Fabrication of high strength β-sialon by reaction sintering

The reaction sintering of β-sialon (Si₄Al₂O₂N₆) from a powder mixture of Si₃N₄, Al₂O₃ and AIN was studied to clarify factors affecting the densification. The presence of sufficient SiO vapour on the compact and excess oxide with respect toβ-sialon composition was the most important factor. High densityβ-sialon was fabricated by heating the compact at 1800° C under 1 atm. N₂. The sintering was carried out with sufficient SiO vapour pressure to prevent thermal decomposition of sintered sialon by packing the compact with a powder mixture of Si₃N₄ and SiO₂. Care was taken to minimize the amount of excess oxide in the starting composition to obtain a high density sialon with a small amount of intergranular X-phase. The maximum density of 3.04 g cm⁻³ was obtained from the compact with 2 wt % excess Al₂O₃ in the composition. The strength of the sinteredβ-sialon was 490 MN m⁻² at room temperature and 480 MN m⁻² at 1200° C. The values are the best among those so far published for sinteredβ-sialons.     

Phase relationships in the system Si3N4-SiO2-La2O3

Phase relationships in the system Si₃N₄-SiO₂-La₂O₃ have been investigated after cooling from 1700° C. Two phases, 2Si₃N₄·La₂O₃ (monoclinic) and La₅ (SiO₄)₃N (hexagonal), were identified; the other two phases in the system, LaSiO₂N (monoclinic) and La₄Si₂O₇N₂ (monoclinic), were found to dissociate to La₅ (SiO₄)₃N and a glass after cooling from temperatures above 1650° C. The unit cells of 2Si₃N₄·La₂O₃, LaSiO₂N and La₄Si₂O₇N₂ have been determined and compared with those of preceding works. The results are discussed in relation to the intergranular phases observed when Si₃N₄ is sintered with La₂O₃ additions.     

Thermal expansion coefficient of Y-α′-sialon

A sialon composite composed of Y-α′-sialon and β′-sialon has been fabricated by hot pressing mixtures of Si₃N₄, Y₂O₃ and AlN powders. Thermal expansion coefficients of the Y-α′-sialon and β′-sialon were determined by the high-temperature X-ray diffraction technique. The thermal expansion coefficient of Y-α′-sialon depended on the composition, being minimum at x=0.3 in the formula Y_x(Si_12-4.5x, Al_4.5x)(O_1.5x, N_16-1.5x). The coefficient of β′-sialon increased with increasing lattice constant, that is, the z value in the formula Si_6-zAl_zO_zN_8-z. The thermal expansion coefficient of sialon composites determined by a differential dilatometer increased with increasing amount of Y-α′-sialon. This revised version was published online in November 2006 with corrections to the Cover Date.     

Phase relationships in the system Si3N4-Y2O3-SiO2

Examination of compositions in the system Si₃N₄-Y₂O₃-SiO₂ using sintered samples revealed the existence of two regions of melting and three silicon yttrium oxynitride phases. The regions of melting occur at 1600° C at high SiO₂ concentrations (13 mol% Si₃N₄ + 19 mol% Y₂O₃ + 68 mol% SiO₂) and at 1650° C at high Y₂O₃ concentrations (25 mol % Si₃N₄ + 75 mol % Y₂O₃). Two ternary phases 4Y₂O₃ ·SiO₂ ·Si₃N₄ and 10Y₂O₃ ·9SiO₂ ·Si₃N₄ and one binary phase Si₃N₄ ·Y₂O₃ were observed. The 4Y₂O₃ ·SiO₂ ·Si₃N₄ phase has a monoclinic structure (a= 11.038 Å, b=10.076 Å, c=7.552 Å, =108° 40) and appears to be isostructural with silicates of the wohlerite cuspidine series. The 10Y₂O₃ ·9SiO₂ ·Si₃N₄ phase has a hexagonal unit cell (a=7.598 Å c=4.908 Å). Features of the Si₃N₄-Y₂O₃-SiO₂ systems are discussed in terms of the role of Y₂O₃ in the hot-pressing of Si₃N₄, and it is suggested that Y₂O₃ promotes a liquid-phase sintering process which incorporates dissolution and precipitation of Si₃N₄ at the solid-liquid interface.Visiting Research Associate at Aerospace Research Laboratories, Wright-Patterson Air Force Base, Ohio 45433, under Contract No. F33615-73-C-4155 when this work was carried out.     

