Aqueous colloidal processing of SiC with Y3Al5O12 liquid-phase sintering additives

The aqueous colloidal processing of SiC with Y₃Al₅O₁₂ liquid-phase sintering additives was investigated for two different additive systems, one the mixture of Y₂O₃ and Al₂O₃ in a 3:5 molar ratio and the other directly Y₃Al₅O₁₂. The investigation involved the study of the colloidal stability of the different components, and the comparison of the rheological behaviour of concentrated suspensions of SiC, SiC + 3Y₂O₃:5Al₂O₃, and SiC + Y₃Al₅O₁₂ as a function of the sonication condition, dispersant content, and solid loading. This allowed appropriate conditions for the preparation of well-dispersed, single-phase, and multi-component concentrated suspensions of SiC to be identified. It was found that the multi-component suspensions have better rheological behaviour than the single-phase ones, and that in terms of rheology and slip casting the Y₃Al₅O₁₂ additives are more functional than the conventional 3Y₂O₃ + 5Al₂O₃ additives. It was also demonstrated that the Y₃Al₅O₁₂ additive is as effective as the 3Y₂O₃ + 5Al₂O₃ additive in densifying SiC via liquid-phase sintering, with there existing no differences either in the microstructure or in room-temperature mechanical properties (hardness, toughness, and fracture mode). Implications of interest for the wet-shaping of complex SiC parts are discussed.     

Effects of Y2O3 additives and powder purity on the densification and grain boundary composition of Al2O3/SiC nanocomposites

Sub-micron sized SiC additions can be used to increase the wear resistance and change the fracture mode of Al₂O₃. However, these additions also restrict sintering.Al₂O₃ and Al₂O₃–5%SiC ‘nanocomposites’ were prepared from alumina powders of high purity and of commercial-purity, with or without the addition of Y₂O₃. The effects of these compositional variables on sintering rate, final density and grain boundary composition were investigated. A direct comparison with Al₂O₃–SiO₂ composites was also made, as it has been proposed that SiC partially oxidises during processing of Al₂O₃–SiC nanocomposites.The addition of 5 vol.% SiC to Al₂O₃ hindered densification, as did addition of 0.15 wt.% Y₂O₃ or 0.1 wt.% SiO₂. In contrast, the addition of 0.15 wt.% Y₂O₃ to Al₂O₃–5% SiC nanocomposites improved densification.The composition of Al₂O₃–Al₂O₃ grain boundaries in these materials was studied using STEM and EDX microanalysis. The addition of SiC and SiO₂ caused segregation of Si, and Y₂O₃ addition caused segregation of Y. The segregation of each element was equivalent to <10% of a monolayer at the grain boundary. However, if SiC and Y₂O₃ were simultaneously added the segregation increased to 40% of a monolayer. The enhanced segregation was attributed to increased oxidation of SiC in the presence of Y₂O₃ allowing formation of a SiO₂–Al₂O₃–Y₂O₃ eutectic phase or a segregated layer which may explain the improvement in sintering rate when Y₂O₃ was added to nanocomposites.     

Effects of Re2O3 (Re = La,Nd, Y and Yb) addition in hot-pressed ZrB2–SiC ceramics

ZrB₂–20 vol% SiC composites with 3 vol% Re₂O₃ rare-earth oxide (Re = La, Nd, Y or Yb) were hot pressed to near full-density at 1900 °C. The La₂O₃ and Nd₂O₃ additions not only caused the formation of an amorphous grain boundary phase and enhanced densification, but also resulted in substantial ZrB₂ and SiC grain growth. In contrast, the Y₂O₃ and Yb₂O₃ additions resulted in the formation of crystalline (Y/Yb)₂Zr₂O₇ and enhanced densification without ZrB₂ and SiC grain growth. The hardness was improved by the rare-earth oxide addition, especially with Y₂O₃ and Yb₂O₃. The La₂O₃ and Nd₂O₃ only had a minor effect on the fracture toughness, whereas the Y₂O₃ and Yb₂O₃ additions increased the fracture toughness. The type of Re₂O₃ addition was found to influence the nature of the grain boundary and the concomitant fracture and toughening mechanisms.     

