between Growth Kinetics and Microstructure for Scales Formed by High-Temperature Oxidation of Pure Nickel. II. Growth Kinetics

The oxidation kinetics of high-purity nickel were studied between 500 and 1200°C, in pure oxygen at atmospheric pressure, for average oxide-scale thicknesses of 1, 5, 10, and 30 m. In the overall temperature range studied, a decrease in the parabolic rate constant k_p with increasing scale thickness was observed. Depending on temperature and oxide-scale thickness, growth kinetics can be interpreted as a mixture of parabolic- and cubic-growth kinetics. Possible correlations between growth kinetics and microstructures of the oxide scales were investigated. From this set of experimental data, oxidation-kinetics models were tested. In particular, the effect of grain-boundary diffusion on NiO-growth kinetics was discussed. The correlations between growth kinetics and oxide microstructures appear to be more complex than usually reported.     

Oxidation-Rate Excursions During the Oxidation of Copper in Gaseous Environments at Moderate Temperatures

The kinetics of oxidation of copper powders in oxygen and in dry and humid air was investigated using thermogravimetric analysis (TGA). The extent of oxidation grew linearly with time until the weight-based thickness of the oxide film reached 0.13–1.22 nm, depending on the temperature. Between 30 and 90°C there was little difference between the kinetic curves observed in air and in oxygen, respectively. Higher humidity of the air resulted in an increased oxidation rate. Following the initial linear segment, the oxidation kinetics could be best described in terms of a logarithmic rate law between 30 and 45°C and in terms of a power law between 60 and 90°C. The activation energy for the initial linear stage was (44±2) kJ and for the subsequent oxidation (102±12) kJ. Delayed increases in oxidation rate were observed with a ca. 0.1-m powder around 100°C, with a ca. 1-m powder around 320°C, and with a < 10m powder around 360°C. A three-stage model consisting of an initial linear stage, parabolic growth culminating in cracking of the oxide film, and subsequent re-start of the parabolic growth, gave good agreement with the experimental data. Whenever the powder is relatively uniform and the distribution of film-cracking times among the powder grains is narrow, e.g., within 23% of the median cracking time, an increase in the oxidation rate of the entire sample can be observed.     

Nb对TiNiAl合金高温氧化行为的影响

对Ti50Ni44Al6和Ti50Ni41Al6Nb3合金在1073K循环氧化行为的测试表明,Nb的加入显著改善合金的高温抗氧化性能．Ti50Ni44Al6合金在1073K经过100h循环氧化后形成外层以TiO2为主并含有少量Al2NiO4、内层为TiNiO3的氧化层,合金的氧化动力学服从线性规律;Ti50Ni41Al6Nb3合金生成以TiO2为主的氧化膜,在外氧化层下面形成了一层富Nb和Al的复合氧化物,显著阻碍氧以及合金元素的扩散,降低了合金的氧化速率,合金高温氧化动力学遵从抛物线规律．     

Effect of Shot-peening on the Oxidation Behaviour of Boiler Steels

The presence of short diffusion paths is very important for rapid diffusion processes which are involved in forming protective oxide layers against high temperature corrosion, e.g. on boiler steels. Rapid diffusion paths can be produced by applying cold work such as shot-peening to the surface of the boiler steels prior to oxidation. The effect of shot-peening on oxidation behaviour was tested experimentally on 12 wt% Cr martensitic steel and 18 wt% Cr austenitic steel. Isothermal oxidation tests were performed at 700 and 750 °C. The surface treatment proved to be very effective in improving oxidation protection at 700 °C. Shot-peening the surface prior to the oxidation has an influential effect in changing the diffusion mechanisms of the elements involved in oxidation and changes the oxidation kinetics substantially at the applied conditions in this study.     

高温氧化防护涂层寿命预测的基础理论问题

介绍了高温氧化的动力学理论和高温循环氧化膜剥落的统计规律；理论计算了高温氧化动力学常数k p，氧化膜裂纹密度指数m和氧化剥落常数q；讨论了高温循环氧化动力学模型与高温防护涂层寿命预测的关系.      

Isothermal oxidation behavior of Ti3Al-based alloy at 700-1000℃ in air

The isothermal oxidation behavior of a Ti3Al-based alloy (Ti-24Al-14Nb-3V-0.5Mo-0.3Si, molar fraction, %) at 700- 1 000 ℃ in air was investigated. The oxidation kinetics of tested alloy approximately obeys the parabolic law, which shows that the oxidation process is dominated by the diffusion of ions. The oxidation diffusion activity energy is 241.32 kJ/mol. The tested alloy exhibits good oxidation resistance at 700 ℃. However, when the temperature is higher than 900 ℃, the oxidation resistance becomes poor. The XRD results reveal that the oxide product consists of a mixture of TiO2 and Al2O3. Serious crack and spallation of oxide scale occur during cooling procedure after being exposed at 1 000 ℃ in air for 16 h. According to the analysis of SEM/EDS and XRD, it is concluded that the Al2O3 oxide forms at the initially transient oxidation stage and most of it keeps in the outer oxide layer during the subsequent oxidation procedure.     

A MODEL FOR BAINITIC TRANSFORMATION KINETICS WITHPARABOLIC NUCLEATION RATE

1. IntroductionDue to the good toughness and high strength, bainitic steels are widely used in structural engineering such as supporting rollers, rail steels and high-pressure vessels. Manysteels are treated to obtain bainitic structure as more as possible. Relative heat treatmentprocessing parameters are determined convelltionally by try--and-error methods. The development of numerical simulation makes it possible to optimize heat treatment processingwith less cost and time. One of the impor…     

Interfacial Reactions between Cu-Zr filler metal and alumina and kinetics of reaction layer growth

The interfacial reactions and kinetics of the reaction layer growth in Cu-Zr/A1₂O₃ system were investigated and compared with those in Cu-Ti/Al₂O₃ system. Therrnodynamic analysis showed that the interfacial reaction can proceed until the activity of aluminum in the Cu-5 at.% Zr filler metal reaches about 0.27 at 1373 K. Growth of reaction layer, ZrO₂, was controlled by the diffusion of oxygen through ZrO₂ layer. The activation energy for ZrO₂ growth was 126 kJ/mol. Instead of using a complex redox reaction, a simple oxidation model between reactive metal and oxygen was found to adequately describe the reaction layers growth in ceramic/metal systems. The parabolic rate constant could be expressed in terms of oxygen vacancy concentration at the reactive metal/reactive metal oxide interface. The slower growth of TiO, in comparison with ZrO₂, can be rationalized using the parabolic rate constant. The lower diffusion coefficient of oxygen vacancy and a less negative free energy change of TiO formation have a dominant effect over the higher oxygen vacancy concentration at the Ti/TiO interface which resulted in slower TiO growth.