Sintering of Si3N4 in the presence of additives from Y2O3-SiO2-Al2O3 system

The sintering process of Si₃N₄ in the presence of a liquid phase from the Y₂O₃-SiO₂-Al₂O₃ system was investigated. The starting composition of liquid phase was varied according to data in the phase diagram of the Y₂O₃-SiO₂-Al₂O₃ system, in order to lower the temperature of liquid formation because it might exhibit an influence on the sintering behaviour of Si₃N₄. Densification as well as phase analysis were followed as a function of composition and the amount of liquid phase, both in the sintered and in hot pressed samples.     

Luminescence properties of the Ca-alpha-sialon:Eu solid solution

The Ca,Eu-α-sialon powders with the mixed solid solution composition have been manufactured via the solid-state reaction process in flowing nitrogen in a graphite furnace at a relatively low temperature of 1650 °C without an external overpressure. XRD data with Rielveld refinement and XPS measurements were used for characterization of the lattice constants and the surface chemical composition. The monophase Ca-Eu-α-sialon was obtained with the nominal composition of Eu_0.048Ca_0.702Si_7.75Al_2.25O_0.75N_15.25. The highest emission intensity in a yellow-orange region at 590 nm and quantum efficiency of 66% was found for this pure Ca,Eu-α-sialon. Estimation of m,n values from the lattice constant and EDS results showed a small deviation from the nominal composition of designed α-sialon. XPS results demonstrated significant changes of the chemical composition in the oxidized surface of phosphor particles. Possible reasons of emission redshift and relationship between the actual solid solution composition and luminescence properties are discussed in terms of simultaneous presence of Eu²⁺ and Eu³⁺ ions in the sialon crystal lattice and residual oxynitride glass.     

The stability of mother glass for porous glass-ceramics of the TiO2-SiO2 system

The stability of the glasses of TiO₂-SiO₂-Al₂O₃-B₂O₃-CaO-MgO and TiO₂-SiO₂-Al₂O₃-P₂O₅-CaO-MgO systems during formation has been investigated as a basic study on the preparation of porous glass-ceramics. The main factor affecting the stability of these glasses which are used as mother glasses of porous glass-ceramics was CaO content. The stability was remarkably improved by increasing the CaO content.The preparation of porous glass-ceramics with an appropriate amount of pore volume was possible from a glass containing CaO up to 30 mol%. The DTA trace of the glasses showed two distinct exothermic peaks in the ranges 30–130° C and 140–300° C above glass transition temperatures. The porous glass-ceramics of TiO₂-SiO₂ system containing more than 60 mol% TiO₂ and having a surface area larger than 400m²g^–1, a pore volume of 0.3–0.5 ml g^–1, and average pore radius between 1 and 20 nm were fabricated.     

Sintering process of Y2O3-added Si3N4

The sintering process of Y₂O₃-added Si₃N₄ has been investigated by dilatometry and microstructural observations. Densification was promoted above 1440 ° C by the formation of eutectic melts in the Y₂O₃-SiO₂-Si₃N₄ triangle. However, the dilatometric curves indicated no shrinkage corresponding to the rearrangement process, despite liquid-phase sintering. The kinetic order for The Initial-stage sintering was 0.47 to 0.49. These values indicated that the phase-boundary reaction was rate controlling. The apparent activation energy (323 kJ mol^–1) was smaller than the dissociation energy for the Si-N bond (435 kJ mol^–1). ESR data and lattice strain indicated that the disordered crystalline structure of the Si₃N₄ starting powder promoted the reaction of Si₃N₄ with eutectic melts. After a period of initial-stage sintering, the formation of fibrous -Si₃N₄ grains resulted in interlocked structures to interrupt the densification.     

Decomposition of some Si-Al-O-N powders during plasma spheroidization

An attempt to prepare Si-AI-O-N glasses with compositions lying along the mullite-Si₃N₄ junction, by subjecting powders to rapid melting in a nitrogen plasma followed by quenching (10⁶ C sec^–1), resulted in their decomposition. Powders (–53, + 37m) containing SiO₂/Si₃N₄ in the ratio 3/1 tended to decompose to give spheroidized-AI₂O₃/-AI₂O₃ particles, SiO and N₂. For SiO₂/Si₃N₄>3 the particles consisted of-AI₂O₃ stabilized by the presence of SiO₂ in solution, whereas if SiO₂/Si₃N₄<3, the particles consisted predominantly of the AI₂O₃-AIN spinel. Larger particle size powders (–75, + 53m) did not decompose to the same extent and there was evidence that a nitrogen-containing glass was formed with a devitrification temperature of 1100° C compared with 1000° C for AI₂O₃-SiO₂ glasses.     

