Effects of oxidation on intergranular phases in silicon nitride ceramics

The effects of oxidation on changes in the secondary phases of two Si₃N₄ ceramics were investigated by transmission electron microscopy. The Si₃N₄ materials were oxidized at 1400 °C for 168 h in laboratory air. One material, sintered with 5 vol% Yb₂O₃+0.5 vol% Al₂O₃, containing a Yb₂Si₂O₇ crystalline secondary phase, displayed no gross changes following oxidation. However, the thickness of the amorphous intergranular film was observed to have decreased by 20% from its initial thickness of 1.0 nm. The second Si₃N₄ material, sintered with 5 wt% Y₂O₃+1 wt% MgO, had a completely amorphous secondary phase. Devitrification of the secondary phase at multiple-grain junctions to -Y₂Si₂O₇ accompanied the outward diffusion of additive and impurity cations occurring in the residual amorphous intergranulàr films during oxidation. Substantial cavitation and intergranular phase depletion was observed at both multiple-grain junctions and two-grain boundaries. The equilibrium thickness of the amorphous intergranular film consequently decreased from 1.2 to 0.9 nm following oxidation. Purification of the amorphous intergranular films by diffusion of cations to the surface led to a reduction in impurity concentration, resulting in the observed thinning of grain-boundary films.     

Crystallization of the glassy phase in an Si3N4 material by post-sintering heat treatments

It is shown that post-sintering heat treatments in air in the temperature range 1100 to 1400° C result in substantial crystallization of the glassy phase in an Si₃N₄ material which was produced by the nitridation pressureless sintering (NPS) method using Y₂O₃ and Al₂O₃ as sintering aids. X-ray diffraction combined with analytical electron microscopy showed that the secondary crystalline phases which form are strongly dependent upon time and temperature of heat treatment as well @S depth below the oxide scale. This effect is primarily due to the outward diffusion of cations (yttrium, aluminium and impurities) as well as the inward diffusion of oxygen. Small glassy pockets and thin amorphous intergranular films remain in the microstructure after heat treatment.     

Imaging and microanalysis of liquid phase sintered silicon-based ceramic microstructures

This review paper is focussed on the characterization of the microstructural development during liquid phase sintering and post-densification crystallisation heat treatment of ceramic materials based on the Si₃N₄ or SiC structures. Grain shape and size distributions, assessed by quantitative microscopy in combination with stereological methods, and fine scale microstructures, investigated by electron diffraction and high resolution imaging and microanalysis in the TEM, are discussed and related to the fabrication process and the overall composition of the ceramic material. It is demonstrated that combined high resolution analytical and spatial information from chemically and structurally distinct fine scale features, such as grain boundary films of residual glass, is obtained by electron spectroscopic imaging and subsequent computation of elemental distribution images. These images reveal that residual glassy grain boundary films are rich in oxygen and cations originating from the metal oxide/nitride additives, consistent with fine probe EDX analysis in the FEGTEM. Elemental analysis with high spatial resolution has also shown that grain growth into pockets of residual liquid/glass is associated with diffusion profiles in the glass in front of the growing grain. High resolution imaging in the TEM and elemental maps computed from electron energy filtered images show that the intergranular film thickness, in general, varies within a particular silicon nitride or sialon microstructure. Furthermore, grain boundaries, apparently free from residual glass may co-exist with glass-containing grain boundaries in some silicon nitride microstructures. In addition to the choice and weight fraction of sintering additives, factors such as the ionic radius of the cations originating from the additives, the local nano-scale chemistry and the relative grain orientation have an effect on the volume fraction and morphology of the intergranular microstructure.     

Extended X-ray absorption fine structure (EXAFS) study of secondary phases in Yb2O3-doped Si3N4 ceramics