Preliminary investigation of flash sintering of SiC

The feasibility of flash sintering a covalent ceramic, SiC, has been investigated for the first time. Flash sintering involves the application of an electrical potential difference across a powder compact during heating, which leads to sintering at low furnace temperatures in a few seconds and has only been demonstrated with ionic ceramics previously. Near-theoretical density was achieved using Al₂O₃ + Y₂O₃ sintering aids at a furnace temperature of only 1170 °C and in a time of 150 s. Specimen temperatures were significantly higher than the furnace temperature owing to Joule heating and consequently heat loss limited densification in the near surface region. It was not possible to reach high densities using “ABC” sintering aids (aluminium–boron–carbon) or pure SiC. The mechanisms involved and potential commercial advantages are briefly discussed.     

Pressureless sintering of β-SiAlON ceramic compositions using fluorine and oxide additive system

SiAlONs are silicon aluminium oxynitride ceramic materials with a range of technically important applications, from cutting tools to specialised refractories and the properties of SiAlONs can be tailored for specific purposes. In this study, different β-SiAlON compositions were prepared using fluoride (MgF₂ as fluorine source plus Y₂O₃) and oxide (MgO plus Y₂O₃). These compositions were pressureless sintered under nitrogen atmosphere in the range of 1450–1750 °C for 0.5–2.5 h for comparison of densification behaviour and mechanical properties. Densities of samples were measured and analyses of result products were carried out using SEM and XRD. The F-doped sintered β-SiAlON ceramics showed better densities and less pore micrographs especially at lower temperatures compared with the fluorine free samples. Full densifications were achieved for β-SiAlON ceramics with fluoride addition at 1700 °C for 60 min. Consequently, fluorine addition to additive system has a good effect on mechanical properties and densification behaviour.     

A high strength alumina-silicon carbide-boron carbide triplex ceramic

A ceramic particulate composite composed of oxide, and carbide ceramics was found to have high strength, hardness, and fracture toughness values. A composition consisting of Al₂O₃ with 15 vol% SiC and 15 vol% B₄C additions was produced by hot-pressing at 1650 °C for 30 min, with full density reached after ~5 min at temperature. Both WB and WB₂ were observed, with the W source presumably an impurity from WC milling media, and Al₁₈B₄O₃₃ was also detected following densification. Strength was ~880 MPa, which is greater than values reported for comparable composites of Al₂O₃ containing 30 vol% SiC or B₄C. Vickers hardness was ~21 GPa, and fracture toughness was ~4.5 MPa m^½, comparable to values reported for the binary mixtures. The calculated critical flaw size of the material was similar to the size of the SiC/B₄C clusters and microcracking at grain boundaries. The latter resulting from thermal expansion mismatch between the Al₂O₃ matrix and SiC/B₄C reinforcing phases.     

Aqueous colloidal processing of submicrometric SiC plus Y3Al5O12 with diamond nanoparticles

Aqueous colloidal processing was used for the environmentally friendly preparation of well-dispersed concentrated suspensions and powder mixtures of submicrometric SiC powders with submicrometric Y₃Al₅O₁₂ as sintering additive plus diamond nanoparticles as reinforcing phase. It is shown that the addition of nano-diamond markedly increases the viscosity and thixotropy of the SiC + Y₃Al₅O₁₂ suspensions, and also that, by adjusting the pH, deflocculant content, and sonication time it is possible to co-disperse these three rheologically different ceramic phases (i.e., non-oxide, oxide, and hydrophobic compounds) in aqueous media, thereby avoiding the otherwise irremediable severe hetero-aggregation. Moreover, the microstructural characterization of the powder mixtures obtained by freeze-drying the suspensions confirmed the homogeneous dispersion of the diamond nanoparticles among the submicrometric SiC and Y₃Al₅O₁₂ particles in the form of isolated or adhered nanoclusters and nanodeposits. Implications for engineering the microstructure of non-oxide ceramics with diamond nanodispersoids are discussed.     

