Phase Transitions and Oxidation Behavior During Oxyacetylene Torch Testing of TaC–HfC Solid Solutions

Tantalum carbide (TaC) and hafnium carbide (HfC) have some of the highest melting temperatures among the transition metal carbides, borides, and nitrides, making them promising materials for high-speed flight and high-temperature structural applications. Solid solutions of TaC and HfC are of particular interest due to their enhanced oxidation resistance compared to pure TaC or HfC. This study looks at the effect of Hf content on the oxidation resistance of TaC–HfC sintered specimens. Five compositions are fabricated into bulk samples using spark plasma sintering (2173 K, 50 MPa, 10 min hold). Oxidation behavior of a subset of the compositions (100 vol% TaC, 80 vol% TaC + 20 vol% HfC, and 50 vol% TaC + 50 vol% HfC) is analyzed using an oxyacetylene torch for 60 s. The TaC–HfC samples exhibit a reduction in the oxide scale thickness and the mass ablation rate with increasing HfC content. The improved oxidation resistance can be attributed to the formation of a Hf₆Ta₂O₁₇ phase. This phase enhances oxidation resistance by reducing oxygen diffusion and serving as a protective layer for the unoxidized material. The superior oxidation resistance of TaC–HfC samples makes these materials strong contenders for the development of high-speed flight coatings.     

液态SiBCN前驱体转化陶瓷的抗氧化性能及机制

前驱体转化法制备的SiBCN陶瓷具有优异的耐高温抗氧化性能,有望作为高温热结构材料应用于航空航天领域。本文主要对前驱体转化法制备的SiBCN陶瓷在1 200、1 400℃下的抗氧化性能进行研究。采用XPS对陶瓷氧化前后化学键结合方式进行表征,分析了氧化前后化学结构的变化;采用XRD和SEM对陶瓷氧化前后表面相组成、微观形貌和截面氧化层进行分析,并通过氧化层厚度随时间变化对高温抗氧化动力学进行了研究。结果表明:SiBCN陶瓷经高温氧化后在表面形成了致密的氧化膜,氧化层主要以无定形态存在,且与基体结合紧密;陶瓷的高温氧化速率受氧扩散控制,其在1 200、1 400℃下的氧化动力学常数分别为0.0224 μm2/h和0.1045 μm2/h,小于SiC陶瓷的0.0449 μm2/h和0.1288 μm2/h。由于SiBCN陶瓷形成的BN （C）结构以及高温氧化后形成的SiO_xN_y致密氧化膜降低了氧气在氧化层中的扩散速率以及反应活性,使得SiBCN陶瓷具有比SiC陶瓷更加优异的高温抗氧化性能。      

掺杂改性C/C复合材料研究进展

陶瓷掺杂改性碳/碳(C/C)复合材料在保持C/C复合材料原有优异高温力学性能及尺寸稳定性等特性的前提下,显著提高了C/C复合材料的高温抗氧化、抗烧蚀性能,且其具有可设计性和良好的抗热震性能等优势,是新型高超声速飞行器和新一代高性能发动机热防护部件的理想候选材料。综述了国内外在SiC陶瓷掺杂改性C/C复合材料,ZrC,ZrB2超高温陶瓷掺杂改性C/C复合材料以及TaC,HfC超高温陶瓷掺杂改性C/C复合材料等方面的最新研究进展和应用情况,并分析了陶瓷掺杂改性C/C复合材料目前研究及应用中存在的主要问题和今后潜在的研究发展方向。     

高温氧化对超高温陶瓷材料耦合传热的影响

超高温陶瓷材料暴露于极端高温飞行环境中会导致其发生氧化,表面生成的氧化物具有不同的热物性从而对传热过程造成影响。针对预氧化的ZrB₂和ZrB₂-SiC,基于氧化模型预测氧化层(ZrO₂、B₂O₃、SiO₂和SiC耗尽层)厚度,利用有限元建立圆柱形代表性体积单元,并与外部高超声速流场的CFD (Computational Fluid Dynamics)求解器相耦合,研究了高温氧化对超高温陶瓷材料的耦合传热的影响。计算中采用分区求解方法,通过耦合界面处非匹配网格间的插值完成实时数据交换,实现了基于Navier-Stokes方程的流动求解器与有限元求解器的多场耦合计算。ZrB₂、ZrB₂-SiC以及氧化生成物的热物性均为温度相关,通过理论计算给出了B₂O₃挥发及SiC耗尽导致的多孔结构的有效热导率和有效比热容。瞬态耦合传热分析的结果表明:ZrB₂在预氧化后其热阻能力略有提高, ZrB₂-SiC氧化前后的热阻变化很小,并且在相同流动环境条件下,氧化后ZrB₂的热阻能力高于氧化后ZrB₂-SiC的热阻能力。      

