Ultrafine-grained β-Sialon fabricated by two-stage sintering and study on diffusion toughening of Ti–22Al–25Nb

The ultrafine-grained β-Sialon ceramics were fabricated by spark plasma sintering at different temperatures with inorganic Al₂O₃–Y₂O₃ and Ti–22Al–25Nb intermetallic powder as composite additives. The research showed that β-Sialon ceramics achieve two-stage sintering densification. Al₂O₃–Y₂O₃ inorganic additives promoted the synthesis and densification of β-Sialon ceramics at 1125–1215°C. Ti–22Al–25Nb intermetallic powder diffused Ti and Nb elements at 1240–1425°C, thereby improving the fracture toughness of β-Sialon ceramics. The maximum fracture toughness (∼9.69 MPa m^1/2) under 19.6 N was obtained for β-Sialon ceramics sintered at 1600°C.     

Study on the toughening mechanism of in-situ synthesis (TixZr1−x)B2 in solid-state sintered SiC composite ceramics

High-dense SiC-(Ti_xZr_1?x)B₂ composite ceramics were fabricated by in-situ synthesis of (Ti_xZr_1?x)B₂ solid solution using solid-state spark plasma sintering (SPS). 64 vol% SiC, 20 vol% ZrB₂, 15 vol% TiB₂, and 1 vol% graphite powders are chosen as raw materials. The composite ceramics has the relative density of 99.97 %, the Vickers hardness of 24.71 GPa, the flexure strength of 435 MPa and the fracture toughness of 8.05 MPa ? m^1/2. Compared with the single-phase SiC ceramics and SiC-TiB₂ composite ceramics, the fracture toughness of SiC-(Ti_xZr_1?x)B₂ composite ceramics increased by 242.6 % and 53.6 %, respectively. A shell-core structure is found in the SiC-(Ti_xZr_1?x)B₂ composite ceramics, in which (Ti_xZr_1?x)B₂ solid solution is the core and fine SiC grain is the shell. The results show that the toughening effect of solid-state sintered SiC-(Ti_xZr_1?x)B₂ composite ceramics is attributed to the shell-core structure.     

Preparation,oxidation property and mechanism of Si3N4/O′-SiAlON composite ceramics

The applications of Si₃N₄ ceramics were significantly restricted because of the disastrous failure resulted from the oxidation weight gain. The generation of O′-SiAlON could effectively address this issue. The effect of N₂ gas pressure on the phase evolution of the Si₃N₄/O′-SiAlON was studied. It was found that high N₂ gas pressure (3 MPa) was more favorable for the formation of the O′-SiAlON than low N₂ gas pressure (0.6 MPa). Furthermore, the effects of SiO₂ content on the phase evolution, microstructure, oxidation properties and mechanism of the Si₃N₄/O′-SiAlON ceramics were investigated. The results revealed that the relative content of the O′-SiAlON phase evidently enhanced from 0 wt% to 18.15 wt%, and the bulk density decreased from 3.01 g/cm^?3 to 2.62 g/cm^?3 with an increase in SiO₂ from 0 wt% to 12.5 wt%. Additionally, the weight gain, oxide layer thickness and roughness similarly reduced from 2.02 mg/cm² to 0.85 mg/cm², 133.87 μm to 2.31 μm and 21.91 μm to 6.34 μm, respectively. The addition of SiO₂ could also reduce bubbles and cracks formation and hinder the diffusion of Al and Y elements from the interior to the surface. Finally, the oxidation resistance mechanism was mainly credited to the pinning effect of O′-SiAlON phases at the grain boundaries.     

Effect of Ta2O5 additions on phase formation during synthesis and sintering of β-alumina based ceramics

Conclusions We demonstrated the effect of the Ta₂O₅ additive on the process of phase formation during the synthesis of the powders and during sintering of -alumina ceramics (as compared to stoichiometric sodium polyaluminate Na₂O·5Al₂O₃). The presence of the additive increases the quantity of -Al₂O₃ phase and stabilizes it during low-temperature isothermal synthesis; during high-temperature sintering, it hinders the formation of the nonconducting -Al₂O₃ phase; this is one of the main conditions required for obtaining -alumina ceramics having a high ionic conductivity.Translated from Ogneupory, No. 2, pp. 13–15, February, 1991.     

