Sintering process of Y2O3 and Al2O3-doped Si3N4

The sintering process of Y₂O₃- and Al₂O₃-doped Si₃N₄ has been investigated by dilatometry and microstructural observations. The densification progressed through three processes. The bulk density increased to 85% theoretical without the formation of -Si₃N₄ in the initial process. The densification once terminated after the second process. The / transformation of Si₃N₄ and the related formation of prismatic grains reduced the densification rate in the second process, although the grain size and the aspect ratio were very small. The final process was the densification of -Si₃N₄, where the fibrous grains grew remarkably. The kinetic order for the densification of -Si₃N₄ indicated a diffusion-rate controlling mechanism with the activation energy of 244 kJ mol^–1 (<1450 ° C) and 193 kJ mol^–1 (>1450 ° C). The influence of heating rate on the grain growth was characterized by a parameter derived from kinetic parameters. The relationships between grain growth and densification behaviour have also been discussed.     

Electrical conductivity of Cr2O3-doped Y2O3-stabilized ZrO2

The electrical conductivity of Cr₂O₃-doped Y₂O₃-stabilized ZrO₂ (YSZ) has been studied as functions of composition, temperature and oxygen pressure. The specimens have been prepared by hot preoning of co precipitated oxides to yield >99.7% density. The Cr₂O₃ added above the solubility limit ( 0.7 mol %) precipitated as a secondary phase at the grain boundaries. The conductivity of Cr₂O₃-doped YSZ was almost independent of the oxygen pressure in the range 10¹⁸ to 10⁵ Pa, indicating a dominant ionic condition. The electronic conductivity of dopant CR₂O₃ would be hindered by the higher ionic conductivity in thep _O2 ranges studied. The conductivity and the activation energy for conduction decreased slightly with the addition of Cr₂O₃. These phenomena seemed to be caused by vacancy trapping or polarization at the grain boundaries with the Cr₂O₃ precipitates. The samples with 1 mol % Cr₂O₃ addred to zirconia containing various Y₂O₃ contents showed similar conduction behaviour to those without Cr₂O₃ addition; that is, the conductivity maxima are observed at around 8 mol % Y₂O₃ addition to zirconia, and the activation energies increased with tha Y₂O₃ addition.     

Thermal conductivity of unidirectionally oriented Si3N4w/Si3N4 composites

-silicon nitride whiskers were aligned unidirectionally in silicon nitride sintered with 2 wt% Al₂O₃ and 6 wt% Y₂O₃. It was be densified by the Gas Pressure Sintering (GPS) method. Thermal conductivity of the sintered body with different amount of - silicon nitride whiskers was measured by the direct contact method from 298 K to 373 K. This unidirectionally oriented -silicon nitride whiskers grew into the large elongated grains, and improved also the thermal conductivity. The amount of -silicon nitride whiskers changed the microstrcuture, which changed the thermal conductivity.     

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.     

Pressureless sintering of Si3N4 with Y2O2 and Al2O3

Pressureless sintering of Si₃N₄ with Y₂O₃ and Al₂O₃ as additives was carried out at 1750°C in N₂ atmosphere. Si₃N₄ materials which had more than 92% relative density were obtained with 20wt% addition of additives. The flexural strength of as-sintered materials containing 5 to 8.6wt% Al₂O₃ and 15 to 11.4wt% Y₂O₃ was in the range of 480 to 560 MPa at room temperature. The glassy grain-boundary phase of as-sintered materials crystallized to 3Y₂O₃ · 5Al₂O₃ (YAG), Y₂O₃ · SiO₂ (YS), Y₂O₃ · 2SiO₂ (Y2S) and 10Y₂O₃ · 9SiO₂ sd Si₃N₄ (NA) by heat-treatment at 1250° C for 3 days. A specimen containing 15wt% Y₂O₃ and 5wt% Al₂O₃ sintered at 1750° C for 4 h was heat-treated at 1250° C for 3 days to precipitate YAG and YS. The nitrogen concentration of the grain-boundary glassy phase of the specimen was found to be very high, and therefore the flexural strength of the crystallized specimen scarcely decreased at elevated temperatures (the flexural strength of this specimen is 390 MPa at room temperature and 360 MPa at 1300° C). Resistance to oxidation at 1200° C of the specimen was good as well as the flexural strength, compared with that of as-sintered materials.     

Hot isostatic pressing of Si3N4 with Y2O3 additions

The effect of Y₂O₃ additive on the properties of hot isostatically pressed silicon nitride was studied. The influence of small additions of Y₂O₃ on the densification of silicon nitride was investigated. The density and elastic moduli of the product increase with increasing of the Y₂O₃ additions. The hot isostatically pressed pure silicon nitride consists of -Si₃N₄, -Si₃N₄and Si₂N₂O; phase content of the hot isostatically pressed silicon nitride with 10 wt % Y₂O₃addition consists of -Si₃N₄, yttrium silicate and Y₂Si₃O₃N₄. The effect of the outgassing of the specimens prior to hot isostatical pressing on the properties of the final material is discussed.     

Thermal conductivity measurements of PTFE and Al2O3 ceramic at sub-Kelvin temperatures

The design of low temperature bolometric detectors for rare event searches necessitates careful selection and characterization of structural materials based on their thermal properties. We measure the thermal conductivities of polytetrafluoroethylene (PTFE) and Al₂O₃ ceramic (alumina) in the temperature ranges of 0.17–0.43 K and 0.1–1.3 K, respectively. For the former, we observe a quadratic temperature dependence across the entire measured range. For the latter, we see a cubic dependence on temperature above 0.3 K, with a linear contribution below that temperature. This paper presents our measurement techniques, results, and theoretical discussions.     

