Grain boundary glasses in silicon nitride: A review of chemistry,properties and crystallisation

Silicon nitride for engineering applications is densified by liquid phase sintering using oxide additives such as yttria and alumina. The oxynitride liquid remains as an intergranular glass. This paper provides a review of microstructural development in silicon nitride, grain boundary oxynitride glasses and effects of chemistry on properties. Nitrogen increases T_g, viscosities, elastic moduli and microhardness. These property changes are compared with known effects of grain boundary glass chemistry in silicon nitride ceramics where significant improvements in fracture resistance of silicon nitride can be achieved by tailoring the intergranular glass chemistry.Crystallisation of the grain boundary Y–Si–Al–O–N glass phase can improve properties. Nucleation and crystallisation of a Y–Si–Al–O–N glass, similar to that found in grain boundaries of silicon nitride densified with yttria and alumina, can be optimised to form different Y-disilicate polymorphs at different temperatures. One solution to provide a single disilicate phase over a range of temperatures is discussed.     

Influence of intergranular phases on edge integrity of Si3N4/SiC wood cutting tools

Si₃N₄/SiC composites used for industrial wood cutting were processed by a near net shape route involving gas pressure sintering with sintering additives such as Al₂O₃, La₂O₃, Y₂O₃ and MgO. The cutting edge integrity of these knives was tested in a cutting trial and compared to knives made by a hot pressing route. It was found that the intergranular phase has a crucial influence on the cutting edge integrity. The boundary phase was analysed by EFTEM and EDX mapping on TEM samples: in gas pressure sintered composites the crystallisation of the apatite Y₅Si₃O₁₂N phase was identified. In the hot pressed composite the boundary phase consisted only of silicates. These composites showed better edge stability than cutting tools with a Y-N-apatite phase. The formation of the type of intergranular phase was found to be determined by the amount of MgO sintering aid and the temperature of the post sintering heat treatment.     

Crystallographic characterization of silicon nitride ceramics sintered with Y2O3–Al2O3 or E2O3–Al2O3 additions

Silicon nitride ceramics were sintered using Y₂O₃–Al₂O₃ or E₂O₃–Al₂O₃ (E₂O₃ denotes a mixed oxide of Y₂O₃ and rare-earth oxides) as sintering additives. The intergranular phases formed after sintering was investigated using high-resolution X-ray diffraction (HRXRD). The use of synchrotron radiation enabled high angular resolution and a high signal to background ratio. Besides the appearance of β-Si₃N₄ phase the intergranular phases Y₃Al₅O₁₂ (YAG) and Y₂SiO₅ were identified in both samples. The refinement of the structural parameters by the Rietveld method indicated similar crystalline structure of β-Si₃N₄ for both systems used as sintering additive. On the other hand, the intergranular phases Y₃Al₅O₁₂ and Y₂SiO₅ shown a decrease of the lattice parameters, when E₂O₃ was used as additive, indicating the formation of solid solutions of E₃Al₅O₁₂ and E₂SiO₅, respectively.     

Electrical resistivity of silicon nitride produced by various methods

It has been shown that the grain growth and amount of the glass phase influence the electrical resistivity of pressureless sintered and spark plasma sintered silicon nitride. Sintering additives strongly affect the impurity conductivity of pressureless sintered silicon nitride and slightly influence the intrinsic conductivity due to the longer sintering process as compared with the spark plasma sintering. It was demonstrated that Al₂O₃-Y₂O₃ lead to decrease in the electrical resistivity of SPSed silicon nitride due to increase in the band gap width as opposed to Al₂O₃-MgO. Effect of the sintering additive on the impurity conductivity is practically absent but there is a strong dependence of the sintering temperature for reported spark plasma sintered silicon nitride. However, intrinsic conductivity of SPSed silicon nitride is affected by both sintering temperature and sintering additive. It was also shown that electrical resistivity of produced ceramics is linearly depends on the content of β-Si₃N₄ and microhardness. Electrical resistivity of manufactured silicon nitride varied from 3.16·10⁹ to 1.73·10¹¹ Ω?m. It has been observed strong influence of the sintering additive and sintering temperature on the electrical properties of SPSed and pressureless sintered silicon nitride.     

