High-temperature oxidation of Ti3Al−Nb alloys

Titanium aluminide (Ti₃Al–Nb) has potential for high-temperature applications because of its low density and high-temperature strength. This research is aimed at improving the high-temperature oxidation resistance of a Ti₃Al–Nb alloy by modification of its composition. The oxidation rates of Ti₃Al–Nb alloys were measured from 600 to 900°C in air. The oxide layer was examined by X-ray diffraction, scanning electron microscopy, and electron probe microanalysis. The experimental results reveal that alloys with added Nb tend to form denser oxide layers and that oxidation rate can be reduced by increasing Nb content (up to 11 at.% in this study), which is in good agreement with other investigators. The only exception is a Ti₆₅Al₂₅Nb₁₀ alloy, which shows better oxidation resistance than the commercial Ti₆₅Al₂₄Nb₁₁ alloy. The oxidation resistance of Ti₆₅Al₂₅Nb₁₀ alloy can also be improved slightly by the addition of small amounts of Si or Cr. An increase in the oxidation resistance of Ti₆₅Al₂₅Nb₁₀ alloy containing Y was observed at 900°C but not at 800°C or below. The parabolic oxidation rate equation is adequate to describe the high-temperature oxidation reaction of the Ti₃Al–Nb alloys in the atmosphere.     

High-temperature oxidation of Al-Mg alloys

Surface-analysis techniques (x-ray photoelectron spectroscopy and Auger electron spectroscopy) and electron microscopy (SEM and TEM) have been used to study the mechanism of steady-state high-temperature oxidation of Al-Mg alloys. Two high-purity alloys containing 0.4 and 2.0 wt.% Mg were heat-treated in dry air at 550°C up to 90 hr. It was found that the oxide layer was composed of MgO and spinel (MgAl₂O₄), the major constituent being MgO. The molar concentration of MgO decreased with increasing depth, while that of spinel increased. The rate-controlling mechanism for the growth of the oxide layer in the Al-0.4Mg alloy was the solid-state diffusion of Mg in the MgO-spinel constituents. For alloys of higher-magnesium content, the growth of the oxide layer was controlled by solid-state diffusion of Mg through the adherent protective oxide areas and by the transport of Mg vapor across voids formed between the alloy substrate and the oxide layer.     

High-temperature oxidation and thermal cycling of aluminum-electroplated stainless steels

An alumina coating, produced from the oxidation of an aluminum-electroplated deposit, improved the oxidation resistance in air of a ferritic, AISI-type 446 stainless steel, Fe-24Cr-1.2Al containing 0.15% of mischmetal, and an austenitic AISI 321 stainless steel containing 0.53% Ti, at least up to 1100°C. In thermal-cycling tests from 1000°C to room temperature, the alumina coating was adherent on the ferritic and austenitic steels, for at least 1000 and about 700 cycles, respectively. The addition of rare earths to the ferritic steels and titanium to the austenitic, provided good adhesion between the coating and substrate. The porous nature of the coating was found to be very beneficial by causing the coating to be more resistant to thermal and growth stresses. Oxidation mechanisms are discussed in the light of results obtained from the thermogravimetric tests and metallographic observations by SEM-ED analysis.     

钴基超合金铝化物涂层的高温氧化寿命

通过分析钴基超合金外扩散型铝化物涂层的高温氧化及退化行为 ,并采用近似方法推算 ,得出了这类涂层氧化和退化与时间的关系。研究表明 ,涂层外侧退化主要由氧化反应驱动力所控制 ,涂层的外侧退化速率正比于其氧化速率 ;而涂层的氧化寿期近似正比于其主体层厚的平方。运用氧化退化与时间的关系式 ,进行简便的辅助实验 ,即可预测出这类涂层的高温氧化寿命。     

High-temperature oxidation of a rapidly solidified amorphous Ta-Ir alloy

The oxidation products formed at 500 and 700°C on an amorphous Ta-44.5 at% Ir alloy in an Ar-0.1% O₂ gas mixture were characterized using SEM, XRD, EPMA, TEM, STEM, AES, and XPS. Initially, a thin (3–4 nm) layer of Ta₂O₅ formed at the surface of the alloy. Continued growth of the Ta₂O₅, which occurred very rapidly, involved diffusion of oxygen anions from the Ta₂O₅/gas interface to the alloy/Ta₂O₅ interface, where tantalum was selectively oxidized. Because the oxide grew more quickly than iridium could diffuse back into the alloy, the iridium coalesced into platelets of crystalline iridium-rich alloy that were oriented approximately parallel to the oxide/alloy interface, and which became embedded in a matrix of Ta₂O₅. The unoxidized core remained in the glassy state. The oxidation process and/or the dissolution of oxygen into the unoxidized alloy caused the alloy to become embrittled.     

