Nd2O3-Doped Sialons with ZrO2/ZrN Additions Formed by Sintering and Hot Isostatic Pressing

β-sialon and Nd₂O₃-doped α-sialon materials of varying composition were prepared by sintering at 1775° and 1825°C and by glass-encapsulated hot isostatic pressing at 1700°C. Composites were also prepared by adding 2–20 wt% ZrO₂ (3 mol% Nd₂O₃) or 2–20 wt% ZrN to the β-sialon and α-sialon matrix, respectively. Neodymium was found to be a fairly poor α-sialon stabilizer even within the α-phase solid solution area, and addition of ZrN further inhibited the formation of the α-sialon phase. A decrease in Vickers hardness and an increase in toughness with increasing content of ZrO₂(Nd₂O₃) or ZrN were seen in both the HIPed β-sialon/ZrO₂(Nd₂O₃) composites and the HIPed Nd₂O₃-stabiIized α-sialons with ZrN additions.     

β-Sialon Ceramics Prepared at 1700°C by Hot Isostatic Pressing

Dense, single-phase β-sialon ceramics were sintered at 1700°C and 200 MPa using the glass-encapsulated hot isostatic pressing technique. The materials were very hard, 1500 to 1700 kg / mm² (98 N load), but were fairly brittle, with an indention fracture toughness of about 3 MPa · m^1/2. The addition of 1 wt% Y₂O₃ before sintering had a positive effect on the toughness, especially at the low x compositions of Si_3-xAl_xO_xN_4-x, where K_IC∼4 MPa · m^1/2.     

Farbication of Optically Transparent Lead Magnesium Niobate Polycrystalline Ceramics Using Hot Isostatic Pressing

The physical, dielectric, and optical properties of hot isostatically pressed lead magnesium niobate polycrystalline ceramics modified with 1/2 mol% La₂O₃, Pb_{1–3/2 x} La _x □ _{x /2}-(Mg_1/3Nb_2/3)O₃, have been investigated. Methods used to characterize the ceramics included determination of the dielectric permittivity, optical transmittance, and refractive index dispersion. The materials exhibited relaxor ferroelectric type behavior with a peak dielectric constant K > 14000 and average T _c ∼−35°C. Various sintering, hot isostatic pressing, and annealing conditions were examined to produce highly dense and optically transparent materials. Through the use of hot isostatic pressing, densities more than 99.5% theoretical and transmittance greater than 50% at 633-nm wavelength were obtained. Hot isostatic pressing technique appears to be a good alternative to hot uniaxial pressing without the associated problem of PbO volatility, reactivity with the pressure vessel, and geometrical constraints.     

Effect of the Amount of Additives and Post-Heat Treatment on the Microstructure and Mechanical Properties of Yttrium–α-Sialon Ceramics

The yttrium–sialon ceramics with the composition of Y_0.333Si₁₀Al₂ON₁₅ and an excess addition of Y₂O₃ (2 or 5 wt%) were fabricated by hot isostatic press (HIP) sintering at 1800°C for 1 h. The resulting materials were subsequently heat-treated in the temperature range 1300–1900°C to investigate its effect on the α→β-sialon phase transformation, the morphology of α-sialon grains, and mechanical properties. The results show that α-sialons stabilized by yttrium have high thermal stability. An adjustment of the α-sialon phase composition is the dominating reaction in the investigated Y–α-sialon ceramics during low-temperature annealing. Incorporation of excess Y₂O₃ could effectively promote the formation of elongated α-sialon grains during post-heat-treating at relatively higher temperature (1700° and 1900°C) and hence resulted in a high fracture toughness ( K _IC= 6.3 MPa·m^1/2) via grain debonding and pullout effects. Although the addition of 5 wt% Y₂O₃ could promote the growth of elongated α grains with a higher aspect ratio, the higher liquid-phase content increased the interfacial bonding strength and therefore hindered interface debonding and crack deflection. The heat treatment at 1500°C significantly changed the morphology of α-sialon grains from elongated to equiaxed and hence decreased its toughness.     

Improvement of Mechanical and Electrical Properties of Scandia-Doped Zirconia Ceramics by Post-Sintering with Hot Isostatic Pressing

Significant improvement in the fracture strength, accompanied by an enhancement in the electrical conductivity, of zirconia polycrystals that were doped with 3–7 mol% Sc₂O₃ was obtained by sintering at 1300°C for 1 h in air, followed by hot isostatic pressing (HIP) at 196 MPa at 1300° and 1450°C for 1.5 h in an argon-gas atmosphere. Dense bodies (with an average grain size of <0.5 μm) that were doped with 3.5 mol% of Sc₂O₃ showed the highest average fracture strength up to 1770 MPa and an electrical conductivity of 0.08 S/cm at 1000°C. The present zirconia ceramics, which consisted of submicrometer-sized grains of tetragonal phases and were stabilized with 5 and 6 mol% of Sc₂O₃, exhibited high strength (1330 and 1140 MPa, respectively) and good conductivity (0.15 and 0.18 S/cm, respectively); values for both properties were greater than those previously reported. The present HIPed zirconia ceramics, which have excellent properties, are candidates for an electrolyte of planar-type solid oxide fuel cells.     