Anisotropic properties of textured h-BN matrix ceramics prepared using 3Y2O3-5Al2O3(-4MgO) as sintering additives

Textured hexagonal boron nitride (h-BN) matrix composite ceramics were prepared by hot pressing using 3Y₂O₃-5Al₂O₃ (mole ratio of 3:5) and 3Y₂O₃-5Al₂O₃-4MgO (mole ratio of 3:5:4) as liquid phase sintering additives, respectively. During the sintering process with liquid phase environments, platelike h-BN grains were rotated to be perpendicular to the sintering pressure, forming the preferred orientation with the c-axis parallel to the sintering pressure. Both h-BN matrix ceramic specimens show significant texture microstructures and anisotropic mechanical and thermal properties. The h-BN matrix ceramics prepared with 3Y₂O₃-5Al₂O₃-4MgO possess higher texture degree and better mechanical properties. While the anisotropy of thermal conductivities of that prepared with 3Y₂O₃-5Al₂O₃ is more significant. The phase compositions and degree of grain orientation are the key factors that affect their anisotropic properties.     

Influence of boron substitution on the crystallisation behaviour of tetracalcium phosphate phase in the 4.5SiO2-3Al2O3-1.5P2O5-5CaO glass system

This study focuses on the effect of boron substitution on the crystallisation behaviour of an important bioceramic phase, tetracalcium phosphate (TTCP, Ca₄P₂O₉), in the 4.5SiO₂-3Al₂O₃-1.5P₂O₅-5CaO glass system. The influence of phase separation on the crystallisation activation energy as well as the microstructure is systematically analysed. The results indicate that increasing the extent of substitution of B for Al tends to lead to a decrease of the glass-transition temperature (T_g) and crystallisation temperature (T_p). When the substitution amount of B reaches 15 mol%, phase separation is observed. Weak phase separations during glass making can promote the nucleation of crystals due to heterogeneous nucleation with reduced nucleation activation energy. When 50 mol% B is substituted, serious phase separation is observed, with spherical-shaped TTCP phases appearing in the glass. The growth of striped-shaped TTCP crystals is largely suppressed even when a long holding time (1 h) at 900 °C is applied.     

Fatigue Crack Growth Behavior of Silicon Nitride: Roles of Grain Aspect Ratio and Intergranular Film Composition

The role of microstructure in affecting the fatigue crack growth resistance of grain bridging silicon nitride ceramics doped with rare earth (RE = Y, La, Lu) oxide sintering additives was investigated. Three silicon nitride ceramics were prepared using MgO‐RE₂O₃ and results were compared with a commercial Al₂O₃‐Y₂O₃‐doped material. Decreasing stress intensity range (ΔK) fatigue tests were conducted using compact‐tension specimens to measure steady‐state fatigue crack growth rates. Specimens doped with MgO‐RE₂O₃ additives showed a significantly higher resistance to crack growth than those with Al₂O₃‐Y₂O₃ additives and this difference was attributed to the much higher grain aspect ratio for the MgO‐RE₂O₃‐doped ceramics. When the crack growth data were normalized with respect to the total contribution of toughening by bridging determined from the monotonically loaded R‐curves, the differences in fatigue resistance were greatly reduced with the data overlapping considerably. Finally, all of the MgO‐RE₂O₃‐doped silicon nitrides displayed similar steady‐state fatigue crack growth behavior suggesting that they are relatively insensitive to the intergranular film.     

Effect of chemical composition of intergranular glass on superplastic compressive deformation of β-silicon nitride

The effect of chemical composition of Y₂O₃–Al₂O₃–SiO₂-based intergranular glass on superplastic deformation of β-Si₃N₄ was studied by compression tests at 1873 K. All hot isostatically pressed Si₃N₄ materials had essentially the same microstructure and the same amount of glass phase, which was different in composition only. The relation between flow stress and glass composition qualitatively corresponded to the effect of chemical composition on viscosity of Y₂O₃–Al₂O₃–SiO₂ glass. However, the flow stress was not proportional to the viscosity of Y₂O₃–Al₂O₃–SiO₂ glass, probably because the composition of intergranular glass phase had changed by dissolving Si₃N₄. The strain hardening (increase of flow stress with deformation) was dependent on the chemical composition of intergranular glass. Actually, the apparent strain hardening was not proportional to the strain but was proportional to time. The crystallization of Si₂N₂O was also proportional to time, and was dependent on the chemical composition of the intergranular glass in a similar way to the strain hardening. Thus, it was suggested that the crystallization of Si₂N₂O reduced the amount of the intergranular glass, thereby increasing flow stress.     

