High temperature sintering of SiC with oxide additives: I. Analysis in the SiC–Al2O3 and SiC–Al2O3–Y2O3 systems

The vaporization behaviour of pure Al₂O₃, Y₂O₃ and SiC as well as SiC–Al₂O₃ and SiC–Al₂O₃/Y₂O₃ mixtures has been analysed by thermodynamic calculations in an open system. Pure Al₂O₃ and Y₂O₃ evaporate congruently in the 1200–2300 K temperature range. Pure SiC vaporizes in a non-congruent manner leading to graphite formation as by-product. A SiC–Al₂O₃ mixture evaporates congruently according to the main vaporization reaction, 2 SiC(s) + Al₂O₃(s) +Al₂O(g) ⇆ 2 SiO(g) + 2 CO(g) +4 Al(g), but the overall composition changes: for SiC rich samples, the mixture tends towards pure SiC in time, and for Al₂O₃ rich samples towards pure Al₂O₃. A SiC–Al₂O₃/Y₂O₃ mixture shows similar behaviour.     

Creep behaviour of Al2O3–SiC nanocomposites

Compared with monolithic fine grained Al₂O₃, Al₂O₃ nanocomposites reinforced with SiC nanoparticles display especially high modulus of rupture as well as reduced creep strain. Taking into account the fracture mode change, the morphology of ground surfaces showing plastic grooving, the low sensitivity to wear and the low dependence of erosion rate with grain size, it can be reasonably assumed that the strength improvement is associated with an increase of the interface cohesion (due to bridging by SiC particles) rather than with a grain size refinement involving substructure formation (as initially suggested by Niihara). In the present work, creep tests have been performed and the results agree with such a reinforcement of the mechanical properties by SiC particle bridging Al₂O₃–Al₂O₃ grain boundaries. Indeed, particles pinning the grain boundaries hinder grain boundary sliding resulting in a large improvement in creep resistance. In addition, SiC particles, while counteracting sliding, give rise to a recoverable viscoelastic contribution to creep. Because of the increased interface strength, the samples undergoing creep support stress levels, greater than the threshold value required to activate dislocation motion. The high stress exponent value as well as the presence of a high dislocation density in the strained materials suggests that a lattice mechanism controls the deformation process. Finally, a model is proposed which fits well with the experimental creep results.     

Effect of La2O3 addition on long-term oxidation kinetics of ZrB2–SiC and HfB2–SiC ultra-high temperature ceramics

Long-term oxidation kinetics of SiC-reinforced UHTCs and La₂O₃-doped UHTCs over an intermediate temperature range (1400–1600 °C) reveal partially protective behavior for the former characterized by an oxidation kinetic exponent 1 < n < 2. In addition, unstable oxidation behavior was observed in HfB₂-based UHTCs due to the presence of SiC agglomerates. On the other hand, La₂O₃-doped UHTCs were found to be protective over the whole temperature range studied (n = 2), in particular at 1600 °C, where oxidation kinetic exponents as high as 8 were observed as a consequence of formation of new oxidation protective particles, MeO_xC_y, where Me is Zr, Hf or Si. Adsorption of oxygen-containing species formed protective MeO_xC_y phases, which enhanced the thermal stability of the oxide scale as well as providing protection against oxidation for long exposure times at 1600 °C.     

In-situ fabrication of Al2O3–SiC nanocomposites using B2O3 as sintering aid

Al₂O₃–SiC nanocomposites with 5 and 10 vol% SiC have been in-situ fabricated by sol-gel method followed by carbothermal reduction of alumina–silica gel using B₂O₃ as sintering aid. Green bodies were formed by cold isostatic pressing of calcined gel, which was prepared by an aqueous sol-containing aluminum chloride, TEOS, sucrose and boric acid. Pressureless sintering was carried out in Ar–12%H₂ atmosphere at 1700 °C. Addition of B₂O₃ (1 or 3 wt%) was an effective densification aid in the Al₂O₃–5 vol% SiC composites, while the densification of Al₂O₃–10 vol% SiC composites was not affected by adding B₂O₃. The composite material containing 5 vol% SiC doped with 3 wt% B₂O₃ reached 98.7% of full density. Nano-sized β-SiC particles were formed in-situ by means of a reaction between mullite and carbon at 1600 °C. Scanning electron microscopy revealed that the spherical in-situ synthesized SiC nanoparticles were well distributed through the composite and located predominantly to the interior of alumina matrix grains.     