微弧氧化对TC4钛合金高温抗氧化性能的影响

采用直流稳压电源,在Na2SiO3、Na3PO4电解液中对TC4钛合金表面进行微弧氧化处理,研究了微弧氧化对TC4钛合金高温抗氧化性能的影响.结果表明,经微弧氧化的TC4合金高温抗氧化性能明显优于TC4钛合金;在750℃循环氧化100h后,经300V电压微弧氧化60 min的TC4钛合金的氧化增重为7.8 mg/cm2,而未经微弧氧化处理的TC4钛合金氧化增重为30.51 mg/cm2;随着微弧氧化时间增长和电压的增大,微弧氧化TC4钛合金的高温抗氧化性能也增强.     

钼金属高温抗氧化能力的研究概况

概述了钼在高温下的氧化机理及其在高温下的防止氧化的方法,例如涂层、合金,改变制备工艺等方法,介绍了最新研制的涂层和钼合金在高温条件下的应用,并指出新材料的研究方向。     

High-temperature oxidation behavior of CeO2-SiO2/Ni-W-P composites

Ni-W-P matrix composites containing CeO₂ and SiO₂ nano-particles were prepared on common carbon steel surface by means of pulse electrodeposition, and the high-temperature oxidation behavior was investigated. The results show that when the oxidation time is controlled in 1 h, oxidation kinetics curve between oxidation mass gain rate and oxidation temperature of CeO₂-SiO₂/Ni-W-P composites accords with the index increasing law. When the oxidation temperature is controlled at 300 °C, the kinetics curve between oxidation mass gain rate and oxidation time accords with the linear increasing law. The composites as-deposited are in the amorphous state and turn into the crystal state at 400 °C. The microstructures of oxidation film on the composites will change from the compact state to the loose state with increasing oxidation temperature to 800 °C. They are still continuous and compact, and there are no crackle, strip and falling-out. CeO₂ and SiO₂ nano-particles co-deposited into Ni-W-P alloy can improve the high-temperature oxidation resistance.     

含铁铜基陶瓷复合材料高温氧化行为与耐磨性研究

在25,250,350和450℃高温摩擦磨损实验条件下,对两种不同铁含量的Cu基摩擦材料进行高温氧化行为及耐磨性研究。结果表明:Fe在Cu基体中的尺寸、分布影响Cu基摩擦材料的高温抗氧化性和耐磨性,随实验温度升高,Cu基摩擦材料试样中Cu氧化产物为Cu2O,Fe从Fe2O3转变为Fe3O4,金属氧化膜厚度逐渐增加;Fe以小尺寸、均匀分布于Cu基体时,更有利于提高Cu基体整体的抗氧化性能,在350~450℃可形成稳定的氧化膜降低粘着磨损,展现出了较好的高温耐磨性能;而Fe以较大尺寸分布在Cu基体中时,则使Cu基体出现氧化不均匀现象,不利于高温耐磨性能的提高。     

Evolution mechanism of the interfacial reaction layers in the joints of diffusion bonded Mo and Ai foils

Mo foil (10-20 μm in thickness) and Al foil (20-60 μm in thickness) were vacuum diffusion bonded at 600-640 ℃ under 20 MPa for 54 min-6 h. The joints were examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) to study the evolution mechanism of the reaction layers. The results show that Al atoms diffuse into Mo grain boundaries and form reaction products as Mo3Als, MoAl4, MoAl5 and MoAl12. The surface oxide film is eroded by the growths of the reaction products that plow into the lamellar texture of Mo grain boundaries. Mo3Al8 layer grows by "taking root" downwards and transforms into MoAl4 and MoAl5 phases upwards by absorbing Al atoms. MoAl12 layer grows up from MoAl5 layer in the same way. When the supplement of Al atoms ceases, MoAl12 transforms reversely into MoAl5 and MoAl3 into MoAl4 via the loss of Al atoms. However, MoAl4 continues to precipitate from Mo3Al8 layer. At last, there are MoAl4 and Mo3Al8 remained on the joint interface.     

High-temperature oxidation behavior of iridium-based alumina-forming ternary intermetallics

The oxidation behavior of iridium-based intermetallics in the ternary iridium-aluminum-silicon system has been investigated. Additions of up to 20 at. % silicon to iridium-aluminum binary alloys reduce the aluminum concentration necessary for the formation of a protective alumina scale from greater than 55 at.% in the absence of silicon to as low as 20 at.% when 20 at.% silicon is present. Ternary iridium-aluminum-silicon alloys with 30–50 at.% aluminum and 8–10 at.% silicon exhibit parabolic oxidation behavior, and the rate constants are in good agreement with those previously determined for binary iridium-aluminum alloys. The oxidation rate of ternary iridium-aluminum-silicon alloys with 10 at.% silicon and 30–40 at.% aluminum deviates from the parabolic-oxidation behavior for alumina scale growth in the later oxidation stage, presumably due to the formation of a silica inner layer. Thermal cycling of the Ir-50 Al-8Si and Ir-60-Al samples does not result in scale spallation due to the coefficient of thermal expansion match between the alumina scale and intermetallic substrate.     

