Effect of Oxygen Content on the Oxidation of Pure Iron

The oxidation of pure iron with various oxygen contents was studied. Pure iron and ferrite containing different amounts of oxygen were oxidized for 1–5 hr in two types of oxidation atmospheres at 850°C. Pure iron (0.0037% oxygen) oxidized more rapidly than ferrite (0.017% oxygen). Oxidation is higher in the moist ambient atmosphere than in dry air. The oxidation rate was not proportional to the amount of oxygen in the samples.     

Comments on the use of the two-stage-oxidation method and surface-analytical techniques in studying growth processes of oxide scales

Application of the two-stage-oxidation methods and surface-analytical techniques, SIMS and SNMS, for determining transport processes occurring in thin oxide scales is discussed briefly. The most fundamental rules relevant to the interpretation of results are formulated, and the practical implications are inferred. The effects related to the morphological and microstructural features are considered.on leave from the Academy of Mining and Metallurgy, Krakow, Poland.     

Ti40合金的超高温氧化行为研究

对Ti40合金进行1000~1500℃的超高温氧化实验。应用SEM、OM、XRD和EDS分析氧化表面以及氧化表面到基体的组织和元素的变化。结果表明,Ti40合金在1000~1500℃氧化过程中,氧化表层分别经历了V2O5的熔化蒸发、TiO_2晶粒的长大,以及表面氧化层由于TiO_2的生长应力而导致的开裂剥落的过程。当氧化层脱落后,原有的氧化次表层推至氧化表面,形成致密的、具有较好保护作用的TiO_2和Cr_2O_3混和氧化层。同时,在氧化层和基体界面依然稳定存在V、Cr元素的富集层。TiO_2、Cr_2O_3混和氧化层和V、Cr元素的富集层使得氧化表层脱落后合金依然具有良好的抗O元素扩散能力。     

Influence of external mechanical loadings (creep,fatigue) on oxygen diffusion during nickel oxidation

This study deals with the influence of various mechanical loadings (fatigue, creep, creep-fatigue) on oxygen diffusion in a particular system, oxidizing nickel. A distinction between the behavior of the oxide layer and underlying nickel was noted during the first step of oxidation at 550°C, in P_{O 2}=1 atm. Mechanical loading causes a decrease of the oxygen mobility through the oxide scale (factor of 10³). The oxide thicknesses on nickel undergoing mechanical loadings are different than for an unloaded sample, due to distinct contributions of the oxygen and nickel fluxes in the growing oxide. In the substrate, the ingress of oxygen becomes easier with a constant tensile load (creep). The intergranular-oxygen diffusion coefficient, D_i, is increased by a factor of 10² with respect to other samples. In creep, oxygen diffusion takes place along grain boundaries of a structure with smaller grains than in unstrained Ni. A short fatigue period during creep-fatigue decreases the sensitivity of nickel to intergranular-oxygen diffusion.     

The use of SIMS to investigate the incorporation of oxygen in CoO scales

SIMS was used to locate O¹⁸ in a thick oxide scale grown on a cobalt specimen oxidized first in O¹⁶ and subsequently in O¹⁸. Analyses were performed in depth profile from the oxide-gas interface and in step scan across a polished cross section. SIMS was found to be well suited to this type of oxygen tracer study. Eighty percent of the O¹⁸ was located in the inner quarter of the scale with a maximum value of 70% 10–15 from the metal-oxide interface. The distribution of the remaining O¹⁸ was essentially uniform in the outer 3/4 of the scale at an average value of 4.6%. There was, however, a layer 150 nm thick highly enriched in O¹⁸ at the oxide-gas interface. The O¹⁸ in the outer 3/4 of the porous scale is probably the result of normal exchange processes. The form of the distribution near the metal-oxide interface cannot be explained at this time.     

An Ultralow Oxygen Partial Pressure-Controlling System and Its Application to Oxidation Studies

An ultralow oxygen partial pressure-controlling system, based on solid-stateelectrochemical principles, has been developed. This system consists of anoxygen sensor and an oxygen pump and is controlled by a PC computer. Theoxygen sensor is used to measure the oxygen partial pressure in an enclosedsystem, while the oxygen pump is used to transport oxygen from the ambientair into the enclosed system or from the enclosed system to the ambientair. The operating conditions of this system have been studied. The resultsshowed that it can be used to establish a stable oxygen partial pressure inthe range of 10–185×105 Pa (1×10–235 atm)in the enclosed system. This system has been used to investigate theselective oxidation of the Cr and the oxide formation on the surface of aNi–Cr alloy under three different low oxygen partial pressures. Theoxide morphology was studied using atomic force microscopy (AFM). The resultsagreed well with those in the literature and also confirm the reliability of this system.     

