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.     

Microstructural Investigation of Protective and Non-Protective Oxides on 11% Chromium Steel

FIB, SEM and STEM/EDX were used to investigate X20 stainless-steel samples exposed to dry O₂, or O₂ containing 40% H₂O, with a flow velocity of 0.5 cm/s or 5 cm/s, for 168 hr or 336 hr at 600°C. Thin protective Cr-rich (Cr,Fe)₂O₃ was maintained on the samples exposed to dry O₂, even after 336 hr, and on the sample exposed to O₂/H₂O mixture with the low-flow velocity (0.5 cm/s) for 168 hr. The oxide scale formed in the latter environment contained less Cr, due to Cr loss through CrO₂(OH)₂ evaporation. Breakaway oxidation occurred on the samples exposed in high-gas-flow velocity for shorter time (168 hr) or in low-gas-flow velocity (0.5 cm/s) for longer time (336 hr). The breakaway scales featured a two-layered structure: an outward-growing oxide “island” consisting of almost pure hematite (α-Fe₂O₃), and an inward-growing oxide “crater” consisting of (Cr,Fe)₃O₄. The transition from a thin protective (Cr,Fe)₂O₃ scale to a non-protective thick scale on this martensitic/ferritic steel originated locally and was followed by rapid oxide growth, resulting in a thick scale that covered the whole sample surface.     

对堆芯熔化条件下锆合金包壳腐蚀动力学有关问题的讨论

针对在堆芯熔化条件下建立铝合金包壳腐蚀动力学模型时所涉及的有关问题和已有的模型进行了讨论和评述。     

微量Ge对大气下液态Sn抗氧化性能的影响

采用观察液态Sn表面氧化行为和刮取表面氧化渣的方法,研究了微量元素Ge对液态Sn在大气和250℃条件下表面抗氧化性能的影响,并与纯Sn的氧化行为进行对比;利用X射线光电子能谱仪(XPS)、扫描电子显微镜(SEM)研究了合金表面元素的含量、价态,及合金氧化后的表面形貌.结果表明:当微量元素Ge浓度达到0.01%时(质量分数),大气下液态Sn表面具有很好的抗氧化性能,同时微量元素在液态Sn表面高度富集.XPS分析表明:表面富集的Ge以4价氧化物形式存在.静态液面氧化时,Ge在液态Sn中迅速偏析,并形成一种保护性的致密氧化膜,是提高液态Sn抗氧化性能的原因.     

The high-temperature oxidation of Ni-20%Cr alloys containing various oxide dispersions

The oxidation behavior of Ni-20%Cr alloys containing approximately 3 vol.% Y₂O₃, ThO₂, and A1₂O₃ as dispersed particles has been examined in the temperature range 900 to 1200° C in slowly flowing oxygen at 100 Torr. The results show that the oxidation behavior of the Y₂O₃-, ThO₂-, Al₂O₃-, and Ce0₂-containing alloys is very similar and that some anomalies in the behavior of the ThO₂-containing alloy might be explained by the slower rate of chromium diffusion in this coarse-grained alloy. Two Al₂O₃-containing alloys were studied. One with a relatively coarse dispersoid size behaved in a manner analogous to a dispersion-free Ni-30% Cr alloy at 1100°C. The other alloy contained a dispersion of fine Al₂O₃ particles and behaved exactly like the Y₂O₃-containing alloy at 1000 and 1100°C, but at 1200° C oxidized at a faster rate. It has been shown that the adherent scales on dispersion-containing alloys have a stabilized fine grain size, whereas the nonadherent scales on dispersion-free alloys undergo grain growth.This work has been supported by the Naval Air Systems Command under Contract No. N00019-72-C-0190.     