Activated carbon/iron oxide composites for the removal of atrazine from aqueous medium

The adsorption features of activated carbon and the oxidation properties of iron oxides were combined in a composite to produce new materials for atrazine removal from aqueous medium. Activated carbon/iron oxide composites were prepared at 1/1 and 5/1 mass ratios and characterized with powder X-ray diffractometry (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and nitrogen adsorption measurements. The adsorption and oxidation processes were evaluated in batch experiments, in order to monitor the atrazine removal capacity of these composites. The main iron oxide actually present in the composites was goethite (alpha-FeOOH). Impregnation with iron oxide reduced the surface area by its deposition in the activated carbon pores. However, a higher iron concentration promoted a higher oxidation rate, indicating that the efficiency of the oxidation reaction is related with the iron content and not with the pre-concentration of the contaminant on the carbon surface through adsorption process.     

Antioxidant deactivation on graphenic nanocarbon surfaces

This article reports a direct chemical pathway for antioxidant deactivation on the surfaces of carbon nanomaterials. In the absence of cells, carbon nanotubes are shown to deplete the key physiological antioxidant glutathione (GSH) in a reaction involving dissolved dioxygen that yields the oxidized dimer, GSSG, as the primary product. In both chemical and electrochemical experiments, oxygen is only consumed at a significant steady-state rate in the presence of both nanotubes and GSH. GSH deactivation occurs for single- and multi-walled nanotubes, graphene oxide, nanohorns, and carbon black at varying rates that are characteristic of the material. The GSH depletion rates can be partially unified by surface area normalization, are accelerated by nitrogen doping, and suppressed by defect annealing or addition of proteins or surfactants. It is proposed that dioxygen reacts with active sites on graphenic carbon surfaces to produce surface-bound oxygen intermediates that react heterogeneously with glutathione to restore the carbon surface and complete a catalytic cycle. The direct catalytic reaction between nanomaterial surfaces and antioxidants may contribute to oxidative stress pathways in nanotoxicity, and the dependence on surface area and structural defects suggest strategies for safe material design.     

SUPERCONDUCTIVE FILMS BY LASER POST-TREATMENT OF THERMAL-SPRAYED FILMS

In an attempt to produce a thick superconductive film of large area, an experimental study was conducted on the preparation of the film through laser post-treatment of thermal-sprayed oxide ceramic film. The ceramic powder of Bi-(Pb)-Sr Ca-Cu-O system was used as raw material. The powder was sprayed onto a stainless steel substrate using two types of spraying systems, conventional plasma spraying system and lower temperature hypersonic spraying system both followed by CO₂ laser beam irradiation with oxygen gas flow to remodify the superconductive crystals in the films. The results showed that, though laser post-treatment can produce superconductive crystals in both sprayed films, higher critical temperature Tc (end) was obtained for the film prepared by the hypersonic spraying system.     

陶瓷前驱体配比对Si-Zr-B掺杂沥青基炭材料抗氧化性能的影响

以SiC、ZrC、ZrB₂前驱体和二甲苯可溶煤沥青为原料共裂解制备了Si-Zr-B掺杂沥青, 掺杂沥青经共炭化、冷压成型以及高温热处理得到了Si-Zr-B掺杂沥青基炭材料。采用XRD、SEM、EDS等手段分析了掺杂沥青基炭材料的组成和微观形貌, 并研究了其在1500℃静态空气环境中的氧化行为。结果表明, 随着SiC前驱体含量的降低, Si-Zr-B掺杂沥青基炭材料的失重率呈现先减少后增大的趋势, 当原料中SiC、ZrC和ZrB₂前驱体质量比为1:2:1时, 所制备的样品具有较好的抗氧化性能, 它在1500℃氧化4 h, 失重为27.5wt%, 氧化深度为0.7 mm。在Si-Zr-B掺杂沥青基炭材料表面氧化形成的致密的SiO₂-ZrO₂-B₂O₃玻璃态阻氧层可以有效降低氧化性气氛向材料内部扩散的速率, 提高其抗氧化性能。     

超高温复相陶瓷基复合材料烧蚀行为研究

采用前驱体浸渍热解(PIP)工艺制备了ZrC-SiC、ZrB2-ZrC-SiC和HfB2-HfC-SiC复相陶瓷基复合材料,复合材料中的超高温陶瓷相均呈现出亚微米/纳米均匀弥散分布的特征,对比研究了上述材料在大气等离子和高温电弧风洞考核环境中的超高温烧蚀行为.研究结果表明,超高温复相陶瓷基复合材料相比传统的未改性SiC...     