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.     

Duplex scale formation during high-temperature oxidation of Ni-0.1 wt.% Al alloy

The development of a duplex NiO scale microstructure on a Ni-0.1 wt.% Al alloy at 900°C has been examined, principally using secondary-ion mass spectrometry and analytical transmission electron microscopy. The¹⁸O-tracer distribution following sequential oxidation in¹⁸O₂/¹⁸O₂ showed that the inner NiO layer formed as a result of gaseous-oxygen penetration of the scale. The provision of pathways for oxygen transport as well as the role of Al, Si, and Ce segregation at oxide grain boundaries in influencing the growth rate and spallation behavior of the scale are discussed.     

The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal

The oxidation behavior at 900°C of pure Cr and Cr implanted with 2×10¹⁶ Y ions/cm² was studied. The kinetics of oxidation were measured thermogravimetrically and manometrically. The mechanisms of oxide growth were studied using¹⁸O-tracer oxidation experiments, and the composition and microstructure of the oxide scales were characterized by TEM and STEM. Segregation of Y cations at Cr₂O₃ grain boundaries was found to be the critical factor governing changes in the oxidation behavior of Cr upon the addition of Y. In the absence of Y, pure Cr oxidized by the outward diffusion of cations via grain boundaries in the Cr₂O₃ scale. When Y was present at high concentration in the scale, as when Cr implanted with 2×10¹⁰ Y ions/cm² was oxidized, anion diffusion predominated. It is concluded that strain-induced segregation of Y at grain boundaries in the oxide reduced the cation flux along the grain boundaries. The rate of oxidation was reduced because the grain-boundary diffusivity of cations became lower than the grain-boundary diffusivity of the anions, which then controlled the rate of oxidation. Changes in the relative rates of Cr³⁺ and O^2– transport, as well as a solute-drag effect exerted by Y on the oxide grain boundaries, resulted in changes in the microstructure of the oxide.     

The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal. II. Effects of temperature and dopant concentration

The oxidation behavior of pure Cr and Cr implanted with Y was studied as a function of temperature (900 and 1025°C) and ion-implantation dose (1×10¹⁵ and 2×10¹⁶ Y ions/cm²). The microstructures of the Cr₂O₃ scales were affected by both of the variables studied. Yttrium ions segregated at the grain boundaries in the Cr₂O₃ scales formed on the implanted alloys and the concentration of Y at the grain boundaries decreased with a decrease in the dose of implanted Y. The mechanism of growth of the Cr₂O₃ scales was altered by the presence of the Y ions at the Cr₂O₃ grain boundaries only when a critical concentration of Y at the grain boundaries was exceeded.     

An experimental setup for the study of gas-solid reequilibration phenomena

The effect of Y additions on the oxidation mechanism of NiAl at 1270 K has been investigated. Mass transport in the alumina scale was examined with¹⁸O tracers. Proton activation analysis (¹⁸O(p, )¹⁵N) and SIMS were used to measure the¹⁸O distribution in the scale. On pure NiAl and low-doped (0.07% Y) NiAl mainly outward scale growth was observed. Addition of 0.5% Y induces oxide formation at both interfaces of the scale. Larger quantities of Y added to the alloy (>0.5%) do not dissolve completely in the NiAl, but form Y-rich segregates. Internal oxidation of these intergranular segregates was observed. The relation between the modification of the scale-growth mechanism and the improved adherence of the scale to the alloy due to the addition of Y is discussed.     

