Synthesis of ZrC–SiC Powders by a Preceramic Solution Route

Homogenous liquid precursor for ZrC–SiC was prepared by blending of Zr(OC₄H₉)₄ and Poly[(methylsilylene)acetylene]. This precursor could be cured at 250°C and converted into binary ZrC–SiC composite ceramics upon heat treatment at 1700°C. The pyrolysis mechanism and optimal molar ratio of the precursor were investigated by XRD. The morphology and elements analyses were conducted by SEM and corresponding energy‐dispersive spectrometer. The evolution of carbon during ceramization was studied by Raman spectroscopy. The results showed that the precursor samples heat treated at 900°C consisted of t‐ZrO₂ (main phase) and m‐ZrO₂ (minor phase). The higher temperature induced phase transformation and t‐ZrO₂ converted into m‐ZrO₂. Further heating led to the formation of ZrC and SiC due to the carbothermal reduction, and the ceramic sample changed from compact to porous due to the generation of carbon oxides. With the increasing molar ratios of C/Zr, the residual oxides in 1700°C ceramic samples converted into ZrC and almost pure ZrC–SiC composite ceramics could be obtained in ZS‐3 sample. The Zr, Si, and C elements were well distributed in the obtained ceramics powders and particles with a distribution of 100 ~ 300 nm consisted of well‐crystallized ZrC and SiC phases.     

Reactive Hot Pressing of ZrC–SiC Ceramics at Low Temperature

Composites of ZrC–SiC with relative densities in excess of 98% were prepared by reactive hot pressing of ZrC and Si at temperature as low as 1600°C. The reaction between ZrC and Si resulted in the formation of ZrC_1?x, SiC, and ZrSi. Low‐temperature densification of ZrC?SiC ceramics is attributed to the formed nonstoichiometric ZrC_1?x and Zr–Si liquid phase. Adding 5 wt% Si to ZrC, the three‐point bending strength of formed ZrC_0.8–13.4 vol%SiC ceramics reached 819 ± 102 MPa with hardness and toughness being 20.5 GPa and 3.3 MPa·m^1/2, respectively.     

Oxidation Behavior of Hot Pressed ZrB2‐ZrC‐SiC Ceramic Composites

Dense ZrB₂‐SiC ceramics containing 40 vol% ZrC particles are fabricated via hot pressing method. Then the sintered ceramics are oxidized in air up to 1500°C, and the oxidation kinetics of the ceramic composites is deduced in combination with the reacted fraction curves. As indicated by the experimental results, the oxidation kinetics changes from reaction‐controlled process to diffusion‐controlled one with increasing of oxidation temperature. In addition, the oxidation kinetics parameters are obtained, which indicates that the oxidation resistance decays at elevated temperatures. Furthermore, the evolution of surface morphology and oxide scale during oxidation process is clarified.     

New Route to Synthesize Ultra-Fine Zirconium Diboride Powders Using Inorganic–Organic Hybrid Precursors

Ultra-fine zirconium diboride (ZrB₂) powders have been synthesized using inorganic–organic hybrid precursors of zirconium oxychloride (ZrOCl₂·8H₂O), boric acid, and phenolic resin as sources of zirconia, boron oxide, and carbon, respectively. The reactions were substantially completed at a relatively low temperature (∼1500°C). The synthesized powders had a smaller average crystallite size (<200 nm), a larger specific surface area (∼32 m²/g), and a lower oxygen content (<1.0 wt%), which were superior to some commercially available ZrB₂ powders. The thermodynamic change in the ZrO₂–B₂O₃–C system was mainly studied by thermogravimetric and differential thermal analysis. The crystallite size and morphology of the synthesized powders were characterized by transmission electron microscopy and scanning electron microscopy.     

Oxidation behavior of C–SiC composites with a Si–W coating from room temperature to 1500°C

Oxidation tests of carbon fiber reinforced silicon carbide composites with a Si–W coating were conducted in dry air from room temperature to 1500°C for 5 h. A continuous series of empirical functions relating weight change to temperature after 5 h oxidation was found to fit the test results quite well over the whole temperature range. This approach was used to interpret the different oxidation mechanisms. There were two cracking temperatures of the matrix and the coating for the C–SiC composite. Oxidation behavior of the C–SiC composite was nearly the same as that of the coated C–C composite above the coating cracking temperature, but weight loss of the C–SiC composite was half an order lower than that of the coated C–C composite below the cracking temperature. As an inhibitor, the SiC matrix increased the oxidation resistance of C–SiC composites by decreasing active sites available for oxidation. As an interfacial layer, pyrolytic carbon decreased the activation energy below 700°C. From 800°C to 1030°C, uniform oxidation took place for the C–SiC composite, but non-uniform oxidation took place for the coated C–C composite in the same temperature range. The Knudsen diffusion coefficient could be used to explain the relationship between weight loss and temperature below the coating cracking temperature and the matrix cracking temperature.     