The effect of rare earth oxides on the pressureless liquid phase sintering of α-SiC

Silicon carbide (SiC) ceramics have been fabricated by pressureless liquid phase sintering with Al₂O₃ and rare-earth oxides (Lu₂O₃, Er₂O₃ and CeO₂) as sintering additives. The effect was investigated of the different types of rare earth oxides on the mechanical property, thermal conductivity and microstructure of pressureless liquid phase sintered SiC ceramics. The room temperature mechanical properties of the ceramics were affected by the type of rare earth oxides. The high temperature performances of the ceramics were influenced by the triple junction grain boundary phases. With well crystallized triple junction grain boundary phase, the SiC ceramic with Al₂O₃–Lu₂O₃ as sintering additive showed good high temperature (1300 °C) performance. With clean SiC grain boundary, the SiC ceramic with Al₂O₃–CeO₂ as sintering additive showed good room temperature thermal conductivity. By using appropriate rare earth oxide, targeted tailoring of the demanding properties of pressureless liquid phase sintered SiC ceramics can be achieved.     

Modelling and optimizing the liquid phase sintering of alumina/CaO–SiO2–Al2O3 ceramics using response surface methodology

Alumina is an attractive material for engineering applications due to its unique properties. In this study, CaO–SiO₂–Al₂O₃ eutectic phase was used as an additive phase and liquid phase sintering of the alumina/CaO–SiO₂–Al₂O₃ samples were investigated. The liquid phase sintering was modelled and optimized by Response Surface Methodology (RSM) using Central Composite Design (CCD) to achieve maximum fracture strength and density as responses. Sintering temperature, alumina particles size distribution (PSD), lubricant and eutectic phase content were selected as independent variables. Two cubic models were developed in terms of these variables to describe the responses. The validity and accuracy of the models were checked using Analysis of Variance (ANOVA).Phase identification of the synthesized eutectic phase was evaluated by XRD and fracture strength of the sintered samples was determined by Ring-on-Ring test method. SEM was used to study the fracture surface of the samples. The obtained models for predicting fracture strength and density of the sintered samples showed high conformity with the experimental results. Sintering temperature and alumina PSD were found as the most effective parameters. Therefore, optimized condition based on the defined constraints was obtained for sintering temperature of 1533 °C, alumina PSD of 25%, and lubricant and eutectic phase content of 1.5 wt% and 7.5 wt%, respectively. Results showed that after ball milling of the eutectic phase, the fracture strength of the optimized ceramic sample was improved and it reached to maximum values at smaller amounts of the additive phase.     

Effects of alumina sols on the sintering of α-alumina ceramics

The effects of two kinds of alumina sols on the densification behavior of sub-micron grain sized α-alumina ceramics have been investigated. Composition of the sol-derived gels was investigated by energy dispersive spectra and Fourier transform infrared spectra. Structural evolution of the gels at different temperatures was characterized by a combination of X-ray diffraction and ²⁷Al magic angle spinning nuclear magnetic resonance spectroscopy. Results showed that the gel containing chlorine and carbon transformed to α-alumina at about 950 °C, significantly lower than the other gel which transformed at about 1050 °C. Density measurements and scanning electron microscopy analyses were used to investigate the sintering of alumina ceramics with or without alumina sols. It was found that the alumina sols had profound effects on the densification of alumina ceramics. The ceramic displayed the best densification behavior when the sol containing chlorine and carbon was added.     