Densification of Yttria Transparent Ceramics: The Utilization of Activated Sintering

Highly transparent 0.5 at.% Tm:Y₂O₃ ceramics were prepared by using solid‐state reaction combined with vacuum sintering method, with ZrO₂ and Al₂O₃ as sintering aids. Doping amount of ZrO₂ was fixed at 1 at.%, while the effect of Al₂O₃ on densification, microstructure evolution, and transmittance of the Y₂O₃ ceramics was carefully studied. It was found that the addition of Al₂O₃ was very effective in improving densification of Y₂O₃, due to the formation of an Al‐rich eutectic phase Y₄Al₂O₉ (YAM) during the sintering process. As the content of Al₂O₃ was increased from 0 to 81.8 wt ppm, porosity of the ceramics was decreased and transmittance was increased. However, when the content of Al₂O₃ was increased to 137 wt ppm, a secondary phase began to segregate at grain junctions. Further increase in the amount of Al₂O₃ led to an increase in both amount and size of the secondary phase. At the optimized content of Al₂O₃ with 81.8 wt ppm, the Tm:Y₂O₃ ceramics sintered at 1860°C for 13 h exhibited an in‐line transmittance of 83.0% at 2000 nm and 76.5% at 600 nm. It is expected that this finding can be readily applied to other transparent ceramics.     

Compositional identification of the intergranular phase in liquid phase sintered SiC

A model system consisting of coarse SiC (32–160 μm) as starting powder and Y₂O₃ and AlN as sintering additives was liquid phase sintered. Coarse-grained starting powder led to large intergranular phase regions which allowed an accurate determination of the chemical composition by wavelength-dispersive X-ray microanalysis (WDS). When N₂ was used as sintering atmosphere, a N-rich amorphous phase (about 44 at.% N) was identified by WDS to be the main triple-junction phase in the sintered SiC ceramics, while three further crystalline intergranular phases were AlN, Y₂SiN₄O₃ and an O-rich phase (Y₁₀Al₂Si₃O₁₈N₄). The overall O content was found to be reduced in comparison to the initial powder composition. The incorporation of N from the sintering atmosphere into the intergranular phase and a subsequent carbothermal reduction are believed to be responsible for the removal of O and the formation of the N-rich amorphous phase.     

Fabrication of Si3N4 ceramics by post-reaction sintering using Si–Y2O3–Al2O3 nanocomposite particles prepared by mechanical treatment

Post-reaction sintering of a powder compact of Si and sintering aids is a useful technique for fabricating silicon nitride (Si₃N₄) ceramics at low costs. In order to inhibit the inhomogeneous and uncontrollable exothermic nitridation of Si in the powder compact, Si–Y₂O₃–Al₂O₃ nanocomposite particles are designed as an aid for post-reaction sintering. These Si–Y₂O₃–Al₂O₃ nanocomposite particles are prepared via mechanical treatment applying high shear stress. Scanning electron microscopy (SEM) observations show that Y₂O₃ and Al₂O₃ particles are homogenously dispersed, and fixed to the Si particles. A green compact prepared using the Si–Y₂O₃–Al₂O₃ nanocomposite particles results in lower electrical resistivity than that prepared using a powder mixed by wet ball-milling, which suggests that Si particles in the green compact prepared using the nanocomposite particles are isolated by Y₂O₃ and Al₂O₃ particles. The isolation of Si particles by the sintering aids successfully prevents the Si particles from melting and agglomerating during the nitridation process, resulting in a higher nitridation ratio and higher α-Si₃N₄ phase content due to the inhibition of rapid heat transfer caused by the exothermic reaction. The nitridation ratio also increases with the applied power during mechanical treatment. As a result of firing the homogeneously nitrided powder compacts at high temperatures, Si₃N₄ ceramics with homogeneous microstructure and improved density are successfully fabricated in this manner.     

Phase formation in porous liquid phase sintered silicon carbide: Part I:: Interaction between Al2O3 and SiC

The structure and phase formation of porous liquid phase sintered silicon carbide (porous LPS-SiC), containing yttria and alumina additives have been studied. The present paper is focused on the system Al–Si–C–O, which is part of the system describing the interactions with sintering additives.The influence of different sintering atmospheres, namely argon and Ar/CO, and different temperatures on structure and composition was investigated by XRD and SEM. Additionally, reaction products were calculated from thermodynamic data and correlated with experimentally determined reaction products. Alumina and SiC reacted at 1950 °C in an argon atmosphere, forming a metal melt of aluminium and silicon. No reduction of Al₂O₃ was observed in a CO-containing argon sintering atmosphere.In the second and third parts of this paper the interactions between Y₂O₃–SiC and Y₂O₃–Al₂O₃–SiC are analysed [J. Eur. Ceram. Soc. (in press), parts II and III].     

