Formation of β-SiAION as an Intermediate Oxidation Product of SiC–AIN Ceramics

The oxidation mechanisms in SiC-AlN solid solutions, exposed at 1370°C for 200 h in air, have been investigated by scanning electron microscopy (SEM), analytical and high-resolution electron microscopy (HREM), and X-ray diffraction techniques. Five hot-pressed compositions, including pure SiC and pure AIN, were examined. Assuming parabolic rate behavior, the values of the parabolic rate constants based on oxide layer thickness increased by over 2 orders of magnitude by increasing AIN contents from 0% to 62%. A continuous amorphous phase containing cristobalite and mullite crystallites was present at the oxide layer in 13% AIN and 27% AIN samples. Two reaction layers were found in the oxidized SiC–62% AIN solid solution. The inner layer consisted of a mixture of β-SiAION and graphite phases, while the outer layer consisted of mullite as a major phase and cristobalite as a minor phase. The oxidation proceeded in two stages: a partial oxidation of SiC–AIN to β-SiAION and carbon (graphite), and a final oxidation of β-SiAION to mullite + SiO₂.     

Mechanism of the carbonitriding reactions of SiO2–Al2O3 minerals in the Si–Al–O–N system

Ceramics of the Si–Al–O–N system and SiC have a great technological interest because of their good thermomechanical properties at high temperatures. It is possible to obtain phases such as β-SiC, Si₃N₄, β′-sialons, O′-sialons, polytype sialons, AlN, Al₂O₃ or mixtures of these phases by means of carbonitriding reactions starting from minerals such as quartz, diatomite and other aluminosilicate minerals. The knowledge of the mechanism of these reactions permits to establish the necessary conditions to achieve the desired phases in the final product. The mechanisms of the carbonitriding reactions of several minerals with increasing aluminium content are studied. Their compositions are from diatomite up to mullite. Reactions of the mineral carbon mixture were carried out at 1300–1650°C in N₂ atmosphere. The phases formed were identified by X-ray diffraction in qualitative and, in some cases, in quantitative form. Intermediate compounds such as β-SiC, X-phase, mullite, glassy phases and gaseous silicon oxide were observed. The formation and importance of these phases depend on the mineral composition as well as on the reaction conditions (temperature, time, etc.). β-SiC, the main intermediate phase, may remain in the final products and may be the major phase depending on the temperature and the carbon content used. The final products of these reactions are phases of the Si–Al–O–N system. The phases obtained were characterized by EPMA, SEM and BET techniques.     

Effect of SiC whiskers on the anti-oxidation properties of Yb2Si2O7/mullite/SiC tri-layer environmental barrier coating for CMCs

The mullite and ytterbium disilicate (β-Yb₂Si₂O₇) powders as starting materials for the Yb₂Si₂O₇/mullite/SiC tri-layer coating are synthesized by a sol–gel method. The effect of SiC whiskers on the anti-oxidation properties of Yb₂Si₂O₇/mullite/SiC tri-layer coating for C/SiC composites in the air environment is deeply studied. Results show that the formation temperature and complete transition temperature of mullite were 800–1000 and 1300°C, respectively. Yb₂SiO₅, α-Yb₂Si₂O₇, and β-Yb₂Si₂O₇ were gradually formed between 800 and 1000°C, and Yb₂SiO₅ and α-Yb₂Si₂O₇ were completely transformed into β-Yb₂Si₂O₇ at a temperature above 1200°C. The weight loss of Yb₂Si₂O₇/(SiC_w–mullite)/SiC tri-layer coating coated specimens was 0.15 × 10⁻³ g cm⁻² after 200 h oxidation at 1400°C, which is lower than that of Yb₂Si₂O₇/mullite/SiC tri-layer coating (2.84 × 10⁻³ g cm⁻²). The SiC whiskers in mullite middle coating can not only alleviate the coefficient of thermal expansion difference between mullite middle coating and β-Yb₂Si₂O₇ outer coating, but also improve the self-healing performance of the mullite middle coating owing to the self-healing aluminosilicate glass phase formed by the reaction between SiO₂ (oxidation of SiC whiskers) and mullite particles.     