Slip-casting properties of Si3N4 with Y2O3 and Al2O3 as sintering additives

The effects of particle charging and powder–liquid suspension stability on the slip-casting properties of Si3N4 powder were examined. Y2O3 and Al2O3, used as sintering additives, were seen to affect the dispersion stability of the base material (Si3N4). The zeta potentials of the three powders and the rheological behaviour of the 55 wt% solids-loaded slips, involving known concentrations of a polymeric deflocculant (Dolapix PC33), showed that the multicomponent system can be dispersed stably within the pH range 9–11. Green compacts, obtained by casting these slips into plaster moulds, were found to give densities in the range 50–61% of the theoretical value. © 1998 Chapman & Hall     

Creep behaviour of Si3N4/Y2O3/Al2O3/AIN alloys

The compression creep behaviour of pressureless sintered Y₂O₃/Al₂O₃/AIN-doped Si₃N₄ was studied between 1473 and 1673 K, under stresses ranging from 100–300 MPa. Strain rate versus stress and temperature analysis give a stress exponent n1 and an activation energy Q=860 kJ mol^–1. Microstructural change was investigated by transmission electron microscopy. The observed strain whorls, the stress exponent and the activation energy are indicative of a solution-diffusion-precipitation accommodated grain-boundary sliding where the diffusion through the glass is rate controlling.     

Study on the structures of N-containing melilite Y2Si3O3N4 and Nd2Si2.5Al0.5O3.5N3.5

Rietveld refinements have been used to determine the structure of Y2Si3O3N4 from X-ray data and Nd2Si2.5Al0.5O3.5N3.5 from neutron powder diffraction data. The refinements show that in the melilite phase Y2Si3O3N4 and melilite solid solution Nd2Si2.5Al0.5O3.5N3.5 the distributions of cations and anions are almost identical. They are analogous to the akermanite (Ca2MgSi2O7) structure, with Si/Si,Al atoms at the origin and centre of the unit cell and with four N/N,O atoms forming the SiN4/(Si,Al)(N3.5O0.5) tetrahedra which share corners with SiO2N2/(Si,Al)O2.25N1.75 tetrahedra to form a continuous sheet structure. Each Y3+ or Nd3+ ion is surrounded by eight N/O atoms forming the coordination polyhedron in Y2Si3O3N4 and Nd2Si2.5Al0.5O3.5N3.5 respectively. The arrangement of Al, Si atoms in the tetrahedra in Nd2Si2.5Al0.5O3.5N3.5 structure is also discussed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Effect of additive-oxide amount on sintering of Si3N4 with Y2O3 and Nd2O3

The effect of additive amount on the gas-pressure sintering of silicon nitride is investigated. Silicon nitride containing 0.5 to 10 mol % (SN10) of equimolar Y₂O₃-Nd₂O₃ is fired at 1600 to 1900 °C for 4 h in 10 M Pa N₂ gas. A small amount of oxide (1 mol %; SN1) is effective for densification as well as a larger amount of oxide (6–10 mol %) when fired at 1900 °C. Composition analysis of sintered specimens indicates that SN1 densifies through a small amount of SiO₂-rich liquid-phase, whereas SN10 densifies by way of a large amount of additive-oxide-rich liquid phase.     

The high temperature creep deformation of Si3N4-6Y2O3-2Al2O3

The creep properties of silicon nitride containing 6 wt % yttria and 2 wt% alumina have been determined in the temperature range 1573 to 1673 K. The stress exponent, n, in the equation ⁿ was determined to be 2.00±0.15 and the true activation energy was found to be 692±25 kJ mol^–1. Transmission electron microscopy studies showed that deformation occurred in the grain boundary glassy phase accompanied by microcrack formation and cavitation. The steady state creep results are consistent with a diffusion controlled creep mechanism involving nitrogen diffusion through the grain boundary glassy phase.     

Si3N4-ZrO2 composites with small Al2O3 and Y2O3 additions prepared by HIP

Si₃N₄-ZrO₂ composites have been prepared by hot isostatic pressing at 1550 and 1750 °C, using both unstabilized ZrO₂ and ZrO₂ stabilized with 3 mol% Y₂O₃. The composites were formed with a zirconia addition of 0, 5, 10, 15 and 20 wt%, with respect to the silicon nitride, together with 0–4 wt% Al₂O₃ and 0–6 wt% Y₂O₃. Composites prepared at 1550 °C contained substantial amounts of unreacted -Si₃N₄, and full density was achieved only when 1 wt% Al₂O₃ or 4 wt % Y₂O₃ had been added. These materials were generally harder and more brittle than those densified at the higher temperature. When the ZrO₂ starting powder was stabilized by Y₂O₃, fully dense Si₃N₄-ZrO₂ composites could be prepared at 1750 °C even without other oxide additives. Densification at 1750 °C resulted in the highest fracture toughness values. Several groups of materials densified at 1750 °C showed a good combination of Vickers hardness (HV10) and indentation fracture toughness; around 1450 kg mm^–2 and 4.5 MPam^1/2, respectively. Examples of such materials were either Si₃N₄ formed with an addition of 2–6 wt% Y₂O₃ or Si₃N₄-ZrO₂ composites with a simultaneous addition of 2–6 wt%Y₂O₃ and 2–4 wt% Al₂O₃.     

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.