Glass-Reduced SiAlONs with Improved Creep and Oxidation Resistance

Ceramics containing α-SiAlON with improved high-temperature properties such as thermal stability and creep and oxidation resistance were synthesized. The influence of starting composition on the amount of residual grain-boundary phase has been explored. Results have been interpreted in terms of compatibility phase relationships in the Si₃N₄–AlN–Al₂O₃–Re₂O₃ system and transient evolutions.     

Nanostructured Solids from Freeze‐Dried Precursors: Multigram Scale Synthesis of TiO2‐Based Powders

Nanocrystalline TiO₂ and Ti_1?xV_xO₂ (x = 0.01) powders have been prepared by thermal decomposition, in air, of amorphous precursors resulting from the freeze‐drying of appropriate solutions. In addition, TiO_2?xN_y (anatase and rutile) and TiO_xN_y (rock‐salt) have been prepared by thermal treatment in ammonia of a crystalline precursor (TiO₂ obtained at 673 K). TEM and SEM images, as well as the analysis of the X‐ray diffraction (XRD) patterns, show the nanoparticulated character of those solids obtained at low temperatures, with typical particle sizes in the 10–20 nm range when prepared at 673 K. The UV–Vis results indicate both the insertion of V in the anatase lattice and the feasibility of nitridation at low temperatures. The photocatalytic properties of these materials (as prepared and after their incorporation to mortar samples) in the degradation of nitrogen oxides have been preliminary evaluated. Although N‐doping enhances the photocatalytic activity of the TiO₂ matrix, V‐doping worsens it.     

Synthesis and Properties of MoSi2–MoB–SiC Ceramics

MoB and SiC particulate reinforced MoSi₂ matrix composites were synthesized in situ from Mo, Si, and B₄C powder mixtures by self‐propagating high‐temperature synthesis (SHS). The SHS MoSi₂–MoB–SiC products were vacuum hot‐pressed (HPed) at 1400°C for 90 min to fabricate high‐density (> 97.5% relative density) bulk composites. Microstructure refinement and improvements in the Vickers hardness and fracture toughness of the HPed composites were observed with increasing B₄C content in the reaction mixture. The HPed composite of composition MoSi₂–0.4MoB–0.1SiC exhibited grain size of 1–5 μm, Vickers hardness of 12.5 GPa, bending strength of 537 MPa, and fracture toughness of 3.8 MPa.m^1/2. These excellent mechanical properties indicate that MoB and SiC particulate reinforced MoSi₂ composites could be promising candidates for structural applications.     

Synthesis of Ultrafine β"-Alumina Powders via Flame Spray Pyrolysis of Polymeric Precursors

Flame spray pyrolysis of a polymeric precursor is used to prepare ultrafine powders that, when sintered, convert to essentially pure phase lithium-doped sodium β"-alumina. The precursor Na_1.67 Al_10.67 Li_0.33 [N(CH₂CH₂O)₃]_10.67-[OCH₂CH₂O]·x(HOCH₂CH₂OH) has been synthesized from stoichiometric amounts of metal hydroxides and tri-ethanolamine (N(CH₂CH₂OH)₃, TEA) in excess ethylene glycol. The precursor is dissolved in ethanol, and an atom-ized spray of the solution is combusted in a specially con-structed flame spray apparatus. Combustion occurs at ∼2000°C, followed by immediate quenching. This proce-dure provides for a measure of kinetic control over the process. The resulting nanopowder particles are 50–150 nm in diameter and exhibit powder X-ray diffractometry pat-terns similar to β"-alumina. Heating the nanopowder at 30°C/min to 1200°C with a 1 hisotherm converts it to pure β"-alumina. In preliminary sintering studies, green powder compacts (∼65% theoretical density) sintered at 1600°C for 12 min densify to 3.0 ± 0.1 g/cm 3 (∼92% theoretical density) with minimal loss of Na₂O. This procedure offers several processing and cost advantages over conventional β"-alumina syntheses.     