Liquid-phase sintered Si3N4 doped with Yb2O3 as a sintering aid was characterized by both transmission electron microscopy and extended X-ray absorption fine structure (EXAFS) measurements. Structural information about the secondary phases was obtained with an emphasis being placed on the evaluation of EXAFS data. Two Si3N4 samples were processed which contained either 5 vol% or 10 vol% Yb2O3 as sintering additive. After sintering, only an amorphous secondary phase was observed in the material doped with 5 vol% Yb2O3. The material with the higher Yb2O3 volume fraction underwent a further heat treatment after the densification, in order to crystallize pockets of the secondary phase. This heat treatment resulted in the formation of Yb2Si2O7 at multi-grain junctions, with however, amorphous phases remaining along the grain and phase boundaries. The EXAFS data obtained from the two doped Si3N4 materials were compared with reference spectra obtained on pure Yb2O3 and synthetic Yb2Si2O7. No residual Yb2O3 was determined in the doped Si3N4 materials, independent of the Yb2O3 volume fraction. Compared to synthetic Yb2Si2O7, the secondary phase formed in the 10 vol% Yb2O3 containing material showed only subtle changes in the EXAFS data. A clear distinction between purely amorphous and a combination of crystalline plus amorphous Yb secondary phases was possible, when both doped Si3N4 materials were compared. However, no distinction between the glass phase present at triple junctions and the amorphous residue along grain/phase boundaries was feasible, since a full numerical data evaluation could not be performed.     

An Inhomogeneous Grain Boundary Composition in Silicon Nitride Ceramics as Revealed by 300 kV Field Emission Analytical Electron Microscopy

The chemical compositions of the grain boundary phases of silicon nitride (Si₃N₄) ceramics containing additives of 1 mole% and 10 mole% of an equi-molar mixture of Y₂O₃ and Nd₂O₃ have been studied by 300 kV field emission analytical electron microscopy. The energy dispersive x-ray spectra (EDS) are obtained from both two-grains and triple-grain junctions, where an electron beam of about 0.5 nm in diameter is focused. The thickness of the intergranular thin film is found to be about 1 nm, whose value is almost the same between two samples. The sintering additives are highly enriched at the triple-grain junctions, while they are less concentrated at the two-grain junctions. It is also shown that the additives are distributed inhomogeneously within the triple-grain junctions. Based on the composition analysis among the grain boundaries, an inhomogeneous grain boundary composition model for the Si₃N₄ ceramics is proposed.     

Formation of intergranular amorphous films during the microstructural development of liquid phase sintered silicon carbide ceramics

The microstructure of liquid phase sintered SiC ceramics was characterised by means of high resolution transmission electron microscopy (HRTEM). The SiC ceramics were pressureless sintered with the additions of Al₂O₃ and Y₂O₃ at sintering temperatures of 1800 and 1950°C, respectively. At a sintering temperature of 1800°C the microstructure of the SiC ceramics has no crystallised secondary phase and the SiC grains are separated by an intergranular amorphous film. In contrast, in the case of the microstructure of SiC ceramics sintered at 1950°C a clean interface without any amorphous layer between the SiC grains was observed. The secondary phase is crystallised into the Y₃Al₅O₁₂ phase and exhibits a clean interface between the SiC grains. An explanation for the existence or the absence of the intergranular glass films are given by an extended Clarke's model of the force balance of attractive van der Waals forces and repulsive steric forces. The chemical decomposition of the intergranular glass film at elevated temperature was considered.     

Microstructure and boundary phases of Lu–Al-doped silicon nitride by pressureless sintering

Various silicon nitride materials were fabricated by pressureless sintering using lutetia and alumina as sintering additives. Densification behavior, microstructure, strength and formation of secondary crystalline phases were investigated. The combination of Lu₂O₃/Al₂O₃ sintering aids can promote the densification and evolution of a fine grain microstructure of Lu–Al-doped silicon nitride because of the low viscosity of the liquid. The J′ phase given by Lu₄Si_2−xAl_xO_7+xN_2−x was considered to be secondary crystalline phase at the grain pockets. The composition with a Lu₂O₃/Al₂O₃ weight ratio 10/10 had highest strength of 690 ± 50 MPa.     

Effect of a small amount of liquid-forming additives on the microstructure of Al2O3 ceramics

Sintering behaviour and microstructure of Al₂O₃ ceramics without additives and with 0.02–0.25 mol% CaO + SiO₂ (CaO/SiO₂ = 1) were investigated. When Al₂O₃ bodies were sintered at 1400 °C, the sinterability and the grain size decreased as the content of CaO + Si₂ increased. When Al₂O₃ ceramics with 0.05 – 0.25 mol% CaO + SiO₂ were sintered at higher sintering temperature, both CaO and SiO₂ reacted with Al₂O₃ to produce the liquid phase along grain boundaries, and exaggerated platelet Al₂O₃ grains, with an aspect ratio of about 4.5, were formed. Because the size of platelet grains decreased as the content of CaO + SiO₂ increased, the distribution of either SiO₂ particles or this intergranular phase of CaO – Al₂O₃ – SiO₂ might control the microstructure.     