Effect of hexagonal-BN additions on the sliding-wear resistance of fine-grained α-SiC densified with Y3Al5O12 liquid phase by spark-plasma sintering

The effect of flaky hexagonal (h) BN additions (1, 5, and 10 vol.%) on the lubricated sliding-wear behavior of fine-grained, liquid-phase-sintered SiC ceramics fabricated by spark-plasma sintering was investigated. It was found that resistance to the initial mild, deformation-controlled wear decreases with increasing h-BN content in the composite, which progressively exhibits a greater wear rate and a sooner transition to severe wear. This is because the softer h-BN particles reduce the hardness and do not act as internal lubricant, while promoting poorer grain cohesion due to their morphologically-favored segregation at grain boundaries. By contrast, their addition is increasingly beneficial in terms of resistance to the subsequent severe, fracture-controlled wear upon prolonged sliding contact, with a lower wear rate. This is because the flaky h-BN particles increase the fracture toughness, and also act efficiently as external lubricant when pulled-out from the microstructure. Finally, implications for the design of advanced triboceramics are discussed.     

Liquid–liquid equilibrium and mechanism study on separation of short carbon chain hydrocarbon mixtures by Cyrene

The separation of short-chain hydrocarbon mixtures is of great significance for the efficient utilization of fossil energy. Liquid–liquid extraction, as one of the commonly used treatment methods, has significant advantages in terms of operation conditions and energy consumption. As a new dipolar aprotic solvent developed in recent years, dihydrolevoglucosenone (Cyrene) has a wide range of sources and a green composition. In this paper, the liquid–liquid equilibrium and extraction mechanism of Cyrene and five hydrocarbon mixtures with short carbon chains, including toluene/n-heptane, toluene/cyclohexane, n-hexane/cyclohexane, n-pentane/pentene, and n-hexane/hexene, have been studied by combining experiments and quantum chemical calculations, and the extraction effects under different conditions have been investigated. The results showed that the forces between Cyrene and the different solutes are mainly van der Waals (VDW) forces dominated by dispersion forces, with some weak hydrogen bonds present. Due to the difference in interaction energy, the order of extraction selectivity was toluene-n-heptane > toluene-cyclohexane > n-hexane-hexene > n-hexane-cyclohexane > n-pentane-pentene, and the order of distribution coefficients of the extracted components (aromatics, olefins, and cycloalkanes) was toluene > pentene > hexene > cyclohexane. The dissolution processes of all systems were heat-absorbing, and they all reached the extraction equilibrium within 60 s. The reliability of the experimental data was verified using the Othmer–Tobias equation and the Hand equation, and the binary interaction parameters of all systems were obtained by the non-random two liquid (NRTL) model, providing basic data and references for the subsequent studies on the separation of Cyrene and short-chain hydrocarbons.     

Preparation and study of the mechanical and optical properties of infrared transparent Y2O3–MgO composite ceramics

In this study, fine Y₂O₃–MgO composite nanopowders were synthesized via the sol–gel method. Dense Y₂O₃–MgO composite ceramics were fabricated by pre-sintering the green body in air at different temperatures for 1 h and then subjecting the sintered bodies to hot isostatic pressing at 1300°C for 1 h. The effects of pre-sintering temperature on the microstructural, mechanical, and optical properties of the resulting ceramics were studied. The average grain size of the ceramics was increased, whereas their hardness and fracture toughness were decreased with increasing pre-sintering temperature. A maximum fracture toughness of 1.42 MPa·m^1/2 and Vickers hardness of 10.4 GPa were obtained. The average flexural strength of the ceramics was 411 MPa at room temperature and reached 361 MPa at 600°C. A transmittance of 84% in the 3–5 µm region was obtained when the composite ceramics were sintered at 1400°C. Moreover, a transmittance of 76% in the 3–5 µm region was obtained at 500°C.     

Conduction and sintering mechanism of high electrical conductivity Magnéli phase Ti4O7

In this paper, the crystal structure and electronic structure of Ti₄O₇ were calculated based on density functional theory, and Magnéli phase Ti₄O₇ bulks were successfully prepared by spark plasma sintering (SPS). Results indicated that the contribution of Ti 3d to Fermi level increased due to the lack of oxygen atom in lattice, and the energy band gap of Ti₄O₇ was reduced compared with that of TiO₂. By calculating the relationship between the densification rate and effective stress in the process of SPS, it can be known that the densification mechanism of Ti₄O₇ powders was controlled by diffusion. Based on this, under the conditions of sintering temperature of 1000 °C, holding time of 10 min and sintering pressure of 30 MPa, Ti₄O₇ bulks with the optimal electrical conductivity (961.5 S cm⁻¹) could be obtained, which was more than 30% higher than the graphite material reported in literature. The results reveals that Ti₄O₇ will be one of the most promising electrode materials in the electrochemical field.     