Effect of grain size on high-temperature oxidation behavior of Cu-80Ni alloy

1　INTRODUCTIONTheoxidationofunalloyedcopperandnickelhasalreadybeenstudiedindetail.Whilethehigh tem peratureoxidationofCu Nialloys ,alsostudiedanumberoftimestodate[13] ,isanexampleofarela tivelysimpleclassofscalingofbinaryalloysbyasin gleoxidant,becausethemetalsformacontinuousse riesofsolidsolutions ,whiletheiroxides ,CuO ,Cu2 OandNiO ,exhibitsmallmutualsolubilitiesandshowsignificantdifferencesinthethermodynamicstabilityandparabolicgrowthrates .Thus ,copper richalloysformexternalscales…     

High-temperature oxidation of SiC in a glow-discharge oxygen plasma

The oxidation kinetics and structure of the oxide scales formed on high-density SiC were studied in molecular oxygen at 740 Torr and in a glow-discharge oxygen plasma at 0.1 Torr at temperatures of 1000, 1100, and 1200°C. The monatomic oxygen formed by the glow discharge markedly increased the reaction rate and the vaporization of some of the oxidation products. The marked differences in kinetics suggest that the rate-controlling step during oxidation in molecular oxygen is the dissociation of adsorbed diatomic oxygen to the monatomic species. Films formed in molecular oxygen were mostly amorphous SiO₂ with small inclusions of SiC and graphite, whereas films formed in dissociated oxygen were primarily amorphous SiO₂ containing SiO, S₂O₃, and the coesite form of SiO₂.     

Numerical modeling of high-temperature corrosion processes

Numerical modeling of the diffusional transport associated with high-temperature corrosion processes is reviewed. These corrosion processes include external scale formation and internal subscale formation during oxidation, coating degradation by oxidation and substrate interdiffusion, carburization, sulfidation and nitridation. The studies that are reviewed cover such complexities as concentration-dependent diffusivities, cross-term effects in ternary alloys, and internal precipitation where several compounds of the same element may form (e.g., carbides of Cr) or several compounds exist simultaneously (e.g., carbides containing varying amounts of Ni, Cr, Fe or Mo). In addition, the studies involve a variety of boundary conditions that vary with time and temperature. Finite-difference (F-D) techniques have been applied almost exclusively to model either the solute or corrodant transport in each of these studies. Hence, the paper first reviews the use of F-D techniques to develop solutions to the diffusion equations with various boundary conditions appropriate to high-temperature corrosion processes. The bulk of the paper then reviews various F-D modeling studies of diffusional transport associated with high-temperature corrosion.     

Influence of Reinforcement Content and Matrix Composition on the Oxidation Resistance of Aluminum-Matrix Composites (A3xx.x/SiCp)

A study was made on the influence of the SiCp proportion and the matrix concentration of four composites (A360/SiC/10p, A360/SiC/20p, A380/SiC/10p, A380/SiC/20p) on their oxidation behavior. Gravimetric tests were used in a kinetics study of the corrosion process at different temperatures (350, 400, 450, and 500°C). The influence of corrosion on mechanical properties was evaluated by hardness measurements. The nature of corrosion products and the influence of the microstructure on the morphology and growth of the oxidation layer were analyzed by SEM and low-angle XRD. The extent of the damage due to oxidation for Al/SiCp composites increases with the SiCp concentration due to the increase of nucleation sites. One of these nucleation sites is in the interface region between the matrix and the particles. Oxidation was influenced more by the percentage of alloy elements in the matrix than by the proportion of SiCp reinforcement. The presence of Cu and Ni in the matrix favors the oxidation process through the formation of different intermetallic compounds.     

Effects of aluminum on the oxidation of 25Cr-35Ni cast steels

The oxidation kinetics and morphological development during reaction of two cast austenitic steels at 1000°C in pure dry oxygen at 20 kPa are reported. Both steels contained approximately 25 wt.% Cr and 35 wt.% Ni and, in addition, one steel contained 3.3 wt. %. Both steels oxidized to form external scales consisting mainly of Cr₂O₃ with a thin outer layer of manganese rich spinel. Scale growth kinetics were parabolic, and somewhat faster rates were observed for the aluminum bearing steel. In both steels, deep internal oxidation occurred at the site of primary (interdendritic) carbides. The kinetics of this process were parabolic, and rate control was attributed to oxygen diffusion along the interface between internal oxide and matrix metal. In the aluminum-free steel, interdendritic carbides were converted to chromium rich oxide, but when aluminum was present, a sheath of aluminum rich oxide formed around the carbides. In this latter case, the rate of interdendritic penetration was somewhat slower. The aluminum bearing steel also formed large numbers of rod-shaped Al₂O₃ precipitates within the austenitic dendrites. Deepening of the Al₂O₃ precipitate zone also proceeded according to parabolic kinetics at a rate consistent with rate control by diffusion of oxygen along the oxide-alloy interfaces.