The microstructure of a ZnO varistor material

The microstructure of a ZnO varistor material has been investigated by a combination of X-ray diffractometry and analytical electron microscopy (SEM, TEM, STEM, EDX). The material was found to consist of: ZnO grains (doped with manganese, cobalt and nickel); smaller spinel grains which hinder the growth of ZnO grains during sintering; intergranular Bi-rich phases (namely -Bi₂O₃, pyrochlore and an amorphous phase); and a small proportion of ZnO-ZnO interfaces which did not have any intergranular film but to which bismuth had segregated. The intergranular microstructure is largely a result of processes which occur during liquid phase sintering and subsequent cooling to room temperature.     

Electron microscopy characterization of hot-pressed Al substituted Li7La3Zr2O12

Hot-pressing was used to prepare a dense (97% relative density) cubic Al substituted Li₇La₃Zr₂O₁₂ material at temperatures lower than typically used for solid-state and/or liquid phase sintering. Electron microscopy analysis revealed equiaxed grains, grain boundaries, and triple junctions free of amorphous and second phases and no Al segregation at grain boundaries. These results suggest that Al₂O₃ and/or Al cannot act as a sintering aid by reducing grain boundary mobility. If Al₂O₃ acts as a sintering aid its main function is to enter the lattice as Al to increase the point defect concentration of the slowest moving species.     

Potential use of only Yb2O3 in producing dense Si3N4 ceramics with high thermal conductivity by gas pressure sintering

Abstract

Yb₂O₃ is an efficient sintering additive for enhancing not only thermal conductivity but also the high-temperature mechanical properties of Si₃N₄ ceramics. Here we report the fabrication of dense Si₃N₄ ceramics with high thermal conductivity by the gas pressure sintering of α-Si₃N₄ powder compacts, using only Yb₂O₃ as an additive, at 1900 °C under a nitrogen pressure of 1 MPa. The effects of Yb₂O₃ content, sample packing condition and sintering time on the densification, microstructure and thermal conductivity were investigated. Curves of the density plotted against the Yb₂O₃ content exhibited a characteristic ‘N’ shape with a local minimum at 3 mol% Yb₂O₃ and nearly complete densification below and above this concentration. The effects of the sample packing condition on the densification, microstructure and thermal conductivity strongly depended on the Yb₂O₃ content. The embedded condition led to more complete densification but also to a decrease in thermal conductivity from 119 to 94 W m^-1 K^?1 upon 1 mol% Yb₂O₃ addition. The sample packing condition had little effect on the density and thermal conductivity (102–106 W m^?1 K^?1) at 7 mol% Yb₂O₃. The thermal conductivity value was strongly related to the microstructure.     

High-resolution interface analysis of SiC-whisker-reinforced Si3N4 and Al2O3 ceramic matrix composites

Whisker/matrix interfaces between -SiC whiskers and -Si₃N₄ or -Al₂O₃ matrices in composites were examined by high-resolution electron microscopy (HREM), and electron energy loss (ELS) and energy dispersive X-ray (EDS) spectroscopies. Most whisker/matrix interfaces were crystalline, with whiskers directly bonded to matrix crystals. Some whisker/matrix interface regions contained amorphous thin films and these occurred more often in the Si₃N₄ composite, which contained sintering additives, than in the Al₂O₃ matrix composite, which did not. No evidence for light element segregation at crystalline whisker/matrix interfaces was detected by ELS or EDS at 5 nm spatial resolution. Impurities were concentrated in glassy regions in matrix grain boundaries, triple junctions, or at infrequent whisker/matrix interfaces containing amorphous films.     