The contamination of nickel surfaces during oxidation in fused silica reaction vessels

In many experiments involving the high temperature oxidation of nickel in fused silica reaction vessels the final oxidation products have been found to include silica as -cristobalite. Prior to oxidation the nickel was decarburized by exposure to oxygen followed by hydrogen reduction of the remaining oxide film. The silicon of the silica was transferred from the vessel walls to the specimen as silicon monoxide formed by the reduction of the silica by the carbon monoxide produced during the decarburization step. The silicon monoxide was reduced at the metal specimen by residual carbon to form silicon which then dissolved in the nickel. Detectable contamination of the surface took place during subsequent oxidation when the silicon was preferentially oxidized at the surface. The reaction of carbon monoxide with the silica tube was enhanced by devitrification caused by previous high temperature (> 700° C) treatment. Contamination could be avoided if the tube was never heated above 700° C and was minimized at 900° C by more complete decarburization of the specimen.     

TaC/Ti3SiC2复合材料的制备与性能

采用反应热压烧结法制备了TaC/Ti₃SiC₂复合材料,借助XRD、SEM、能谱仪以及热重分析等,研究了TaC含量对TaC/Ti₃SiC₂复合材料的相组成、显微结构、力学性能和抗氧化性的影响。结果表明: 采用反应热压烧结法可以制备出致密的TaC/Ti₃SiC₂复合材料,该复合材料的主晶相为Ti₃SiC₂和TaTiC₂,还含有少量的TiC;随着TaC含量的增加,TaC/Ti₃SiC₂复合材料的弯曲强度和断裂韧性呈现先增大后降低的变化趋势,当TaC含量为30wt%时,二者均达到最大值,此时弯曲强度为404 MPa,断裂韧性为4.10 MPa·m^1/2;TaC的引入,使TaC/Ti₃SiC₂复合材料抗氧化性能明显优于Ti₃SiC₂材料。     

Formation of NbC and TaC by solid-state reaction

The formation of NbC and TaC by solid-state reaction of Nb₂O₅ and Ta₂O₅ with carbon, respectively, was studied at 1000 to 1285° C by X-ray diffraction. Factors affecting the formation of the carbides, such as the nature of the reaction vessel, the molar ratio of carbon/oxide, the form of reactant carbon, etc., were examined. By covering the graphite crucible and increasing the molar ratio of carbon to oxide, complete formation of NbC and TaC could be achieved in about 60 min at low temperatures (1170 and 1225° C, respectively). The beneficial effect of covering the crucible is ascribed to the retention of CO which facilitates the reaction at low temperatures. The formation kinetics of NbC and TaC obey a first-order equation, with activation energies of 90 and 93 kcal mol^–1, respectively. Possible mechanisms for the solid-state reactions are discussed.     

Ceramic coated Y1 magnesium alloy surfaces by microarc oxidation process for marine applications

The magnesium alloys occupy an important place in marine applications, but their poor corrosion resistance, wear resistance, hardness and so on, have limited their application. To meet these defects, some techniques are developed. Microarc oxidation is a one such recently developed surface treatment technology under anodic oxidation in which ceramic coating is directly formed on the surface of magnesium alloy, by which its surface property is greatly improved. In this paper, a dense ceramic oxide coating, ∼20 μm thick, was prepared on an Y1 magnesium alloy through microarc oxidation in a Na₃SiO₃-Na₂WO₄-KOH-Na₂EDTA electrolytic solution. The property of corrosion resistance of ceramic coating was studied by CS300P electrochemistry-corrosion workstation, and the main impact factor of the corrosion resistance was also analysed. Microstructure and phase composition were analysed by SEM and XRD. The microhardness of the coating was also measured. The basic mechanism of microarc coating formation is explained in brief. The results show that the corrosion resistance property of microarc oxidation coating on the Y1 magnesium surface is superior to the original samples in the 3·5 wt% NaCl solutions. The microarc oxidation coating is relatively dense and uniform, mainly composed of MgO, MgAl₂O₄ and MgSiO₃. The microhardness of the Y1 magnesium alloy surface attained 410 HV, which was much larger than that of the original Y1 magnesium alloy without microarc oxidation.     