In-situ synthesis and textural evolution of the novel carbonaceous SiC/mullite aerogel via polymer-derived ceramics route

A novel carbonaceous SiC/mullite composite aerogel is derived from catechol-formaldehyde/silica/alumina hybrid aerogel (CF/SiO₂/AlOOH) via polymer-derived ceramics route (PDCR). The effects of the reactants concentrations on the physicochemical properties of the carbonaceous SiO₂/Al₂O₃ aerogel and SiC/mullite aerogel are investigated. The mechanism of the textural and structural evolution for the novel carbonaceous SiC/mullite is further discussed based on the experimental results. Smaller reactants concentration is favorable to formation of mullite. Reactants concentration of 25% is selected as the optimal condition in considering of the mullite formation and bulk densities of the preceramic aerogels. Spherical large silica particles are also produced during heat treatment, and amorphous silica is remained after this reaction. With further heat treatment at 1400 °C, silicon carbide and mullite coexist in the aerogel matrix. The mullite addition decreases the temperature of SiC formation, when compared with the conventional methods. However, after heat treatment at 1450 °C, the amount of mullite begins to decrease due to the further reaction between carbon and mullite, forming more silicon carbide and alumina. The carbonaceous SiC/mullite can be transferred to SiC/mullite binary aerogel after carbon combustion under air atmosphere. The carbonaceous SiC/mullite has a composition of SiC (31%), mullite (19.1%), SiO₂ (14.4%), and carbon (35%). It also possesses a 6.531 nm average pore diameter, high surface area (69.61 m²/g), and BJH desorption pore volume (0.1744 cm³/g). The oxidation resistance of the carbonaceous SiC/mullite is improved for 85 °C when compared with the carbon based aerogel.     

莫来石结合碳化硅高温吸热陶瓷抗氧化性能的研究

以碳化硅及合成莫来石微粉为主要原料,制备了用于非真空太阳能吸热管的莫来石结合碳化硅高温陶瓷涂层。针对碳化硅基材料高温氧化问题,测定了样品的烧成增重率及亮度并结合XRD、SEM研究了莫来石结合碳化硅陶瓷的抗氧化性能。结果表明,莫来石添加量为20%,经1 380℃烧成样品的抗氧化性最好,其增重率为7.49%,亮度值为46.61。XRD分析烧结体主晶相为碳化硅(α-SiC)和莫来石(3Al2O3.2SiO2),并含有少量的方石英(SiO2),莫来石作为结合相在碳化硅晶粒周围形成"骨架",与SiO2玻璃相形成三围的网状保护层包裹在碳化硅表面,阻止碳化硅氧化。     

Wet-oxygen corrosion resistance and mechanism of bi-layer Mullite/SiC coating for Cf/SiC composites

A bi-layer oxidation-resistant coating consisting of a mullite outer coating, and a SiC inner coating on the surface of C_f/SiC composites was prepared by the chemical vapour deposition and an air spray sol-gel process, and its corrosion behavior was evaluated in a wet-oxygen coupling environment. Results show that the formation of SiO₂ glass layer and its reaction with mullite particles to form aluminosilicate glass layer, leading to an increase in the density of the mullite outer coating, so that the weight loss of bi-layer Mullite/SiC coating coated C/SiC sample was only 1.11 × 10^?3 g·cm^?2 in the first 100 h of oxidation. However, the weight loss of the coated sample reached 26.82 × 10^?3 g·cm^?2 after 200 h of oxidation due to a part of the mullite outer coating was detached. The SiO₂ glass phase reacted with water vapour to generate gaseous Si(OH)_x, which created distinct holes on the surface of the SiO₂ glass layer or inside the molten aluminosilicate glass layer. Eventually, the mullite outer coating was blistered and detached from the surface of the sample due to the combination and growth of holes.     

Coal Slag Protection of Silicon Carbide with Chemically Vapor Deposited Mullite Coatings

The corrosion characteristics of bulk alumina, SiC, mullite, and CVD mullite coatings on SiC in contact with coal slag were investigated. Uncoated SiC corroded in the presence of coal slag, forming mixed FeSi phases and carbon. Bulk Al₂O₃ and slag formed a diffusional phase believed to be the spinel hercynite (Fe,Mg)O·(Al,Fe)₂O₃. After exposure to coal slag, a compositional difference was observed at bulk mullite/coal slag interfaces, yet this diffusional phase did not appreciably degrade the mullite samples and no cracking was observed. CVD mullite coatings offered protection to SiC in a simulated coal gasification atmosphere with corrosion protection dependent on the uniformity of the coating. Microprobe analysis of the CVD mullite coating/slag interface showed the formation of a Fe(Mg)Al.     