Effect of La2O3 Particles on the Oxidation of Electrodeposited Nickel Films

Electrodeposited Ni-La₂O₃composite films with nanometer-sizeLa₂O₃ oxide inclusions werefabricated by the codeposition of nickel withLa₂O₃ particles. The comparativeoxidation behavior in air at 900 and 1000°C of nickel coated with theNi-La₂O₃ composite and films withand without nickel-plating was studied by TGA, AE,SEM/EDX, EPMA, and TEM/EDX. In general, theNi-La₂O₃ composite-coated nickelhad the slowest rate and the best resistance tothermal cycling. AE tests revealed that cracking eventsin NiO scales on Ni-La₂O₃composite-coated nickel was significantly reduced incomparison to that of the scale on nickel-coated nickel during thermalcycling at 900°C. SEM investigation showed that theLa₂O₃-free NiO scale was composedof outer coarse columnar grains and inner equiaxed ones.By contrast, the scale on the Ni-La₂O₃composite-coated nickel consisted of only fine equiaxedNiO grains. The scale on theLa₂O₃-free samples wascharacterized by cracks that originated at thescale-substrate interface and spanned the scale thickness. By contrast,no scale cracks formed at theLa₂O₃-doped NiO scale-substrateinterface, but small voids were created at the triplepoints of the grain boundaries of NiO. In the La₂O₃-doped NiOscale, segregation of La ions to the NiO grainboundaries near the scale-surface was observed by EDXmicroanalyses in the TEM. It is believed that the Laions segregated at the grain boundaries of NiO led to an increase in thecohesion between nickel oxides and in a reduction of thescaling rate and the formation of scale with fineequiaxed crystal structure by blocking the outward and lateral growth of scale. The latter was dueto the predominant outward diffusion of nickel along NiOgrain boundaries being inhibited effectively by thesegregated La ions. The mechanism of the effect of the added La₂O₃particles on the nickel electrodeposits is discussed indetail.     

Oxidation Behavior and Breakdown of an Aluminide Coating on DZ40M Alloy at High Temperatures

DZ40M alloy is a new Co-base superalloy, which is suitable for the blade material of gas turbines. In this paper, isothermal oxidation of an aluminide coating on this alloy was examined at 900–1100°C in air. It was observed that the weight gain at lower temperatures (900 and 1000°C) was greater than that at the higher temperature (1050°C), which was due to the formation of both -Al₂O₃ and -Al₂O₃ at 900 and 1000°C but only -Al₂O₃ at 1050 and 1100°C.     

Transport of sulfur in the scale growing on nickel in sulfur dioxide atmosphere at 873 K

SO₂ labeled with³⁵S radioisotope was used to study the diffusion of sulfur in scales growing on nickel in sulfur-dioxide atmosphere at 873 K. It was observed that in addition to the inward molecular transport of SO₂, outward diffusion of sulfur also occurred. This diffusion occurred mainly through the grain boundaries of the scale [D_G873=3×10^–7cm²/s]. The liberation of sulfur inside the scale was caused by the reaction of Ni₃S₂ with oxygen or with sulfur dioxide.     

Pt/Al2O3催化剂用于NO氧化的活化效应研究

柴油机氧化催化剂(DOC)能将尾气中部分NO氧化成NO_2,一定浓度的NO_2有利于柴油机颗粒捕集器(DPF)的连续再生和提高选择性催化还原催化剂(SCR)对NO_x的转化效率。针对DOC的新鲜态Pt/Al_2O_3 催化剂经过1次程序升温NO催化氧化活性明显提升的现象(活化效应),采用原位红外漫反射实验(in situ DRIFTS)、氢气程序升温还原、X射线光电子能谱(XPS)和高分辨透射电子显微镜(HR-TEM)分析Pt/Al_2O_3催化剂相关过程的物理化学状态。分析结果表明,新鲜态Pt/Al_2O_3催化剂在300℃以下时载体上积累了大量的硝酸盐和亚硝酸盐物种,导致新鲜态催化剂活性不高;进一步的分析表明经一次程序升温后催化剂中与载体结合强的PtO_x物种的分解是引起活化效应的主要原因;经过3次程序升温反应,催化剂中Pt粒子的大小没有发生明显改变。     

The influence of reactive-element coatings on the high-temperature oxidation of pure-Cr and high-Cr-content alloys

The influence of various reactive-element (RE) oxide coatings (Y₂O₃, CeO₂, La₂O₃, CaO, HfO₂, and Sc₂O₃) on the oxidation behavior of pure Cr, Fe–26Cr, Fe–16Cr and Ni–25Cr at 900°C in O₂ at 5×10^–3 torr has been investigated using the¹⁸O/SIMS technique. Polished samples were reactively sputtercoated with 4 nm of the RE oxide and oxidized sequentially first in¹⁶O₂ and then in¹⁸O₂. The effectiveness of each RE on the extent of oxidation-rate reduction varied with the element used. Y₂O₃ and CeO₂ coatings were found to be the most beneficial, whereas Sc₂O₃ proved to be ineffective, for example, for the oxidation of Cr. SIMS sputter profiles showed that the maximum in the RE profile moved away from the substrate-oxide interface during the early stages of oxidation. After a certain time the RE maximum remained fixed in position with respect to this interface, its final relative position being dependent on the particular RE. The position of the RE maximum within the oxide layer also varied with the substrate composition. For all coatings¹⁸O was found to have diffused through the oxide to the substrate-oxide interface during oxidation, the amount of oxide at this interface increasing with increasing time. The SIMS data confirm that for coated substrates there has been a change in oxidegrowth mechanism to predominantly anion diffusion. The RE most probably concentrates at the oxide grain boundaries, generally as the binary oxide (RE) CrO₃. Cr³⁺ diffusion is impeded, while oxygen diffusion remains unaffected.     