锆合金表面CrAl基耐高温涂层及氧化行为研究

目的了解锆合金和涂层的高温氧化行为,通过表面涂层提升锆合金的耐高温氧化性能。方法采用多弧离子镀技术在锆合金基体上制备了CrAlN、CrTiAlN涂层,模拟反应堆失水(LOCA)事故时的高温氧化行为,在360～1160℃下进行1 h氧化测试,对原始锆合金和带涂层样品的氧化增重行为进行了研究。通过X射线衍射和扫描电子显微镜对氧化前后样品的物相结构和形貌进行系统表征分析。结果锆合金在760℃及以下形成深色的混合型锆氧化膜,在860℃以上呈现龟裂和局部剥落。两种涂层氧化时,通过形成致密的Cr_2O_3和Al_2O_3混合氧化层,显著降低了氧化增重。CrAlN涂层在760℃时具有较好的抗氧化性,1060℃时开裂而失去保护作用。CrTiAlN涂层在860℃时能保护基体不受氧化,1060℃时局部开裂,基体开始出现氧化层。结论利用多弧离子镀技术制备的锆合金表面CrAlN和CrTiAlN涂层,在模拟反应堆LOCA事故下具有良好的耐高温氧化性,显示出这两种涂层有潜力发展成为核用事故容错燃料(ATF)包壳涂层。     

铝化物高温防护涂层的现状

介绍了高温防护涂层的主要类型、制备方法及其失效方式，重点突出了铝化物涂层在高温防护领域的重要性和高温涂层、高温氧化问题研究的重要性，从而点出了应该进一步深人地研究铝化物涂层高温氧化规律的重要意义。     

Observations on the effect of low sulfur activity on the oxidation of chromium-depleted zones in a stainless steel

Coupon specimens of 20% Cr-25% Ni-Nb-stabilized steel have been oxidized in an atmosphere of CO ₂-2%CO-670 vppb COS at 0.1 MPa pressure for periods up to 500 hr at 1123 K. Standard specimens, annealed at 1203 K prior to testing, showed an enhancement of iron in the surface scale and a much increased propensity to spall compared with control tests in a sulfur-free atmosphere. The main purpose of the work was to examine the effect of sulfur on the ease of formation of a healing layer under duplex attack produced by depleting specimens in chromium by prior vacuum annealing. It is shown that although a chromium-rich layer had formed, extensive breakdown occurred in the sulphidizing atmosphere leading to continued internal oxidation. Sulfur was found to partition at the base of this attack and to be associated with a large concentration of nickel. Spaliation was also enhanced in the depleted specimens, the favored site being the interface between the spinel and outer iron-rich oxide of the duplex structure. Partitioning of both sulfur and carbon was observed at this interface in those regions of the specimen showing healing layer breakdown.     

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.     

High-temperature oxidation of a 20/25 stainless steel in high-pressure carbon dioxide

Kinetics of high-temperature oxidation, and of oxide spallation, are reported for a 20Cr-25Ni Nb-stabilized stainless steel, exposed in carbon dioxide at 40 bar pressure in the temperature range 1115–1240 K. Gross weight-gain kinetics were parabolic with respect to time, with an activation energy of 370±16 kJ/mol. Oxidation rates are shown to be consistent with diffusion control in the inner chromia layer of a two-layer oxide. Intergranular oxidation of silicon was observed beneath the oxide scale. Oxide spallation occurred at all temperatures and increased linearly with gross weight gain. At 1240 K 50% of the oxide which formed spalled at the first weighing. Thereafter, the fraction spalling decreased to about 10%. The difference is attributed to a change in the oxide composition from an M₂O₃ structure to M₃O₄, which requires greater compressive stresses to induce spallation during cooling.     

High-temperature oxidation of copper-manganese alloys

The oxidation behavior of copper-manganese alloys (2–35 wt. % Mn) in pure oxygen at 760 Torr was investigated at 100° intervals between 550 and 850°C. Gravimetric measurements of the oxidation kinetics have been combined with microstructural studies of the reacted samples in order to evaluate the reaction mechanisms. The scales formed on Cu-2Mn, Cu-5Mn, Cu-10Mn are always composed of three different layers; in any case manganese is present only in the inner layer. The scales formed on Cu-20Mn and Cu-35Mn are composed of two layers, both containing manganese, with a more Cu-rich outer layer. In all the samples internal oxidation in combination with external scale formation is observed.     

NbZrTiTa高熵合金的高温氧化行为

采用循环氧化考核法以及借助XRD、SEM等技术对电弧熔炼制备的NbZrTiTa高熵合金的高温氧化行为进行了研究。结果表明:NbZrTiTa高熵合金在1000～1400℃温度范围内的氧化速率常数和氧化激活能分别达到1.1×10~(-7)～1.0×10~(-6) g~2·cm~(-4)·s~(-1)和97 kJ/mol。NbZrTiTa高熵合金的氧化反应类型为内氧化。高温氧化过程中,氧元素沿具有强晶格畸变和大量位错的富TiZr区扩散,并与金属组元发生反应依次生成不饱和氧化物和饱和氧化物。在组元的高活性以及严重的晶格畸变的共同作用下,NbZrTiTa高熵合金具有极高的氧化活性,展现出了较强的作为结构释能材料的应用潜力。