Oxidation of sintered silicon nitride

The influence of oxidation at 1200 °C in air for up to 1000 h on the mechanical properties of two Si₃N₄-Y₂O₃-Al₂O₃ materials with different Y₂O₃/Al₂O₃ ratios, Material A (Si₃N₄-13.9 wt% Y₂O₃-4.5 wt% Al₂O₃) and Material B (Si₃N₄-6.0 wt% Y₂O₃-12.4 wt% Al₂O₃), was investigated. The oxidation significantly improves the high-temperature strength and fracture toughness of both materials, but more for Material A. After oxidation, Material A at 1300 °C retains 93% of its room-temperature strength and 87% higher than that before the oxidation. The oxidation has a different effect on the room-temperature K _IC for the two materials. The room-temperature Weibull modulus of Material A decreased by more than half while the 1200 °C Weibull modulus decreased slightly after oxidation. The annealing treatment prior to oxidation had no effect on the high-temperature strengths of the materials after oxidation. The effect of oxidation on mechanical properties is discussed in terms of the microstructure change of the materials.     

Preparation of Ca-α SiAlON hollow spheres by carbothermal reduction-nitridation of CaO-Al2O3-SiO2 glass

Ca-α SiAlON powders were prepared by carbothermal reduction-nitridation of CaO-Al₂O₃-SiO₂ glasses at 1450 °C for 2 h in nitrogen. The content of Ca-α SiAlON phase was 65-81% in the products, and the other phases were AlN and β-SiAlON. The products contained hollow spheres with the size of around 5 μm in diameter. The particle morphology was almost identical to that of Ca-α SiAlON prepared from CaCO₃-Al₂O₃-SiO₂ powder mixtures.     

Multicomponent toughened ceramic materials obtained by reaction sintering

Fully dense zirconia toughened ceramics with a mullite matrix from the basis of information on the quaternary system ZrO₂-Al₂O₃-SiO₂-CaO, in a temperature range as low as 1425 to 1450° C, have been obtained by reaction sintering of zircon/alumina/calcium carbonate mixtures. The shrinkage, advance of reaction, microstructure and mechanical properties of different compositions are reported. The results are explained in terms of a transitory liquid phase that appears at temperatures lower than 1400° C.     

Hot-pressed β-Si3N4 containing small amounts of Be and O in solid solution

Single phase, hot-pressed Si₃N₄ ceramics with relative densities >95% and equiaxed grain structures have been prepared from high purity Si₃N₄ powders having specific surface areas of 8 to 20 m² g⁻¹ and oxygen contents ⩾2 wt % using a small amount of Be₃N₂ or BeSiN₂ as a densification aid. Densification depended sensitively on the concentration of Be and O in a given Si₃N₄ powder and on the usual hot-pressing parameters of pressure, temperature and time. A close association was found between densification and the conversion ofα- toβ-Si₃N₄ during hot-pressing. Based on the data presented, chemical reactions that occur during hot-pressing involve: (1) reaction of the densification aid with SiO₂ on the Si₃N₄ particle surfaces to form BeO and Si₂N₂O; (2) the further reaction of these two reaction products to give probable formation of a transient liquid phase (TLP); and (3) the reaction between TLP andα-Si₃N₄ particles to cause densification, probably by a solution-reprecipitation process, and conversion ofα-Si₃N₄ into aβ-Si₃N₄ solid solution. The chemical composition of a single phaseβ-Si₃N₄ solid solution prepared in this study by hot-pressing was approximately Si_2.9Be_0.1N_3.8O_0.2.     

Intermediate temperature oxidation in silicon nitride yttria ceramics

Silicon nitride billets with both 4% and 8% Y₂O₃ additives have been subjected to oxidation treatments for up to 300 h, in air, in the temperature range 700 to 1000° C. Flexure strength and weight gain measurements together with both scanning and transmission electron microscopy and X-ray diffraction studies were conducted on these billets in an effort to understand the oxidation process. It appears that the degradation phenomena is associated with both the formation of phases outside the Si₃N₄-Si₂ON₂-Y₂Si₂O₇ compatibility triangle of the system Si₃N₄-SiO₂-Y₂O₃ and with the decomposition of W-containing phases at and near the grain boundaries.     