Fabrication and microstructure of Al2O3–ZrO2(3Y)–SiC nanocomposites

Al₂O₃–ZrO₂(3Y)–SiC composite powder was prepared by the heterogeneous precipitation method. Calcinating temperature of the powder was important to obtain dense sintered body. The nanocomposites were got by hot-pressing, and addition of ZrO₂ did not raise the sintering temperature. Some Al₂O₃ grain shape was elongated, and Al₂O₃ grain size was about μm. Nano SiC particles were observed uniformly distributing throughout the composites, and most of them were located within the matrix grains. Because SiC particles located within ZrO₂ grains influenced the phase transformation of ZrO₂, the sintering of nanocomposites, which controlled grain size and transformable ZrO₂ amount, become important to get high performance. The strength of 80 wt% Al₂O₃–15 wt% ZrO₂–5 wt% SiC nanocomposites was 555 MPa, and toughness was 3·8 MPa m^1/2, which were higher than those of monolithic Al₂O₃ ceramics. ©     

Degradation mechanism of near stoichiometric SiC fibers after air and Ar–H2O–O2 corrosion at 1000–1500°C

The near stoichiometric SiC fiber has been reported to play significant roles in the application of aeroengine field. An in-depth understanding on the degradation mechanism of the fiber during its corrosion in air and under a simulated aeroengine environment (P_H2O:P_O2:P_Ar = 14:8:78 kPa) will shine a light on the performance evaluations of the near stoichiometric SiC fiber-based materials as well as the development of their potential applications. In this study, X-ray diffraction, scanning electron microscope, and FIB-TEM were utilized to analyze the mechanical properties and microstructure of the fiber. After oxidation in dry air and Ar–H₂O–O₂ for 1 h, respectively, the fiber strength retention rate has been found to decrease with the increased oxidation temperature. The raise in oxidation temperature also led to the increase of the thickness and the crystallization rate of the oxide scale. The most different oxidation behaviors of SiC being treated under the simulated environment than in air are the lower oxidation activation energy and the higher crystallization activation energy for cristobalite. Water vapor can promote the oxidation reaction and inhibit the crystallization of cristobalite in the oxide scale. Few significant differences have been observed otherwise in the oxidation process and oxidation chromatography crystallization mechanism of fibers being treated under different conditions. The increase of oxide layer thickness and the formation of cristobalite impair the structural integrity and compactness of the oxide scale and thus lead to the deterioration of the mechanical properties of SiC fibers. Therefore, it is proposed that oxidation resistance of SiC fiber can be improved by insulating the reaction between the oxidizing agents and the SiC fiber or by increasing the crystallization temperature of cristobalite in the oxidation process and reducing the crystallization rate.     

Pressure-less joining of SiCf/SiC composites by Y2O3–Al2O3–SiO2 glass: Microstructure and properties

In this study, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass was prepared from Y₂O₃, Al₂O₃, and SiO₂ micron powders. Thermal expansion coefficient of as-obtained YAS glass was about 3.9 × 10⁻⁶, matching-well with that of SiC_f/SiC composites. SiC_f/SiC composites were then brazed under pressure-less state by YAS glass and effects of brazing temperature on microstructures and properties of resulting joints were investigated. The results showed that glass powder in brazed seam sintered and precipitated yttrium disilicate, cristobalite, and mullite crystals after heat treatment. With the increase in temperature, joint layer gradually densified and got tightly bonded to SiC_f/SiC composite. The optimal brazing parameter was recorded as 1400 °C/30 min and shear strength of the joint was 51.7 MPa. Formation mechanism of glass-ceramic joints was proposed based on combined analysis of microstructure and fracture morphology of joints brazed at different temperatures. Thermal shock resistance testing of joints was also carried out, which depicted decline in shear strength with the increase of thermal shock times. The strength of the joint after three successive thermal shock cycles at 1200 °C was 35.6 MPa, equivalent to 69% of that without thermal shock.     

Electrical conductivity of spark plasma sintered Al2O3–SiC and Al2O3-carbon nanotube nanocomposites

The electrical conductivity of alumina-silicon carbide (Al₂O₃–SiC) and alumina-multiwalled carbon nanotube (Al₂O₃-MWCNT) nanocomposites prepared by sonication and ball milling and then consolidated by spark plasma sintering (SPS) is reported. The effects of the nanophase (SiC and MWCNTs) and SPS processing temperature on the densification, microstructure, and functional properties were studied. The microstructure of the fabricated nanocomposites was investigated using field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The phase evolution was determined using X-ray diffraction (XRD). The room-temperature direct current (DC) electrical conductivity of the monolithic alumina and nanocomposites was determined using the four-point probe technique. The EDS mapping results showed a homogenous distribution of the nanophases (SiC and MWCNTs) in the corresponding alumina matrix. The room-temperature DC electrical conductivity of monolithic alumina was measured to be 6.78 × 10⁻¹⁰ S/m, while the maximum electrical conductivities of the alumina-10 wt%SiC and alumina-2wt%MWCNT samples were 2.65 × 10⁻⁵ S/m and 101.118 S/m, respectively. The electrical conductivity increased with increasing nanophase concentration and SPS temperature. The mechanism of electrical conduction and the disparity in the electrical performance of the two investigated nanocomposite systems (alumina-SiC and alumina-MWCNT) are clearly described.     