Theoretical and experimental analyses of relationship between processing and thermal conductivity of SiC with oxide additives

This paper analyzes theoretically and experimentally the thermal conductivity of the SiC-oxide additive-pore system. In the developed 6 model structures, the thermal conductivity of an SiC compact (κ_b) with oxide was calculated as functions of the volume fractions of SiC, oxide additive and pores. The calculated κ_b decreases in the order of a continuous phase where the other two particulate phases are dispersed: SiC>oxide additive>pores. The measured κ_b values of SiC compacts hot-pressed with 4–50 mass% oxide additive (mixture of 33.3 mass% Al₂O₃-33.3 mass% Y₂O₃-33.3 mass% SiO₂) were well explained by the calculated κ_b in two types of oxide continuous phase models. The thermal conductivities for only SiC grains in SiC compacts hot-pressed with 4 mass% Al₂O₃, Y₂O₃, SiO₂, Al₂O₃-Y₂O₃, Y₂O₃-SiO₂ and Al₂O₃-Y₂O₃-SiO₂ at 1950 °C were also estimated theoretically in the developed two model structures using the measured κ_b (oxide continuous phase model and SiC continuous phase model). Based on the calculated results, the following key factors are identified to achieve a high κ_b: (1) high sintered density, (2) a small amount of oxide additive with a high thermal conductivity, (3) no dissolution of foreign atoms from a liquid phase into SiC grains during solidification process.     

Effect of Al2O3 on the structure and microwave dielectric properties of Ca0.7Ti0.7La0.3Al0.3O3

The effect of excess Al₂O₃ on the densification, structure and microwave dielectric properties of Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) was investigated. CTLA ceramics were prepared using the conventional mixed oxide route. Excess Al₂O₃ in the range of 0.1–0.5 wt% was added. It was found that Al₂O₃ improved the densification. A phase rich in Ca and Al was found in the microstructure of Al₂O₃ doped samples. Additions of Al₂O₃ coupled with the slow cooling after sintering improved the microwave dielectric properties. CTLA ceramics with 0.25 wt% Al₂O₃ cooled at 5 °C/h showed high density and a uniform grain structure with ɛ_r = 46, Q × f = 38,289 and τ_f = +12 ppm/°C at 4 GHz. XRD and TEM examinations showed the presence of (1 1 2) and (1 1 0) type twins arising from a⁻a⁻c⁺ tilt system with the presence of anti-phase domain boundaries from the displacement of A-site cations of the orthorhombic perovskite structure.     

Electrical resistivity of α-SiC ceramics sintered with Al2O3 or AlN additives

Highly resistive SiC ceramics were prepared by hot pressing α-SiC powders with Al₂O₃-Y₂O₃ additives with a 4:1 molar ratio. X-ray diffraction patterns, Raman spectra, electron probe microanalysis (EMPA), and scanning electron microscopy (SEM) images revealed that the bulk SiC ceramics consisted mostly of micron-sized 6H-SiC grains along with Y₂O₃ and Si clusters. As the additive content increased from 1 to 10 vol%, the electrical resistivity of the ceramics increased from 3.0 × 10⁶ to 1.3 × 10⁸ Ω cm at room temperature. Such high resistivity is ascribed to Al₂O₃ in which Al impurities substituting Si site act as deep acceptors for trapping carriers. More resistive α-SiC ceramics were produced by adding AlN instead of Al₂O₃. The highest resistivity (1.3 × 10¹⁰ Ω cm) was achieved by employing 3 vol% AlN-Y₃Al₅O₁₂ (yttrium aluminum garnet, YAG) as an additive.     

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.     

Effect of adding Y2O3 on structural and mechanical properties of Al2O3–ZrO2 ceramics

The effects of adding 1–8 wt% Y₂O₃ on phase formation and fracture toughness of Al₂O₃–xZrO₂–Y₂O₃(AZY) ceramics were studied. Phase formations of the samples were characterized by the X-ray diffraction (XRD) technique. It was found that the major phase was rhombohedral-Al₂O₃, while the minor phase consisted of the monoclinic-ZrO₂, tetragonal-ZrO₂ and monoclinic-Y₂O₃. It was found that Y₂O₃ contents did not clearly influence grain shape of AZY ceramics. The results obtained from the microhardness test could be used to evaluate the fracture toughness. It was found that the smaller grains had high fracture toughness. The maximum fracture toughness of 4.827 MPa m^1/2 was obtained from 4 wt% Y₂O₃. Refinement of lattice parameters using Rietveld analysis revealed the quantitative phases of AZY ceramics. This shows that under adding Y₂O₃ conditions the proportion of tetragonal-ZrO₂ phase plays an important role for the mechanical properties of AZY ceramics.     