Transparency of LiTaO3-SiO2-Al2O3 glass-ceramics in relation to their microstructure

The glasses with various compositions in the LiTaO₃-SiO₂-Al₂O₃ system were heated from room temperature to temperatures ranging from 750° to 1050° C at a rate of 5° C min^–1. From the glasses in the LiTaO₃-SiO₂ system no transparent glass-ceramic was obtained even when their LiTaO₃/SiO₂ mole ratios were as high as 2.33. The diameter and number of the LiTaO₃ crystal grains precipitated in the glasses were 5–15 m and 10⁸–10¹⁰ grains cm^–3, respectively. On the contrary, transparent glass-ceramics were obtained from the glasses containing Al₂O₃; their compositions covered a fairly large area in the LiTaO₃-SiO₂ -Al₂O₃ system, which encompasses the compositions with the LiTaO₃/SiO₂+AlO_1.5 mole ratio as low as 0.25. The diameter and number of the LiTaO₃ crystal grains precipitated in the transparent glass-ceramics were as small as 10–20 nm and as many as 10¹⁶–10¹⁸ grains cm^–3, respectively. High nucleation rates of the LiTaO₃ crystals in the Al₂O₃-containing glasses were interpreted in terms of structural inflexibility induced in the glass-network by the addition of Al₂O₃ to the LiTaO₃-SiO₂ system.     

Multicomponent toughened ceramic materials obtained by reaction sintering

Very dense zirconia-toughened ceramics with a mullite matrix based on the quaternary system ZrO₂-Al₂O₃-SiO₂-MgO in the temperature range as low as 1450 to 1500° C have been obtained by reaction sintering of zircon/alumina/magnesia mixtures. The shrinkage, advance of reaction, microstructure, densification mechanism and mechanical properties are reported. The results are explained in terms of transitory and permanent liquids that appear at 1425° C and ~ 1450° C respectively.     

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.     

Phase relations in the system CaO-B2O3-SiO2

Phase relations in the lime-rich portion of the system CaO-B₂O₃-SiO₂ have been studied by microscopy, infrared spectroscopy and X-ray powder diffraction of heated mixtures and quenched charges. Extensive solid solution of B₂O₃ in Ca₂SiO₄ occurs along the Ca₂SiO₄-Ca₃B₂O₆ boundary, which has been studied in detail. It contains a ternary compound, Ca₁₁B₂Si₄O₂₂, which is stable to liquidus temperatures, melting incongruently to Ca₂SiO₄ and liquid at 1420 °C. Ca₁₁B₂Si₄O₂₂forms a eutectic with Ca₃B₂O₆ at 1400 °C and, in the ternary system, with CaO and Ca₃B₂O₆ at 1390 °C.     

Dielectric properties of sintered materials prepared from glass-ZrO2-SrTiO3 mixtures

(Ca,Sr,Ba)O-Al₂O₃-SiO₂-TiO₂ glass powder was mixed with 6.7 mol % ZrO₂ and 0–11.96 mol % SrTiO₃. The mixtures were sintered at 850 °C, 900 °C or 950 °C. Most of the glass phase changed to crystalline phases of (Ca,Sr,Ba)₂TiSi₂O₆TS, (Ca,Sr,Ba)Si₂O₆AS, ZrO₂ and SrTiO₃ during sintering. The dielectric properties of samples sintered at 900 °C were measured at 1 MHz using silver electrodes. With increasing SrTiO₃ content, the dielectric constant increased from 12 to 19 and the temperature coefficient of dielectric constant, TCD, changed from -30 ppm ^C^-1 to -400ppm^C^-1. Using mixture equations, dielectric constants and TCD values were estimated for the samples and these values were compared with experimental results.     

HIP-sinteredβ- and mixedα-β sialons densified with Y2O3 and La2O3 additions

Various fully dense sialon materials sintered by the glass-encapsulated hot isostatic pressing technique were synthesized using Y₂O₃ and/or La₂O₃ as sintering aids. Constant molar amounts of the oxide mixtures were added in the ratios Y₂O₃/La₂O₃:100/0, 75/25, 50/50, 25/75, 0/100. The samples were sintered at two different temperatures, 1550 and 1825° C. At the lower temperature, unreacted-Si₃N₄ was present in the samples in addition to-sialon and secondary phases. The samples sintered at 1825° C showed that yttrium but not lanthanum favoured-sialon formation. The amount of intergranular phase increased by about 50% when Y₂O₃ was replaced by La₂O₃. The La-sialon ceramics have as good an indentation fracture toughness as the Y-sialon ceramics, about 5 MPam^–1/2, but the Vicker's hardness is slightly lower, being 1400 kg mm^–2 at a 98 N load.