Comparison of hydrothermal corrosion behavior of SiC with Al2O3 and Al2O3 + Y2O3 sintering additives

Fully dense SiC bulks with Al₂O₃ and Al₂O₃ + Y₂O₃ sintering additives were prepared by spark plasma sintering and the effect of sintering additives on the hydrothermal corrosion behavior of SiC bulks was investigated in the static autoclave at 400°C/10.3 MPa. The SiC specimen with Al₂O₃ sintering additive exhibited a higher weight loss and followed a linear law. However, the SiC specimen with Al₂O₃ + Y₂O₃ additive exhibited a lower weight loss and followed a parabolic law, indicating that the corrosion kinetic and mechanism were different for these two SiC bulks. Further examination revealed that, a deposited layer was formed on the surface of SiC specimen with Al₂O₃ + Y₂O₃ sintering additive after corrosion, which can effectively protect the SiC specimen from further corrosion, and thereby improved the corrosion resistance of the SiC specimen with Al₂O₃ + Y₂O₃ sintering additive.     

Preparation and sealing effects of Mg–Al–Si–Ba–O-based glass-ceramic coatings on NTC thermistors

Herein, Mg–Al–Si–Ba–O-based glass ceramics were studied as potential candidates to protect Mn–Co–Ni–O-based negative temperature coefficient (NTC) thermistors at high temperatures such as 900 °C. The ceramics were prepared in three glass formulations (1#: 15MgO–15Al₂O₃-44.7SiO₂–25BaO, 2#: 17MgO–17Al₂O₃–41SiO₂–25BaO and 3#: 17MgO–17Al₂O₃–41SiO₂–20BaO–5Y₂O₃ (in mol%)) and their glass-transition temperatures (T_g) were determined using the differential scanning calorimetry (DSC) method. Scanning electronic microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the parent glasses and glass-ceramic coatings. The sealing effects of the glass ceramics were examined by conducting an insulation test. The glass-ceramic sealing structures were subjected to 1000 thermal shock cycles at temperatures varying from room temperature to 900 °C. Notably, the sealing structure of glass-ceramic coating 1# was compact at a T_g of 760.9 °C. The glass-ceramic coatings effectively maintained the NTC properties of the sensitive ceramics in all three formulations. Interestingly, the glass-ceramic coating 3# containing Y₂O₃ demonstrated an increase in electrical resistance. Both the NTC thermistors coated with 1# and 2# glass formulations successfully passed 1000 thermal shock cycles without visible failures, and their resistance change ratios were well below the requisite 20%.     

Fabrication and mechanical properties of h-BN based composites containing dual glass phases

In this work, h-BN based composites containing amorphous silica and ytterbium silicate glass phases were successfully fabricated by in situ hot pressing process. The powder mixtures of h-BN, Yb₂O₃, SiO₂ and sintering additive (Al₂O₃) were hot pressed at 1880?°C for 1?h under 30?MPa in Ar atmosphere. In the composites, β-Yb₂Si₂O₇ phase produced from the reaction between Yb₂O₃ and SiO₂ disappears completely and transforms to Yb-Si-Al-O glass when the amount of Al₂O₃ is ≥1.5?wt.%. The Vickers hardness, flexural strength, and compressive strength reached the maximum values of 2.38?±?0.08?GPa, 337?±?22?MPa and 950?±?34?MPa, respectively, as 1.5?wt.% Al₂O₃ was added. The strengthening effects were attributed to the fine spherical microstructure of Yb-Si-Al-O glass particles, strong [AlO₄] coordination state, and residual compressive stress in glass phases.     

The effect of Al2O3-MgO additives on the microstructure of spark plasma sintered silicon nitride

It was shown that spark plasma sintered silicon nitride with a high content of Al₂O₃ and MgO consists of α and β silicon nitride, the main phase being α silicon nitride. The increase in the sintering temperature did not lead to significant changes in the phase composition as occurs in silicon nitride added with Al₂O₃-Y₂O₃. It was found that increasing in SPS temperature above 1650 °C leads to an insignificant increase in the density. A complex shaped equiaxed grain microstructure was shown in both cases. However, doping with aluminum and yttrium oxides allows obtaining an elongated grain microstructure. The Hall-Petch effect was observed for the microhardness of the investigated SPSed silicon nitride. The microhardness of the described ceramics was rather high and more than 1900 HV compared to the pressureless sintered at 1800 °C silicon nitride with the microhardness equal to 1511 HV.     