Recycling of waste red mud for fabrication of SiC/mullite composite porous ceramics

SiC/mullite composite porous ceramics were fabricated from recycled solid red mud (RM) waste. The porous ceramics were formed using a graphite pore forming agent, RM, Al(OH)₃ and SiC in the presence of catalysts. The influence of firing temperature and the pore-forming agent content on the mechanical performance, porosity and the microstructure of the porous SiC ceramics were investigated. Optimal preparation condition were determined by some testing. The results indicated that the flexural strength of specimens increased as a function of firing temperature and a reduction in graphite content, which concomitantly decreased porosity. The ceramic prepared under optimal conditions having 15?wt% graphite and sintered at 1350?°C, demonstrated excellent performance. Under optimal preparation conditions the flexural strength and porosity of the ceramic were 49.4?MPa and 31.4%, respectively. Scanning electron microscopy observation result showed that rod-shape mullite grains endowed the samples with high flexural strength and porosity. X-ray diffraction analysis indicated that the main crystallization phases of the porous ceramics were 6H-SiC, mullite, cristobalite and alumina. This work demonstrates that RM can be sucessfully reused as a new raw material for SiC/mullite composite porous ceramics.     

CVD Mullite Coatings in High-Temperature, High-Pressure Air–H2O

Crystalline mullite was deposited by chemical vapor deposition (CVD) onto SiC/SiC composites overlaid with CVD SiC. Specimens were exposed to isothermal oxidation tests in high-pressure air + H₂O at 1200°C. Unprotected CVD SiC formed silica scales with a dense amorphous inner layer and a thick, porous, outer layer of cristobalite. Thin coatings (∼2 μm) of dense CVD mullite effectively suppressed the rapid oxidation of CVD SiC. No microstructural evidence of mullite volatility was observed under these temperature, pressure, and low-flow-rate conditions. Results of this preliminary study indicate that dense, crystalline, high-purity CVD mullite is stable and protective in low-velocity, high-pressure, moisture-containing environments.     

Enhanced mechanical properties of lightweight Al2O3-C refractories reinforced by combined one-dimensional ceramic phases

We prepared a new lightweight Al₂O₃-C refractory material with a higher strength by using microporous corundum aggregates instead of dense tabular corundum aggregates, which was reinforced by in situ formed SiC whiskers, multi-walled carbon nanotubes (MWCNTs), and mullite rods. A comparative study of the microstructure, mechanical properties, and fracture behavior was carried out for dense and lightweight Al₂O₃-C refractories coked at 1200°C and 1400°C, respectively. By using the microporous corundum aggregates, a better aggregate/matrix interface bonding and an optimized distribution of SiC whiskers were obtained. The SiC whiskers formed inside the microporous corundum aggregates and simultaneously in the matrix by a vapor-solid reaction mechanism, resulting in an enhancement at the microporous aggregate/matrix interface. Furthermore, the in situ formed MWCNTs and well-developed mullite rods at 1200°C in the matrix also contributed to the better interface structure. Thus, due to the improved microporous aggregate/matrix interface, the crack propagation along the aggregate/matrix interface was suppressed, resulting in an increased crack propagation within the aggregates. Consequently, the synergy between microporous corundum aggregates and combined one-dimensional ceramic phases caused a lower bulk density but a markedly higher strength, a higher fracture energy, and a higher toughness of lightweight Al₂O₃-C refractories compared to the dense ones. Overall, our study allows to overcome the traditional concept that a higher strength of refractories is reached by a higher density.     

Bonding strength and thermal shock resistance of a novel bilayer (c-AlPO4-SiCw-mullite)/SiC coated carbon fiber reinforced CMCs

Mullite coating, SiC whiskers toughened mullite coating (SiC_w-mullite), and cristobalite aluminum phosphate (c-AlPO₄) particle modified SiC_w-mullite coating (c-AlPO₄-SiC_w-mullite) were prepared on SiC coated C/SiC composites using a novel sol-gel method combined with air spraying. Results show that molten SiO₂ formed by the oxidation of SiC whiskers and molten c-AlPO₄ improved the bonding strength between mullite outer coating and SiC–C/SiC composites due to their high-temperature bonding properties. The bonding strength between mullite, SiC_w-mullite, c-AlPO₄-SiC_w-mullite outer coatings and SiC–C/SiC composites were 2.41, 4.31, and 7.38 MPa, respectively. After 48 thermal cycles between 1773 K and room temperature, the weight loss of mullite/SiC coating coated C/SiC composites was up to 11.61%, while the weight losses of SiC_w-mullite/SiC and c-AlPO₄-SiC_w-mullite/SiC coatings coated C/SiC composites were reduced to 7.40% and 5.12%, respectively. The addition of appropriate SiC whiskers can considerably improve the thermal shock resistance of mullite coating owing to their excellent mechanical properties at high temperature. In addition, c-AlPO₄ particles can further improve the thermal shock resistance of SiC_w-mullite coating due to their high-temperature bonding and sealing properties. No obvious micro-pores and cracks were observed on the surface of c-AlPO₄-SiC_w-mullite coating after 48 thermal cycles due to timely healing effect by formation of secondary mullite.     