Effects of liquid swine manure on dissipation of 17β-estradiol in soil

17β-estradiol (E2), a natural estrogenic hormone, degrades within hours and bind strongly to soils and sediments; however, estrogens are frequently detected in the environment at concentrations that impact water quality. Colloidal (COC) and dissolved (DOC) organic carbon may enhance the persistence and mobility of E2. Soil batch experiments were used to identify the persistence and sorption of radiolabeled E2 dissolved in solutions of (i) COC/DOC derived from liquid swine manure and (ii) CaCl(2). Estradiol disappeared from the aqueous phase before 7 d in the CaCl(2) solution, yet persisted throughout the duration of the 14 d experiment in the liquid manure solution. There was also concomitant formation of estrone (E1; a metabolite of E2) as E2 dissipated in sterile batch experiments, which was attributed to abiotic oxidation. The liquid manure solution appeared to interact with the estrogen and/or oxidation reaction sites, reducing E2 degradation. Furthermore, the liquid manure solution reduced E2/E1 binding to the soil surface resulting in more E2/E1 in the aqueous layer compared to the CaCl(2) solution. Ultrafiltration results of liquid manure indicated that ～1/3 of E2 was associated with COC, which may be responsible for the reduced degradation and sorption of E2 in the liquid manure solution.     

Sintering behaviour of ultrafine NbC and TaC powders

Compositional and microstructural changes upon firing ultrafine (300 to 400 Å) stoichiometric NbC and TaC powder lots have been studied up to a temperature of 1600° C. Substantial amounts of oxygen impurities, mostly oxide particles or layers are eliminated by reductions with hydrogen, free carbon or the carbides themselves. TGA showed these reactions to take place at 700 to 1400° C with maxima around 1000 to 1100° C. Low temperature sintering is inhibited by this impurity and its removal is thus essential. Other impurities (Ni, Cr, Fe) were also found in the starting powders in total concentration 0.5 to 1%. They give rise to a liquid phase located at grain edges at temperatures as low as 1100° C which then controls microstructure development. It dissolves to some extent in the carbide matrix at high temperature, and has a tendency to rise to the free surface of the samples. Compositional and structural heterogeneities are thus produced between bulk and surface at high temperatures. Owing to these impurity effects, it was not possible to clearly evaluate the influence of powder granulometry.     

Catalytic activity of copper oxide added to a sample as a copper-polymer carboxylated complex in the reaction of carbon black oxidation

The catalytic activity of copper oxide in the carbon black reaction with air oxygen has been studied with the catalyst addition to a sample by different methods. It has been shown that copper oxide added as copper acetate from the ether solution accelerates the carbon black oxidation at 700 K approximately by a factor of 110, copper acetate added from a water solution accelerates the carbon black oxidation by a factor of 300, and if the catalyst is added as a copper-polymer carboxylated complex, the carbon black oxidation is accelerated by a factor of 460. It has been assumed that the difference in catalytic activity of copper oxide added by various methods is caused by the nonuniformity of the copper distribution over the carbon black surface.     

The oxidation behaviour of metals and alloys at high temperatures in atmospheres containing water vapour: A review