Potential use of only Yb2O3 in producing dense Si3N4 ceramics with high thermal conductivity by gas pressure sintering

Yb₂O₃ is an efficient sintering additive for enhancing not only thermal conductivity but also the high-temperature mechanical properties of Si₃N₄ ceramics. Here we report the fabrication of dense Si₃N₄ ceramics with high thermal conductivity by the gas pressure sintering of α-Si₃N₄ powder compacts, using only Yb₂O₃ as an additive, at 1900 °C under a nitrogen pressure of 1 MPa. The effects of Yb₂O₃ content, sample packing condition and sintering time on the densification, microstructure and thermal conductivity were investigated. Curves of the density plotted against the Yb₂O₃ content exhibited a characteristic ‘N’ shape with a local minimum at 3 mol% Yb₂O₃ and nearly complete densification below and above this concentration. The effects of the sample packing condition on the densification, microstructure and thermal conductivity strongly depended on the Yb₂O₃ content. The embedded condition led to more complete densification but also to a decrease in thermal conductivity from 119 to 94 W m^-1 K⁻¹ upon 1 mol% Yb₂O₃ addition. The sample packing condition had little effect on the density and thermal conductivity (102–106 W m⁻¹ K⁻¹) at 7 mol% Yb₂O₃. The thermal conductivity value was strongly related to the microstructure.     

AEM investigation of ceramic/lncoloy 909 diffusional reactions after joining by HIP

Diffusion bonding by hot isostatic pressing (HIP) was performed between Incoloy 909 and five different ceramics. Two of the ceramics were composites made from powder mixtures of Si₃N₄ and either 60 vol% TiN or 50 vol% TiB₂, while three were monolithic materials, namely Si₃N₄ with 2.5 wt% Y₂O₃ as a sintering additive, Si₃N₄ without additives, and Si₂ N₂O without additives. A diffusion couple geometry was developed to facilitate the preparation of thin-foil specimens for examination by analytical electron microscopy (AEM). Diffusion bonding was performed by HIP at 927°C (1200K) and 200 MPa for 4 h. The formation of reaction layers was very limited, being less than 1 m in total layer thickness. Two reaction products were found by AEM; a continuous, very thin, (100 nm) layer of fine TiN crystals at the initial ceramic/metal interface, and larger grains extending about 100–500 nm into the superalloy and forming a semi-continuous layer of a G-phase suicide containing mainly nickel, silicon and niobium.     

Piezoelectricity and microstructures of modified lead titanate ceramics

Modified lead titanate ceramics with the composition Pb_0.70 Ca_0.30 Ti_0.94 (Co_1/2W_1/2)_0.06 O₃ with 1 mol% MnO were prepared by the mixed oxide route. By varying the sintering temperature, ceramics with average grain sizes between 2.8 and 5m were obtained. An increase in grain size resulted in an increased electromechanical anisotropy and a decreased dielectric constant. Transmission electron microscopy was used to examine the ferroelectric domain boundaries and intergranular phases. Indications are that during poling favourably oriented domains approximately doubled in size by 90 ° type domain wall switching. Evidence was found for the existence of a vitreous intergranular phase at multiple grain junctions. EDS microanalysis indicated that the amorphous grain boundary phase had a lower lead content than the bulk material.     

The silicon lanthanide oxynitrides

A new group of materials called the silicon lanthanide oxynitrides has been prepared by the reaction between Si₃N₄ and several oxides of the lanthanide series (La₂O₃, Sm₂O₃, Dy₂O₃, Er₂O₃, and Yb₂O₃). These oxides formed compounds of the type Si₃N₄ · R₂O₃ and R₄Si₂O₇N₂ (R being lanthanide). In addition La₂O₃ and Yb₂O₃ formed the compounds 2Si₃N₄ · La₂O₃ and Yb₂Si₃O₅N₂, respectively. Certain similarities in the unit cells of these compounds have been noted, and their structures are discussed in terms of similarity to known minerals. It is suggested that this group of materials contains a large number of compounds.     

Preparation of the rod-like β-Si3N4 particles favoring the self-reinforcing Si3N4 ceramics

The β-Si₃N₄ particles were prepared by heating original α-Si₃N₄ powder with rare earth oxide Nd₂O₃ or Yb₂O₃ additives at 1600-1700 °C for 1.5 h. The transformation ratio of α-Si₃N₄ was also investigated by XRD. The results showed that Yb₂O₃ could accelerate the transformation of Si₃N₄ more effectively than Nd₂O₃ and the powder heated at 1700 °C with over 4 wt.% Yb₂O₃ has a high transformation ratio of over 98%. The morphologies of the heated powders were observed by scanning electron microscopy. The results showed that the powder heated at 1700 °C with 4 wt.% Yb₂O₃ had ideal β-Si₃N₄ rod-like morphology particles. This heated powder was used as a seed by adding it to the original α-Si₃N₄ powder to prepare self-reinforced Si₃N₄ ceramic by hot-pressed sintering. The fracture toughness of the seeded Si₃N₄ ceramics increased to 9.1 MPa m^1/2 from 7.6 MPa m^1/2 of the unseeded Si₃N₄ ceramics, while the high value of strength was still kept at 1200 °C.     