AlN-Pr2O3液相烧结SiC陶瓷

以AlN、Pr2O3做为SiC陶瓷液相烧结的复合助剂,选定不同的助剂含量(5wt％～ 20wt％)和不同的助剂摩尔比例(Pr2O3/AlN=1/3、1/1、3/1),在1800～2000℃温度下,采用热压和无压烧结的方法制备SiC陶瓷样品,并对这些陶瓷样品的性能进行了研究.实验结果表明,助剂比1/3组的样品显示出更有效地促进SiC陶瓷致密化,该组样品无压烧结最大相对密度为87％,热压烧结具有最高的相对密度96.1％、维氏硬度23.4 GPa、抗弯强度549.7MPa、断裂韧性5.36 MPa·m1/2,显微结构中可观察到晶粒拔出现象,断裂模式为沿晶断裂.     

Processing–microstructure–properties relationships of MoSi2–SiC composites

Silicon carbide green bodies with and without carbon-fibre reinforcement have been infiltrated with MoSi₂–Si–X in order to produce high-temperature resistant materials. X is Cr, Ti, Al or B respectively. By adding silicon and one of these components to MoSi₂ the melting point is lowered dramatically. The composites therefore could be gained by melt infiltration at max. 1600 °C. During infiltration the additives react within the infiltrated body with carbon or silicon to form high-temperature resistant carbides or silicides. Thermodynamic calculations have been performed to analyse the reactions during infiltration. The infiltration parameters have been studied with respect to the resulting microstructure and properties. By fitting the amount of additives to the quantity of carbon in the SiC-body (or vice versa) no decrease in strength could be observed up to 1500 °C. The fracture toughness can be increased by the use of high-modulus carbon fibres. The most promising X-element for a high-temperature resistant material is titanium.     

Creep of SiC–SiC microcomposites

The creep behavior of SiC/C/SiC microcomposites at 1200–1400 °C and 140–450 MPa was investigated in the presence and absence of matrix cracking. The microcomposites consisted of single Hi Nicalon or Carborundum fibers coated with a CVD carbon interlayer and a CVD SiC matrix. Since the fibers and matrix had been examined by the identical experimental technique, direct comparisons of the creep of the composite and of the constituents were performed. The creep of uncracked microcomposites was successfully modeled using a simple rule of mixtures algorithm. When matrix cracks were present, the microcomposites were modeled using a series composite consisting of intact microcomposite, exposed fiber at the matrix crack, and the debonded region in between. Trends for behavior with respect to the various mechanical and structural parameters that control creep are presented.     

Preparation and properties of porous SiC–Al2O3 ceramics using coal ash

In this paper, we first reported that porous SiC–Al₂O₃ ceramics were prepared from solid waste coal ash, activated carbon, and commercial SiC powder by a carbothermal reduction reaction (CRR) method under Ar atmosphere. The effects of addition amounts of SiC (0, 10, 15, and 20 wt%) on the postsintering properties of as-prepared porous SiC–Al₂O₃ ceramics, such as phase composition, microstructure, apparent porosity, bulk density, pore size distribution, compressive strength, thermal shock resistance, and thermal diffusivity have been investigated. It was found that the final products are β-SiC and α-Al₂O₃. Meanwhile, the SEM shows the pores distribute uniformly and the body gradually contacts closely in the porous SiC–Al₂O₃ ceramics. The properties of as-prepared porous SiC–Al₂O₃ ceramics were found to be remarkably improved by adding proper amounts of SiC (10, 15, and 20 wt%). However, further increasing the amount of SiC leads to a decrease in thermal shock resistance and mechanical properties. Porous SiC–Al₂O₃ ceramics doped with 10 wt% SiC and sintered at 1600°C for 5 hours with the median pore diameter of 4.24 μm, room-temperature compressive strength of 21.70 MPa, apparent porosity of 48%, and thermal diffusivity of 0.0194 cm²/s were successfully obtained.     