Microstructural Studies in Alkoxide-Derived Mullite/Zirconia/Silicon Carbide-Whisker Composites

Mullite composites toughened with ZrO₂ (with or without a MgO or Y₂O₃ stabilizer) and/or SiC whiskers (SiC( w )) were fabricated by hot-pressing powders prepared from Al, Si, Zr, and Mg(Y) alkoxide precursors by a sol–gel process. Micro-structures were studied by using XRD. SEM, and analytical STEM. Pure mullite samples contained prismatic, preferentially oriented mullite grains. However, the addition of ZrO₂, as well as the hot-pressing temperature, affected the morphology and grain size in the composites; a fine, uniform, equiaxed microstructure was obtained. The effect of SiC( W ) was less pronounced than that of ZrO₂. Glassy phases were present in mullite and mullite/SiC( W ) composites, but were rarely observed in Al₂O₃-rich or ZrO₂-containing samples. The formation of zircon due to the reaction between ZrO₂ and SiO₂ and the considerable solid solution of SiO₂ in ZrO₂ prevented the formation of the glassy phase, whereas the reaction between Al₂O₃ and MgO in MgO-containing samples formed a spinel phase and also deprived the ZrO₂ phase of the stabilizer. Intergranular ZrO₂ particles were either monoclinic or tetragonal, depending on size and stabilizer content; small intragranular ZrO₂ inclusions were usually tetragonal in structure.     

Oxidation of Silicon Carbide-Reinforced Oxide-Matrix Composites at 1375° to 1575°C

Oxidation studies were conducted on Al₂O₃-SiC and mullite-SiC composites at 1375° to 1575°C in O₂ and in Ar-1% O₂. The composites were prepared by hot-pressing mixtures of Al₂O₃ or mullite and SiC powders. The reaction products contained alumina, mullite, an aluminosilicate liquid, and gas bubbles. The parabolic rate constants were about 3 orders of magnitude higher than those expected for the oxidation of SiC. Higher rates are caused by higher oxygen permeabilities through the reaction products than through pure silica. Our results suggest that oxygen permeabilities are comparable in the three condensed phases observed in the reaction products.     

Reactive Synthesis and Phase Stability Investigations in the Aluminum Nitride–Silicon Carbide System

The effect of AlN on the structure formation of SiC was investigated. SiC was synthesized in the presence of AlN under vacuum at 1500°C, and the result was cubic SiC. The synthesis of AlN–SiC composites through the reaction Si₃N₄+ 4Al + 3C = 3SiC + 4AlN was also investigated and compared with synthesis via field-activated self-propagating combustion (FASHS). Reactants were heated in a vacuum furnace at temperatures ranging from 1130° to 1650°C. Below 1650°C, the reaction is not complete and at this temperature the product phases are AlN and cubic SiC. At 1650°C, the product contained an outer layer which contained β-SiC only and an inner region which contained AlN and cubic SiC. 2H-SiC and AlN composites synthesized via field-activated self-propagating combustion were annealed at 1700°C under vacuum. The AlN dissociated and evaporated and the 2H-SiC transformed to the cubic β phase. Reasons for the differences in products of furnace heating and FASHS are discussed.     

SiC_w/莫来石和SiC_w/Y-TZP/莫来石复合材料的力学性能与显微结构

以莫来石为基体,SiC晶须(SiC_w)和Y-TZP(Y_2O_3稳定的四方ZrO_2多晶)为两种补强剂,采用热压烧结工艺,制备SIC_w/莫来石和SIC_w/Y-TZP/英来石复合材料。研究了复合材料的力学性能与显微结构,并对强化增韧机制进行了分析。结果表明,SiC晶须补强莫来石,可以改善其强度和断裂韧性。若SiC晶须和Y-TZP共同补强英来石,则可以进一步提高其强度和断裂韧性。晶须引起裂纹偏转,晶须拔出以及由ZrO_2相变引起的微裂纹增韧是该复合材料的主要增韧机制。SiC晶须和Y-TZP两种补强剂的共同作用,对莫来石强度和断裂韧性的提高具有叠加或协同效应。     

Effect of Atmosphere on Weight Loss in Sintered Silicon Carbide during Heat Treatment

Heat treatment was performed on β-SiC with different sintering additives in the temperature range 1873–2073 K, in both argon and nitrogen-gas atmospheres. In the case of the specimens heat-treated at 2073 K in argon, the weight loss was more than the total weight of the sintering additives, except for B,C-doped β-SiC. On the other hand, weight loss was suppressed by about one-third to one-half in nitrogen gas. Weight loss depended mainly on the reaction at the interface between the SiC grains and the grain-boundary phase.     