有机硅高沸物制备β-SiC粉体的初步研究

以有机硅高沸物为原料高温热解制备β—SiC粉体。实验证明：有机硅高沸物在1450℃下晶化2h，可以得到晶型较好的β—SiC，用Pt和FeSO4作为复合催化剂可有效提高有机硅高沸物的陶瓷转化率。     

碳化硅材料的氧化及抗氧化研究

本文在简要介绍SiC材料的氧化机理之上，就人们在改善SiC材料的抗氧化性能方面的工作做了一个小结。     

Fabrication of 2D C/ZrC–SiC composite and its structural evolution under high-temperature treatment up to 1800 °C

Two-dimensional C/ZrC–SiC composites were fabricated by chemical vapor infiltration (CVI) process combined with a modified polymer infiltration and pyrolysis (PIP) method. Two kinds of ZrC slurries (ZrC aqueous slurry and ZrC/polycarbosilane slurry) were employed to densify composites before the PIP process. The as-produced C/ZrC–SiC composites exhibited better mechanical properties than the C/SiC composites densified only by CVI and PIP process. Structural evolution for C/ZrC–SiC composites treated in the range 1200–1800 °C mainly consisted of the change of SiC whiskers and the decomposition of polymer derived ceramic.     

Oxidation Behavior of ZrB2–SiC Composites at Low Pressures

ZrB₂‐60 mol%SiC composite with a eutectic microstructure was oxidized at 1573 to 1873 K with reduced total pressures (P_tot) and low oxygen partial pressures (). The mass change was continuously measured by a thermobalance, and then fit with a multiple paralinear model. Oxidation scale of SiO₂/ZrO₂+SiO₂/ZrO₂/ZrB₂ was formed at  > 0.13 kPa, whereas only porous ZrO₂ remained at  < 0.13 kPa, P_tot < 1.33 kPa and higher than 1773 K. With increasing , the parabolic oxidation constant decreased, whereas the linear oxidation constant increased.     

Preparation of C/C‐SiC Composites from All‐Cellulose Precursors

All‐cellulose composites (ACCs) are manufactured from high‐performance cellulose fibers and a cellulose‐containing ionic liquid (IL) as matrix‐forming dope via wet‐winding processes, using different concentrations of cellulose in the IL. ACCs are carbonized at 1650 °C and then infiltrated with liquid silicon. Application of a carbonization aid (ammonium dihydrogenphosphate, ADHP) substantially improves the carbon yield after carbonization but also results in the depletion of the mechanical properties of the final carbon/carbon silicon carbide (C/C‐SiC) material. The microstructure of the porous carbon/carbon preforms strongly depends on both the concentration of cellulose in the IL and the concentration of ADHP. A C/C‐SiC composite manufactured from 6 wt% cellulose in the matrix‐forming dope, in the absence of ADHP, has a maximum flexural strength of 60 MPa. New C/C‐SiC composites with different shapes including Z‐profiles and tubes are successfully manufactured from pre‐shaped ACC precursors. These composites keep their shape during carbonization and the final siliconization process step.     

碳化硅纤维高温抗氧化性研究进展

SiC纤维作为SiC_f/SiC复合材料的重要承载部分,在高温氧化环境下的微观结构演变和性能变化直接影响SiC纤维的实际应用。本文综述了SiC纤维的氧化机理和氧化模型、氧化行为的影响因素以及提高抗氧化性的方法。根据氧分压将SiC纤维的氧化行为分为被动氧化与主动氧化;氧化环境如水氧环境下的高温氧化加快了SiC纤维氧化层厚度的增加和裂纹的产生,致使SiC纤维的力学性能下降;SiC纤维的自身组成与微观结构也会对氧化结果产生各不相同的影响。本文对SiC纤维在高温环境下的应用具有一定的借鉴作用。     

Oxidation protection of CaO–ZrO2–C refractories by addition of SiC

The effect of SiC used as antioxidant in carbon-containing CaO–ZrO₂ refractories and the behaviour of SiC in CO gas were studied. SiC was found to react initially with CO to form SiO₂(s) and C(s) at 1200 °C, and then the formed SiO₂ reacted with CaO in the refractories to form belite (2CaO·SiO₂). The refractory microstructure was modified by addition of SiC. Due to the deposition of SiO₂ in the large (2–10 μm) pores of the refractory through the reaction of SiO(g) with CO, the percentage of large pores decreased and a dense layer, mainly consisting of belite, was formed near the surface of the refractory after it was heated at high temperature (1500 °C). The oxidation resistance of CaO–ZrO₂–C refractories was improved by reaction of SiC with CO to deposit C(s) and decrease the size of the large pores. The oxidation resistance of such refractories can be improved significantly when such a dense layer is formed near their surfaces.     