Stability in the system CaO–Al2O3–H2O

The solubility of AH₃, CAH₁₀, C₂AH_7.5, and C₃AH₆ was determined experimentally at 7 to 40 °C and up to 570 days. During the reaction of CA, at 20 °C and above initially C₂AH_7.5 formed which was unstable in the long-term. The solubility products calculated indicate that the solubilities of CAH₁₀, C₂AH_7.5 and C₄AH₁₉ increase with temperature while the solubility of C₃AH₆ decreases. Thus at temperatures above 20 °C, C₃AH₆ is stable, while at lower temperature also CAH₁₀ and C₄AH₁₉ are stable, depending on the C/A ratio.At early hydration times, CAH₁₀ can be stable initially at 30 °C and above, as the formation of amorphous AH₃ stabilises CAH₁₀ with respect to C₃AH₆ + 2AH₃. With time, as the solubility AH₃ decreases due to the formation of microcrystalline AH₃, CAH₁₀ becomes unstable at 20 °C and above.     

Chemical Stability of ZnO–Na2O–SO3–P2O5 Glasses

We report on chemical stability and corrosion behavior of highly depolymerized sulfophosphate glasses from the system ZnO–Na₂O–SO₃–P₂O₅ in aqueous solution, providing data on weight loss, ion release rates, and modifications of surface topology as a function of time, temperature and pH value. Observations seem consistent with the previously developed structural model of chemical heterogeneity, where cations Na⁺ and Zn²⁺ cluster selectively in the vicinity of sulfate and phosphate anions, respectively.     

Surface and bulk crystallization in Nd2O3–Al2O3–SiO2–TiO2 glasses

Neodymium aluminosilicate (Nd₂O₃–Al₂O₃–SiO₂; NdAS) glasses have been investigated for the effect of concentration of TiO₂ on the crystallization mechanism and for the effect of surface condition on crystal growth. NdAS glasses with 0–10 wt.% TiO₂ were heat-treated for nucleation and crystal growth and were examined for phase separation and morphology of surface crystals as well as for crystal growth rate. All the glasses exhibit surface crystallization, however, the glass having 8 wt.% TiO₂ also exhibits internal crystallization after a two-stage heat treatment. Surface crystallization was dependent on the condition of the glass surface and the amount of TiO₂. The crystal growth on the cut surface was faster than on the fractured surface and the growth rate in surface increased with increasing TiO₂. The phase separation found in NdAS glasses containing above 8 wt.% TiO₂, was confirmed to be an important factor controlling the internal crystallization process in Nd₂O₃–Al₂O₃–SiO₂–TiO₂ glasses.     

Decomposition reactions in the SiC–Al–Y–O system during gas pressure sintering

The substantial densification, that occurred in the SiC–Al–Y–O system was explained in the present work by analysing possible chemical reactions and their dependence on initial particle associations, i.e. homogeneity of mixing, the physical and chemical state of additives, pressurised sintering environment over the reactants and temperature of sintering. Hydroxyhydrogel powder precursors were found to be better than mechanically mixed SiC–YAG powder and pre-forming of YAG by holding the specimens at the temperature of 1400°C for 2 h were found to be the best. Decomposition reactions within the system could be controlled by using finer SiC and applying gas pressure over the reactants.     

Dielectric Characteristics of Ceramics in BaO–Nd2O3–TiO2–Ta2O5 System

Dielectric ceramics in the BaO–Nd₂O₃–TiO₂–Ta₂O₅ system were prepared and characterized. The ceramics with tungsten–bronze structure based on the compositions Ba₂NdTi₂Ta₃O₁₅ and Ba₅NdTi₃Ta₇O₃₀ had a high dielectric constant (>100) with a lower frequency-dependency when complete densification was achieved; a low dielectric loss was obtained in the former.     

Dielectric Relaxation in CaO–Bi2O3–B2O3 Glasses

Glasses in the system CaO–Bi₂O₃–B₂O₃ (in molar ratio) have been prepared using melt-quenching route. Ion transport characteristics were investigated for this glass using electric modulus, ac conductivity and impedance measurements. The ac conductivity was rationalized using Almond–West power law. Dielectric relaxation has been analyzed based on the behavior of electric modulus behavior. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.76 eV, close to that the activation energy for dc conductivity (1.71 eV) indicating that the same species took part in both the processes. The stretched exponent β (0.5–0.6) is invariant with temperature for the present glasses.     

Si2N2O结合SiC棚板的研制

本文研究分析了SiO2细粉加入量与泥料的颗粒组成对Si2N2O结合SiC材料常规性能与使用性能的影响,并通过X-射线衍射和扫描电镜分析了材料的矿物组成和显微结构。试验表明,Si2N2O结合SiC材料具有比较高的常温与高温抗折强度,并具有良好的抗热震性与抗氧化性能。制作出440×460×12mm的试验板,用于烧卫生洁具隧道窑的棚板。