Diffusion of18O in massive Cr2O3 and in Cr2O3 scales at 900°C and its relation to the oxidation kinetics of chromia forming alloys

The lattice and grain-boundary diffusion coefficients of¹⁸O atP _{O 2}=0.1 atm and at 900°C were determined in massive Cr₂O₃ and in Cr₂O₃ scales which were grown on a Ni–30Cr alloy. The diffusion profiles were established by SIMS and analyzed considering two domains in the case of polycrystalline Cr₂O₃ (massive or scales), the first one relative to apparent diffusion and the second to grain-boundary diffusion. A ridge model is proposed for Cr₂O₃ scales to modify thef value, fraction of sites associated with the grain boundary. With such a model,f is equal to 0.0006 and 0.0005 for the scales formed during 15 hr and 165 hr, respectively. The oxygen-lattice diffusion coefficients determined in Cr₂O₃ scales are in very good agreement with those in massive Cr₂O₃. With some assumptions, our diffusion data lead to a calculated parabolic oxidation constant equal to the experimental one. Scale growth occurs by countercurrent diffusion of oxygen and chromium, mainly by grain-boundary diffusion.     

An investigation of the growth-mechanism of Cr2O3 on pure chromium in 1 atm oxygen at 950° C

The growth mechanism of Cr₂O₃ scale formed when pure chromium was oxidized at 950°C in oxygen at 1 atm pressure has been investigated. Isotope tracer techniques were used to determine the growth sites of the oxide. The scale was buckled extensively, with the convex side always toward the gas, never the reverse. The following growth-mechanism is proposed. Initially growth occurs entirely by cation diffusion, with new oxide being formed at the oxide-gas interface. Then, at a time that is not the same for all parts of the scale, the growth mechanism changes to one in which new oxide is formed within the outer part of the scale.     

Oxidation behavior of Ti3AlC2 at 1000-1400 °C in air

The isothermal oxidation behavior of bulk Ti₃AlC₂ has been investigated at 1000-1400 °C in air for exposure times up to 20 h by means of TGA, XRD, SEM and EDS. It has been demonstrated that Ti₃AlC₂ has excellent oxidation resistance. The oxidation of Ti₃AlC₂ generally followed a parabolic rate law with parabolic rate constants, k_p that increased from 4.1×10⁻¹¹ to 1.7×10⁻⁸ kg² m⁻⁴ s⁻¹ as the temperature increased from 1000 to 1400 °C. The scales formed at temperatures below 1300 °C were dense, adherent, resistant to cyclic oxidation and layered. The inner layer of these scales formed at temperatures below 1300 °C was continuous α-Al₂O₃. The outer layer changed from rutile TiO₂ at temperatures below 1200 °C to a mixture of Al₂TiO₅ and TiO₂ at 1300 °C. In the samples oxidized at 1400 °C, the scale consisted of a mixture of Al₂TiO₅ and, predominantly, α-Al₂O₃, while the adhesion of the scales to the substrates was less than that at the lower temperatures. Effect of carbon monoxide at scale/substrate was involved in the formation of the continuous Al₂O₃ layers.     

High-Temperature Oxidation of Ni Coated with La2O3 by Atomic-Layer Chemical-Vapor Deposition (ALCVD)

The effects of superficial (30–100 nm) La₂O₃ surface coatings on the oxidation kinetics of Ni from 700 to 1100°C in air and the oxide morphology of the NiO scales have been investigated. The parabolic rate constant is lower than for uncoated Ni by a factor of 5 to 10. The oxide morphology changes with the La₂O₃ coatings: The oxide scale consists of an outer fine-grain layer with an inner region of coarser, but still equiaxed, grains. SIMS shows that the majority of the La remains at the surface where a highly oxygen-defective spinel, La₂Ni₄O₇, was found by TEM. Two-stage oxidation followed by SIMS profiling reveals that the oxide growth occurs inside the scales.