Carbon nanotube toughened aluminium oxide nanocomposite

This paper describes the mechanical properties of carbon nanotube-reinforced Al₂O₃ nanocomposites fabricated by hot-pressing. The results showed that compared with monolithic Al₂O₃ the fracture toughness, hardness and flexural strength of the nanocomposites were improved by 94%, 13% and 6.4% respectively, at 4 vol.% CNT additions. For 10 vol.% CNT additions, with the exception of the fracture toughness, which was improved by 66%, a decrease in mechanical properties was observed when compared with those for monolithic Al₂O₃. The toughening mechanism is discussed, which is due to the uniform dispersion of CNTs within the matrix, adequate densification, and proper CNT/matrix interfacial connections.     

Densification,microstructure and mechanical properties of ZrB2–SiCw ceramic composites

ZrB₂–SiCw composites were prepared through hot-pressing at a low temperature of 1800 °C, and Al₂O₃ plus Y₂O₃ were added as sintering aids. Analysis revealed that additives may react with impurities (i.e. surface oxygen impurities and residual metallic impurities) to form a transient liquid phase, thus promote the sintering and densification of ZrB₂–SiCw composites. The content of additives was found to have a significant influence on the sinterability, microstructure and mechanical properties of ZrB₂–SiCw composites. ZrB₂–SiCw composite prepared with a small amount of additives (3 vol.%) provided the optimal combination of microstructure (relative density of 98.3%) and excellent properties, including flexural strength of 783 MPa and fracture toughness of 6.7 MPa m^1/2. With further addition of additives, SiC whiskers were inclined to gather together and be enveloped by excessive liquids to form core-rim-like structures, which lead to little decrease in mechanical properties.     

B6O materials with Al2O3/Y2O3 additives densified by FAST/SPS and HIP

Fully densified B₆O materials with Al₂O₃/Y₂O₃ sintering additives amounts systematically varied between 0 and 15 vol.% and Al₂O₃/(Al₂O₃ + Y₂O₃) molar ratios of 0.05–1 were prepared by FAST/SPS and HIP at sintering temperatures between 1725 °C and 1900 °C. Their densification and microstructure were correlated with measured mechanical properties. The addition of low additive amounts in the range of 2–3 vol.% was found to increase the fracture toughness and strength from 2.0 MPa m^1/2 (SEVNB) and 420 MPa for pure B₆O to about 3.0 MPa m^1/2 and 540 MPa, but it had no effect on the hardness, which remained at a high level of 30–36 GPa (HV_0.4). Higher additive contents did not yield a further improvement in the toughness but resulted in a reduction in hardness and strength.     

Effects of sintering atmosphere on grain morphology of liquid-phase-sintered SiC with Al2O3 additions

The effects of sintering atmospheres of Ar and N₂ on grain morphology were investigated for pressureless liquid-phase-sintered (LPS) SiC with Al₂O₃ additions. When increasing the sintering temperature, the SiC grain size and its aspect ratio increased in both sintering atmospheres. With a 2 mass% Al₂O₃ addition, no distinct difference was observed between the grain morphology of SiC sintered in the Ar atmosphere and that sintered in the N₂ atmosphere. With a 15 mass% Al₂O₃ addition, sintering in a N₂ atmosphere led to retarded grain growth and this resulted in a fine homogeneous microstructure, whereas sintering in an Ar atmosphere enhanced the grain growth compared with that in 2 mass% Al₂O₃. The effects of atmosphere on the grain morphology depend on the amount of Al₂O₃ addition, and this also affects the grain growth process of solution-reprecipitation. The mechanical properties of the SiC are also considered.     