Influence of stabilizing ions and sintering process on the thermal conductivity of α-SiAlON ceramics

α-SiAlON ceramics with different stabilizing ions of Yb, Dy, Nd, Y, Ca, and binary stabilizing ions of (Yb + Ca) and (Yb + Nd) were prepared by spark plasma sintering at 1600°C and gas pressure sintering at 1800 and 1900°C, and their thermal conductivity was investigated. It was found that α-SiAlON ceramics with larger and heavier stabilizing ions had lower thermal conductivity and the thermal conductivity could be further reduced by using binary stabilizing ions, which can be explained by phonon scattering from point defects. At the same time, the samples prepared at lower sintering temperatures showed smaller grain sizes and lower thermal conductivity. The relationship between the thermal diffusivity of samples and temperature was studied, where the dependence of inverse thermal diffusivity on temperature was better fitted by a quadratic fitting function than the usual linear one over a wide temperature range from 25 to 800°C.     

Mechanical properties and thermal conductivity of dense β-SiAlON ceramics fabricated by two-stage spark plasma sintering with Al2O3-AlN-Y2O3 additives

Fully dense β-SiAlON ceramics with excellent mechanical properties and good thermal conductivity were fabricated by two-stage spark plasma sintering (SPS) processes without and with applying pressure respectively, using α-Si₃N₄ powder and 6 Al₂O₃-3 AlN-6 Y₂O₃ (in wt.%, label with 636), 424 and 422 additives. In the first stage SPS process without pressure, the relative dense β-SiAlON ceramics with interlock microstructures of elongated grains and density of 3.14˜3.18 g cm⁻³, hardness of 14.00˜14.82 GPa and fracture toughness of 6.00˜6.63 MPa m^1/2 were obtained by sintering at about 1600 °C for 20 min. In the second stage SPS process at about 1425 °C for 5 min under pressure of 24 MPa, the fully dese β-SiAlON ceramics with density of 3.22˜3.24 g cm⁻³, high hardness of 15.68˜15.95 GPa, high fracture toughness of 6.38˜7.03 MPa m^1/2 and thermal conductivity of 13.5˜19.6 Wm^-1K^-1 were obtained. The reaction between the samples and the graphite mold can be avoided in this fabrication method.     

Effect of CaO on the optical quality and microstructure of transparent MgO·1.5Al2O3 spinel ceramics prepared by reactive sintering

Transparent MgO·1.5Al₂O₃ spinel ceramics were successfully prepared via reactive sintering of Al₂O₃ and MgO raw powders followed by hot isostatic pressing (HIP) using CaO as the sintering additive. The effects of CaO on the densification process, microstructure and optical quality of samples were investigated. It was found that the amount of CaO played an important role in the sintering process. By adding 0.05?wt% CaO, the sample with high transmittance (82.3% at 400?nm), small grain size (<5?μm) and high strength (228?±?15?MPa) was obtained after HIPing at 1550?°C. However, when the amount of CaO increased to 0.1?wt%, non-cubic and columnar-shaped grains generated at low HIP temperatures (1550–1650?°C), which severely reduced the optical quality of resulting samples. The grains were calcium aluminates, whose formation was closely related to the molar ratio of Al₂O₃/MgO, CaO amount and sintereing temperature.     