The change of phase composition in kaolinite- and illite-rich clay-based ceramic bodies

Raw material for ceramics consists mainly of kaolinite, illite, quartz and feldspar. Three representative clays, a high kaolinitic (HB), illitic- and quartz-rich (KW) and naturally mixed kaolinite–illite (P1) clays of Westerwald area, were chosen for this study [Kromer, H., 1980. Tertiary clays in the Westerwald area. Geol. Jb. D. Rhei D Hanover, 69–84]. The largest and oldest clay mining area of Germany is in the Westerwald area. These clays were mixed with each other and also with K, and Ca–Na feldspar. The high temperature phases of the mixed bodies were of three groups: crystalline phase, amorphous/glassy phase and porosity.The aim of this study was to determine: (1) the effect of kaolinite–illite–quartz ratios, (2) the effect of heat treatment and (3) the effect of feldspar on the fired mineralogy of the fired products. The crystalline phases are cristobalite, mullite, quartz, hematite and anatase. The bodies consist of crystalline phases such as quartz, mullite and cristobalite in a composite structure where crystals and pores are often embedded in amorphous/glassy phase. The formation of mullite and cristobalite is very distinctive in kaolinitic clay, and the structure is dominated by the spiky primary mullite. In the illite/sericite-rich mixtures, the high K content causes a large amount of melt superimposed on the mullite formation. The cristobalite formation is completely suppressed in illite/sericite-rich bodies. After dehydroxylation, metakaolinite and illite/sericite anhydride structures are formed. The persistence of illite/sericite anhydride peaks above 950 °C in KW clay indicates the presence of sericite/muscovite mineral. The disappearance temperatures and firing behaviour of K and Ca–Na feldspar observed within the XRD patterns of mixed bodies are different. K feldspar lines disappear earlier in HB bodies than in KW bodies, but Ca–Na feldspar shows a reverse behaviour. While Ca–Na feldspar peak intensity gradually decreases but persists at 1150–1250 °C, K feldspar suddenly disappears at 1150 °C.     

The preparation of mullite foamed ceramics reinforced by in-situ SiC whiskers and their reinforcement mechanism

A SiC whisker-bonded mullite foamed ceramic was prepared by using white clay, industrial alumina and silicon powder as raw materials without solid carbon sources. The XRD, SEM, EDS, and Factsage® software were used to investigate the effect of sintering temperature on the phase composition, microstructure, compressive strength, and Young's modulus of foamed ceramics. Additionally, the synthesis reaction of in-situ SiC whiskers and the effect of their formation on the properties of ceramics were studied. The results showed that the in-situ SiC whiskers with dendrite shapes were formed after firing above 1300 °C at the expense of Si/SiO vapors as well as CO vapor, though there were no solid carbon sources in raw materials, which provided a new idea for the synthesis of SiC whiskers. The formation of SiC whiskers was helpful for improving the compressive strength and Young's modulus of mullite foamed ceramics remarkably. Furthermore, the reinforcement mechanism has been investigated systematically.     

Mullite whisker toughened mullite coating to enhance the thermal shock resistance of SiC pre-coated carbon/carbon composites

In order to improve the thermal shock resistance of the coated carbon/carbon (C/C) composites, a mullite whisker toughened mullite coating was fabricated on the surface of SiC pre-coated C/C composites (SiC-C/C) by molten-salt method with a later hot dipping process. The phase compositions, surface and cross-section microstructures, high temperature thermal shock resistance of the as-prepared multi-layer coatings were investigated. Results show that the introduction of mullite whiskers can effectively improve the density of the mullite outer coating and decrease the cracking of the coating during the thermal shock cycle process. After 100 times thermal shock cycles between 1773 K and room temperature, only 1.87 × 10⁻³ g cm⁻² weight loss has been detected, indicating the achievement of the excellent thermal shock resistance.     

锆莫来石-碳化硅材料反应烧结过程的研究

研究了用锆英石、氧化铝和炭黑的混合物制备原位SiC颗料复合锆莫来石材料的反应烧结进程和显微结构特征。结果表明：反应烧过程中,SiC、莫来石的生成反应滞后于锆莫来石的分解反应;反应前期,SiC的生成占主导作用。反应后期,莫来石的形成及致密化进程占主导作用;材料中存在大量气孔,ZrO3以均匀分布和聚集体两种形式分布于莫来石、SiC及玻璃相构成的基质中。