Structural-phase state and lasing of 5–15 at% Yb3+:Y3Al5O12 optical ceramics

Yttrium aluminum garnet (Yb³⁺:Y₃Al₅O₁₂) laser ceramics doped by 5, 10 and 15 at% of ytterbium ions were obtained by reactive sintering. Optimal sintering temperature range for the formation of highly-dense transparent Yb³⁺:Y₃Al₅O₁₂ ceramics under normal recrystallization conditions was found to be T = 1750–1800 °C. The influence of Yb³⁺ ions on structural-phase state, phase composition, microstructure, optical and luminescent properties of sintered samples was experimentally investigated. It was shown that lattice parameter a of Yb³⁺:Y₃Al₅O₁₂ ceramics decreases linearly with increasing of Yb³⁺ concentration in a good agreement with L. Vegard’s rule, that indicates to the formation of (Y_1−xYb_x)₃Al₅O₁₂ (х = 0.05–0.15) substitutional solid solutions. No concentration quenching of Yb³⁺ luminescence was observed in Yb³⁺:Y₃Al₅O₁₂ within the 5–15 at% doping range. Quasi-CW lasing of Yb³⁺:Y₃Al₅O₁₂ ceramics was studied under diode-pumping at 970 nm. A highest slope efficiency of about 50% was obtained for 15 at%-doped Yb³⁺:Y₃Al₅O₁₂ ceramics sintered at T = 1800 °C for 10 h.     

Processing of microcellular silicon carbide ceramics with a duplex pore structure

A novel processing route for producing microcellular SiC ceramics with a duplex pore structure has been developed using a polysiloxane, carbon black, SiC, Al₂O₃, Y₂O₃, and two kinds of pore former (expandable microspheres and PMMA spheres). The duplex pore structure consists of large pores derived from the expandable microspheres and small windows in the strut area that were replicated from the PMMA spheres. The presence of these small windows in the strut area improved the permeability of the porous ceramics. The gas permeability coefficients of porous SiC ceramics were 0.13 × 10¹² m² for the porous SiC without PMMA spheres, 0.47 × 10¹² m² for the porous SiC with 10 wt% PMMA spheres, and 0.82 × 10¹² m² for the porous SiC with 20 wt% PMMA.     

Influence of Y2O3 addition on electrical properties of β-SiC ceramics sintered in nitrogen atmosphere

The influence of Y₂O₃ addition on electrical properties of β-SiC ceramics has been investigated. Polycrystalline SiC samples obtained by hot-pressing SiC–Y₂O₃ powder mixtures in nitrogen (N) atmosphere contain Y₂O₃ clusters segregated between SiC grains. Y₂O₃ forms a Y–Si-oxycarbonitride phase during sintering by reacting with SiO₂ and SiC and by dissolution of N from the atmosphere; this induces N doping into the SiC grains during the process of grain growth. The SiC samples exhibit an electrical resistivity of ～10^?3 Ω cm and a carrier density of ～10²⁰ cm^?3, which are ascribed to donor states derived from N impurities. The increase in defect density with increasing Y₂O₃ content is likely to be a main limiting factor of the electrical conductivity of SiC ceramics.     

Inhibition of grain growth in liquid-phase sintered SiC ceramics by AlN additive and spark plasma sintering

SiC ceramics were prepared from nanosized β-SiC powder with different compositions of AlN and Y₂O₃ sintering additives by spark plasma sintering (SPS) at 1900 °C for 600 s in N₂. The relative density of the sintered SiC specimens increased with increasing amount of AlN, reaching a relative density higher than 99%, while at the same time grain size decreased significantly. The smallest average grain size of 150 nm was observed for SiC sample sintered with 10 vol% of additives consisting of 90 mol% AlN and 10 mol% Y₂O₃. Fully dense nanostructured SiC ceramics with inhibited grain growth were obtained by the AlN additive and SPS technique. The flexural strength of the SiC body containing 70 mol% AlN and 30 mol% Y₂O₃ additives reached the maximum value of 1000 MPa. The SiC bodies prepared with AlN and Y₂O₃ additives had the fracture toughness of around 2.5 MPam^1/2.