有机前驱体中添加ZrB2和SiC微粉制备Cf/SiC-ZrB2复合材料

通过在有机前驱体溶液中加入惰性填料ZrB_2和SiC微粉,制备了C_f/SiC-ZrB_2复合材料。分别研究了三组不同含量的料浆对复合材料浸渍裂解效果的影响,并借助扫描电镜(SEM)和能谱分析(EDS)对制备的Cf/SiC-ZrB2复合材料的微观结构和元素组成进行了分析。研究表明:在有机前驱体溶液中添加无机粉体浸渍复合材料能够起到缩短制备周期、提高材料强度的目的。当加入惰性填料的质量分数为15%时,能够在8个制备周期内将复合材料的密度快速提升到2.0g?cm~(-3),而且制备的材料内部结构致密,力学性能优异。     

Oxidation Behavior of SiC Whiskers at 600–1400°C in Air

The oxidation behavior of SiC whiskers (SiC_W) with a diameter size of 50–200 nm has been investigated at 600°C–1400°C in air. Experimental results reveal that SiC_W exhibit a low oxidation rate below 1100°C while a significant larger oxidation rate after that. This can be attributed to the small diameter size of SiC_W, which determines that it is hard to form a protective SiO₂ layer thick enough to hamper the diffusion of oxygen effectively. Both nonisothermal and isothermal oxidation kinetics were studied and the apparent oxidation energy was calculated to further understand the oxidation behavior of the SiC_W.     

Resistance to Thermal Shock and to Oxidation of Metal Diborides–SiC Ceramics for Aerospace Application

Two SiC-containing metal diborides materials, classified in the ultra-high-temperature ceramics (UHTCs) group, were fabricated by hot-pressing. SiC, sinterability apart, promoted resistance to oxidation of the diboride matrices. Both the compositions, oxidized in air at 1450°C for 1200 min, had mass gains lower than 5 mg/cm². Slight deviations from parabolic oxidation kinetics were seen. The resistance to thermal shock (TSR) was studied through the method of the retained flexure strength after water quenching (20°C of bath temperature). Experimental data showed that the (ZrB₂+HfB₂)–SiC and the ZrB₂–SiC materials retained more than 70% of their initial mean flexure strength for thermal quenchs not exceeding 475° and 385°C, respectively. Certain key TSR properties (i.e., fracture strength and toughness, elastic modulus, and thermal expansion coefficient) are very similar for the two compositions. The observed superior critical thermal shock of the (ZrB₂+HfB₂)–SiC composite was explained in terms of more favorable heat transfer parameters conditions that induce less severe thermal gradients across the specimens of small dimensions (i.e., bars 25 mm × 2.5 mm × 2 mm) during the quench down in water. The experimental TSRs are expected to approach the calculated R values (196° and 218°C for ZrB₂+HfB₂–SiC and ZrB₂–SiC, respectively) as the specimen size increases.     

Growth Mechanism of Nanometer-Sized SiC and Oxidation Resistance of SiC-Coated Diamond Particles

Diamond particles were coated with a thin SiC layer by the reaction of SiO vapor with diamond, and the growth mechanism of SiC as well as the oxidation resistance of the SiC-coated diamond were studied. The growth process of the SiC layer can be separated into two steps. In the first step, a thin layer of SiC with a thickness of about 15 nm is formed due to the reaction between SiO vapor and diamond. In the second step, nanometer-sized SiC granules are deposited on the SiC layer by the reaction between SiO vapor and CO. The apparent activation energy for the formation of SiC layer on diamond was found to be 100 kJ/mol. This value suggests that the SiC coating process occurred mainly by vapor-phase reaction. The oxidation resistance of the SiC-coated diamond was improved depending on the thickness of the SiC layer. Oxidation of the SiC-coated diamond particles began at 950°C, which was 400°C higher than that of uncoated diamond.