Thermal-assisted cold sintering study of Al2O3 ceramics: Enabled with a soluble γ-Al2O3 intermediate phase

Thermal-assisted cold sintering process (TA-CSP) has been applied to fabricate high dense α-Al₂O₃ ceramics with submicron grain sizes. The α-Al₂O₃ (80 wt%) and γ-Al₂O₃ (20 wt%) powders are firstly mixed and then cold sintered at 300 °C to produce a green bulk with a relatively high density of ～ 86.9 %, and then later a second heat treatment (800–1350 °C) is applied to finally fabricate (～ 98 % dense) α-Al₂O₃ ceramics with grain sizes of 720 nm. A microstructural analysis with XRD and TEM suggests that the TA-CSP samples not only complete the final densification but also drive a phase transition of γ-Al₂O₃ to α-Al₂O₃. To put into perspective the Hardness and Young's modulus of TA-CSP samples reach ～ 14 GPa and ～ 335 GPa, respectively, which is comparable to conventional sintered samples processed at higher temperatures of 1500–1700 °C. Therefore, it is feasible to utilize TA-CSP to prepare α-Al₂O₃ ceramics with small grain sizes at low sintering temperatures.     

Gelcasting and pressureless sintering of silicon carbide ceramics using Al2O3–Y2O3 as the sintering additives

In this paper, silicon carbide ceramics were prepared by aqueous gelcasting and pressureless sintering using Al₂O₃ and Y₂O₃ as the sintering additives. In order to develop well dispersed SiC slurries in the presence of sintering additives, the Al₂O₃ and Y₂O₃ powder was treated in the citric acid solution in advance. Zeta potential measurement showed that the isoelectric point (IEP) of Al₂O₃ and Y₂O₃ powder moved toward low pH region after treatment. Rheological measurement confirmed that the addition of as-treated powder showed very limited influence on the slurry properties as compared to that of untreated powder. SiC slurries with solid content of 54 vol% and enough fluidity can be developed. After gelcasting and pressureless sintering, SiC ceramics with nearly full density, fine grained and homogeneous microstructure can be obtained. Results showed that the surface treatment of Al₂O₃ and Y₂O₃ with citric acid is effective for the gelcasting process of SiC.     

Effect of temperature on the structure and mechanical properties of SiC–TiB2 composite ceramics by solid-phase spark plasma sintering

SiC composite ceramics have good mechanical properties. In this study, the effect of temperature on the microstructure and mechanical properties of SiC–TiB₂ composite ceramics by solid-phase spark plasma sintering (SPS) was investigated. SiC–TiB₂ composite ceramics were prepared by SPS method with graphite powder as sintering additive and kept at 1700 °C, 1750 °C, 1800 °C and 50 MPa for 10min.The experimental results show that the proper TiB₂ addition can obviously increase the mechanical properties of SiC–TiB₂ composite ceramics. Higher sintering temperature results in the aggregation and growth of second-phase TiB₂ grains, which decreases the mechanical properties of SiC–TiB₂ composite ceramics. Good mechanical properties were obtained at 1750 °C, with a density of 97.3%, Vickers hardness of 26.68 GPa, bending strength of 380 MPa and fracture toughness of 5.16 MPa m^1/2.     

Selective growth of p-doped SiC on diamond substrate by vapor–liquid–solid mechanism from Al–Si liquid phase

This works deals with the localized growth of SiC on monocrystalline (100) diamond surface. It describes an attempt of selective epitaxy using vapor–liquid–solid (VLS) transport. Patterns of Al–Si stacking were melted and fed by propane. Morphology, structure and doping type of the SiC deposit were evaluated. The deposit was found to be successfully selective but polycrystalline, with the 3C-SiC polytype. Study of the initial step of growth showed that SiC nucleation occurs without any propane addition but just through the interaction of liquid Al–Si and diamond via a dissolution/precipitation process. The VLS transport mainly assists the growth of these nuclei by providing a secondary carbon source. This explains the random nucleation and the polycrystalline growth. Despite this, the deposit was dense enough to perform some preliminary electrical measurements which show encouraging results.     

Comments on the mechanism of the vapour‐phase catalytic synthesis of thiophenes

A study of the synthesis of thiophene from the reaction of butanol and CS₂ over potassium‐promoted Cr₂O₃/γ‐Al₂O₃ has been performed by examination of the reactivity of model intermediates. This study indicates that the reaction path involves successive dehydrogenation, O/S exchange and dehydroheterocyclization. This revised version was published online in July 2006 with corrections to the Cover Date.