The kinetics of oxide formation in the presence of water vapour are discussed and compared with oxidation in dry atmospheres. The main protective oxide systems are considered, i.e. alumina, chromia, silica, titania and iron and nickel oxides, and with the possible exceptions of alumina and nickel oxide, oxidation rates are increased by the presence of water vapour. Scale morphology is also influenced by water vapour, and an important observation is that whisker formation is encouraged; this is believed to be due to the more rapid dissociation of water vapour compared to oxygen. In general, water vapour promotes the formation of a more porous scale. This is related to an increase in cation diffusion and consequent vacancy condensation, thereby developing a porous structure. The thermochemistry of oxide formation is discussed, and here oxide stability and hydroxide formation are considered. A significant observation is that where hydroxides or oxyhydroxides form, they generally have higher volatility than the corresponding oxide, and this leads to loss of protection.The effect of water vapour on oxide growth processes is considered. It is demonstrated that all aspects of oxide growth including adsorption, dissociation and diffusion of reactants are altered in the presence of water vapour compared with similar processes in dry conditions. The important first stages of the reaction involving adsorption and dissociation are controlled by the catalytic activity and acid base nature of oxides. For oxides formed at high temperatures very limited information is available, but, in general, data obtained at room temperature is confirmed and strongly suggests that dissociation of any gas molecule is favoured by defects in the surface. Dissociation of water seems to be more rapid at lower temperatures than, for example, oxygen, but this difference may be less pronounced at higher temperatures. Fast diffusion of water in oxides is possible due to “proton hopping”, in which protons localised at oxide ions move by transfer from one oxygen to another. Since the OH⁻ ion concentration is increased there is a resultant increase in cation vacancies, and this, in part, is responsible for the observed increase in oxidation rates. A further factor to consider is the possibility of molecular diffusion, and it has been demonstrated that where pores or voids are present in the scale, and the void contains both hydrogen and water vapour, oxidation of the surface nearest the metal will occur by reaction with water to form new oxide and the reaction product hydrogen, while a reduction reaction occurs at the surface of the void nearest the gas phase to produce water vapour. Thus it can be seen that this process provides for rapid inward diffusion of oxygen while the void gradually moves outwards from the metal/oxide interface to the oxide/gas interface.Finally, the review considers the effect of water vapour on the mechanical properties of the scale. Scale adhesion can be improved (iron oxides) or made worse (alumina and chromia) by the presence of water vapour. It is shown that while there is experimental evidence for altered mechanical behaviour, there is very little data on relevant mechanical properties. It is possible, therefore, that water vapour either alters mechanical properties of some oxides, or, as has been demonstrated, the oxide growth process has been changed. Alternatively, at least for the cases where increased oxidation rates were caused by the presence of water vapour, the observed differences between wet and dry behaviour may simply be a function of the greater scale thickness. A significant effort has been made to develop models that can be used to predict the onset scale spallation observed in industrial boilers using process steam. The further development of these models is strongly dependent upon obtaining relevant input data, and this is considered a major challenge for materials scientists.Some areas for future research are proposed.     

液相浸渍C/C复合材料反应生成TaC的形貌及其形成机制

采用Ta有机溶剂浸渍C/C复合材料,经固化、热处理制备C/C-TaC复合材料.研究发现:在2MPa浸渍压力下,Ta有机溶剂易于浸渍C/C复合材料和固化;1500℃热处理后,Ta有机溶剂全部转变为TaC,其尺寸细小,结晶度高,呈颗粒状或聚集成团簇均匀分布在热解炭层面上;1800和2000℃热处理后的TaC形貌与1500℃热处理后的相似,Tac颗粒无明显长大现象.Ta有机溶剂转化生成Tac的机理研究表明:热处理过程中,Ta有机溶剂先生成中间相的氧氟化钽,转变为Ta₂O₅后,再与C还原-化合生成TaC.     

Recombination of atomic oxygen on sintered zirconia at high temperature in non-equilibrium air plasma

High temperature ceramic materials are necessary for the design of primary heat shields for future re-usable space vehicles re-entering atmospheric planet at hypersonic velocity. During the re-entry phase on earth, one of the most important phenomena occurring on the heat shield is the recombination of atomic oxygen and this phenomenon is more or less catalyzed by the material of the heat shield.     

Synthesis of TaC nanopowders by liquid precursor route

TaC nanopowders were synthesized by a liquid precursor route. The synthesis procedures include (1) preparation of tantalum ethylate solution by sufficient mixing TaCl₅ powders with ethanol, (2) adding activated carbon nanopowders to the solution, (3) dispersing activated carbon nanopowders in the solution evenly to form a liquid precursor by an ultrasonic equipment, (4) brushing the liquid precursor on an alumina crucible and blowing the liquid precursor to dry, (5) heat treatment in a graphitization furnace in a vacuum, and (6) brushing the alumina crucible to obtain products. X-ray diffraction patterns indicated that the products were cubic TaC. The formation temperature (1300 °C) of TaC in this process is lower than that (1700 °C) in the conventional method. The reaction time of forming TaC in this process is half an hour. The observed size of TaC powders by TEM was smaller than 50 nm. The specific surface area of the powders by a surface area analyzer was 28.399 m²/g.