Effects of attrition milling and post-sintering heat treatment on fabrication,microstructure and properties of transformation toughened ZrO2

The effect of attrition milling and post-sintering heat treatment on the fabrication, phase relations, microstructure and properties of ZrO₂ (+2.3vol% Y₂O₃) powder used to produce a transformation toughened material was examined. Powder used to fabricate the unmilled material was treated and consolidated by a colloidal method. The same powder, treated and consolidated by the same method, but ball milled in a commercial alumina mill before consolidation, was used to fabricate the milled material. Both materials were sintered at 1400° C for 1 h and then heat treated at higher temperatures. Milling introduced Al₂O₃ inclusions (< 1 vol%) and a glass phase (7 to 10 vol%). The milled powder was more difficult to sinter and exhibited more bloating (density decrease) during subsequent heat treatment. Transmission electron microscopy observations indicated that the larger glass content of the milled material beneficially reduced residual stresses that arose due to thermal contraction anistropy. Post-sintering heat treatment at temperatures > 1450° C produced detectable amounts of cubic ZrO₂ consistent with previously reported phase studies of the ZrO₂-Y₂O₃ system. The development of a bimodal grain structure was concurrent with the formation of detectable cubic phase. The larger grains in this bimodal distribution were primarily observed on the external surface and co-ordinating pores produced during the post-sintering heat treatments which were responsible for the bloating phenomenon. It is hypothesized that the pores were produced by the release of high pressure oxygen during cubic phase formation. Both fracture toughness (K _c) and hardness of the as-sintered materials were unaffected by milling. Hardness decreased with bloating and the decrease was more pronounced for the milled material which exhibited more bloating.     

Corrosion of silicon nitride ceramics in aqueous HF solutions

The leaching behaviours of hot-pressed Si₃N₄ ceramics containing Y₂O₃, Al₂O₃ and AIN as additives and hot isostatically pressed Si₃N₄ without additives were studied in 0.1 to 10 M HF aqueous solutions at 50 to 80° C. Silicon and aluminium ions were dissolved into the HF solutions, but yttrium ion did not dissolve at all and formed insoluble YF₃. The dissolution of silicon and aluminium ions was controlled by the surface chemical reaction and the apparent activation energies were 70.5 to 87.6 kJ mol^–1, respectively. The corrosion rate increased with increasing degree of crystallization of the grain boundary phases. The corrosion resulted in roughness of the surface and degradation of the fracture strength. Si₃N₄ ceramics containing an amorphous phase at the grain boundaries showed the most excellent resistance to corrosion with HF solution, and kept a fracture strength of above 400 M Pa even after leaching 40% of the silicon ions.     

The effects of pre-oxidation on the sintering and mechanical property of powder injection moulded SiC material

Usually, injection moulded SiC green parts are debound in inert atmosphere or vacuum, which induces the residual carbon and increases forming cycle and production cost. In this paper, injection moulded SiC with Al₂O₃ and Y₂O₃ as sintering assistant was thermal debound in air and Ar, respectively. The paper investigates the effects of pre-oxidation during debinding stage on the sintering and mechanical property of SiC material. During sintering, the oxide SiO₂ is in favour of the shrinkage of debound samples at lower temperature. After sintering, the linear shrinkage of sintered samples with pre-oxidation is bigger than the sample without pre-oxidation. Test results by TEM and XRD indicate that SiO₂ disappear from the inside of the sintered samples. The loss of SiO₂ decreases the content of Al₂O₃, which affects the formation of YAG (Y₃Al₅O₁₂). Sintered Sic samples contain α-SiC phase and intergranular phase. There is no hetero-phase between the boundaries of α-SiC phase and intergranular phase. The bending and compression strength values of sintered samples with pre-oxidation reach to 537 MPa and 2.89 GPa, respectively. These values approach the strength of sintered samples without pre-oxidation (594 MPa and 3.0 GPa).