Densification of liquid phase sintered silicon carbide

The densification and phase formation of liquid phase sintered silicon carbide (LPSSiC) with 10 wt.% additives were investigated. The ratio of the Al₂O₃/Y₂O₃-additives was changed between 4:1 and 1:2. Densification was carried out by hot pressing and gas pressure sintering. The different densification routes result in different major grain boundary phases—aluminates in gas pressure sintered materials and silicates in hot pressed samples. Thermodynamic calculations were carried out to determine the amount of liquid phase during densification and for the interpretation of the results.     

CaO–SiO2–Al2O3–Y2O3 glasses as model grain boundary phases for Si3N4 ceramics

The glasses with compositions derived from the eutectic composition [37.78 (Y₃Al₅O₁₂)·62.22 (SiO₂)] of the quasi-binary glass system (Y₃Al₅O₁₂)-(SiO₂) with addition of up to 20 mol.% CaO were investigated as model grain boundary phases for Si₃N₄ ceramics. The influence of CaO as model impurity on the physical properties of the glass (density, thermal expansion) and on the crystallisation behaviour was studied. Although the initial composition of the basic glass was that of yttrium-aluminium garnet (Y₃Al₅O₁₂–YAG), no crystalline YAG was detected. Apart from yttrium disilicate (Y₂Si₂O₇), anorthite (CaAl₂Si₂O₈), tricalcium aluminate (Ca₃Al₂O₆), and calcium yttrium oxide silicate (Ca₄Y₆O(SiO₄)₆), a new phase was detected, not found in the powder diffraction file (PDF) database. Cavities were formed within the devitrified glass due to the volume contraction after crystallisation. Possible implications for the mechanical properties of Si₃N₄ ceramics sintered with addition of Y₂O₃–Al₂O₃ are discussed in terms of the observed compositional dependences of the physical properties of CaO–Y₂O₃–Al₂O₃–SiO₂ glasses.     

Fabrication and thermal conductivity of AlN/BN ceramics by spark plasma sintering

Aluminum nitride/boron nitride (AlN/BN) ceramics with 15–30 vol.% BN as secondary phase were fabricated by spark plasma sintering (SPS), using Yttrium oxide (Y₂O₃) as sintering aid. Effects of Y₂O₃ content and the SPS temperature on the density, phase composition, microstructure and thermal conductivity of the ceramics were investigated. The results revealed that with increasing the amount of starting Y₂O₃ in AlN/BN, Yttrium-contained compounds were significantly removed after SPS process, which caused decreasing of the residual grain boundary phase in the sintered samples. As a result, thermal conductivity of AlN/BN ceramics was remarkably improved. By addition of Y₂O₃ content from 3 wt.% to 8 wt.% into AlN/15 vol.% BN ceramics, the thermal conductivity increased from 110 W/m K to 141 W/m K.     

Crystallisation and characterisation of dielectric glass ceramics in Li2O–Al2O3–SiO2 system

Abstract

Glass ceramics in the Li₂O–Al₂O₃–SiO₂ system have been synthesised to produce bulk materials grown in a glass phase via quenching followed by controlled crystallisation. The crystallisation and microstructure of Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramic with nucleating agents (B₂O₃ and/or P₂O₅) are investigated by differential thermal analysis, X-ray diffraction and scanning electron microscopy and the effects of B₂O₃ and P₂O₅ on the crystallisation of LAS glass are also analysed. The introduction of both B₂O₃ and P₂O₅ promotes the crystallisation of LAS glass by decreasing the crystallisation temperature and adjusting the crystallisation kinetic parameters, allows a direct formation of β spodumene phase and as a result, increases the crystallinity of the LAS glass ceramic. Microstructural observations show that the randomly oriented, nanometre sized crystalline is found with residual glass concentrated at crystallite boundaries. Furthermore, it is interesting that codoping of B₂O₃ and P₂O₅ creates not much effect on the crystallisation temperature. The dielectric properties of the glass–ceramics formed through controlled crystallisation have a strong dependence on the phases that are developed during heat treatment. The dielectric constant is continuously increased and the dielectric loss is decreased with addition of additives where mobile alkali metal ions (e.g. Li⁺) are incorporated in a crystal phase and minimise the residual glass phase.