Temperature Dependent Luminescence of Yellow-Emitting α-Sialon:Eu2+ Oxynitride Phosphors for White Light-Emitting Diodes

Yellow-emitting α-sialon:Eu²⁺ phosphors have been reported as interesting down-conversion luminescent materials in white LEDs. In this work, the thermal quenching of α-sialon:Eu²⁺ with the compositions of M^val+_{( m /val+)}Si_{12−( m + n )}Al _{m + n} O _n N_{16− n} (M=Ca, Mg, Lu) is studied by investigating the effects of chemical composition, activator concentration, and substitution cation on the temperature-dependent luminescence. The chemical composition of α-sialon:Eu²⁺ was varied in a wide range (0.5≤ m ≤2.0, 1≤ n ≤1.8). It shows that the m value significantly affects the thermal quenching of α-sialon, whereas the n value hardly does. This difference is ascribed to the obvious lattice expansion and the increase of absolute activator concentration as m increases. The thermal quenching increases with increasing the Eu²⁺ concentration, which is due to enhanced Stokes shift. The type of substitution cation also has an influence on thermal quenching. Among the substitution cations in this work, Lu-α-sialon:Eu²⁺ exhibits largest thermal quenching. Photoionization is considered as the mechanism for the thermal quenching of Lu-α-sialon: Eu²⁺.     

Reaction Sintering and Properties of Silicon Oxynitride Densified by Hot Isostatic Pressing

Silicon oxynitride ceramics were reaction sintered and fully densified by hot isostatic pressing in the temperature range 1700°C to 1950°C from an equimolar mixture of silicon nitride and silica powders without additives. Conversion to Si₂N₂O increases steeply from a level around 5% of the crystalline phases at 1700°C to 80% at 1800°C, and increases a few percent further at higher temperatures. α -Si₃N₄ is the major residual crystalline phase below 1900°C. The hardness level for materials containing 85% Si₂N₂O is approximately 19 GPa, comparable with the hardness of Si₃N₄ hot isostatically pressed with 2.5 wt% Y₂O₃, while the fracture toughness level is around 3.1 MPa. m^1/2, being approximately 0.8 MPa.m^1/2 lower. The three-point bending strength increased with HIP temperature from approximately 300 to 500 MPa.     

Strengthening of Silicon Carbide Ceramics by Surface Nitridation during Hot Isostatic Pressing

Surface strengthening of SiC by in situ surface nitridation during post-hot isostatic pressing (post-HIPing) in N₂ was investigated. The formation of a thin (5–15 μm) layer of submicrometer β-Si₃N₄ on the surface of SiC was obtained at 1850°C and 200 MPa. While SiC HIPed in Ar attained a mean bending strength of 660 MPa, a significant increase in strength (with a maximum fracture stress above 1000 MPa) was observed for the SiC/Si₃N₄-layer composite material. Generation of residual compressive stresses on the surface layer caused by the differences in thermal expansion may account for the observed strengthening. Thus, in situ surface nitridation by post-HIPing in N₂ may offer an attractive way to improve surface-sensitive mechanical properties of complex-shaped SiC components.     

Homogeneity Region and Thermal Stability of Neodymium-Doped α-Sialon Ceramics

Dense sialon ceramics along the tie line between Si₃N₄ and Nd₂O₃·9AlN were prepared by hot-pressing at 1800°C. The materials were subsequently heat-treated in the temperature range 1300–1750°C and cooled either by turning off the furnace (yielding a cooling rate (T_cool) of ∼50°C/min) or quenching (T_cool≥ 400°C/min). It was found necessary to use the quenching technique to reveal the true phase relationships at high temperature, and it was established that single-phase α-sialon forms for 0.30 x 0. 51 in the formula Nd_xSi_{12–4S x} Al_{4.5 x} O_{1. 5 x} , N_{16–1.5 x} . The α-sialon is stable only at temperatures above 1650°C, and it transforms at lower temperatures by two slightly different diffusion-controlled processes. Firstly, an α-sialon phase with lower Nd content is formed together with an Al-containing Nd-melilite phase, and upon prolonged heat treatment thus-formed α-sialon decomposes to the more stable β-sialon and either the melilite phase or a new phase of the composition NdAl(Si_6-zAl_z)N_10-zO_z. Nd-doped α-sialon ceramics containing no crystalline intergranular phase show very high hardness (HV10 = 22. 5 GPa) and a fracture toughness ( K _lc= 4.4 MPa·m^1/2) at room temperature. The presence of the melilite phase, which easily formed when slow cooling rates were applied or by post-heat-treatment, reduced both the fracture toughness and hardness of the materials.     

Hot Isostatic Pressing and Characterization of Sol-Gel-Derived Chromium(III) Oxide

Chromium (III) oxide (Cr₂O₃) crystallizes at low temperatures from an amorphous material prepared by adding hydrazine monohydrate to an aqueous solution of Cr(NO₃)₃-9H₂O. Individual particles of Cr₂O₃ tend toward a hexagonal morphology above 800°C. Well-densified Cr₂O₃ pellets (98.8% of theoretical density) have been fabricated by hot isostatic pressing for 2 h at 1100°C and 196 MPa. Their fracture toughness is 4.4 MPa.m^1/2. The sample annealed in air for 12 h at 1300°C exhibits a high electrical conductivity of 3.6 Ω^-1.m^-1at 700°C.     

Hot Isostatic Pressing of YBa2Cu3O7-x

Hot isostatic pressing (HIPing) with an oxygen donor was studied as a method for processing bulk superconductors. Superconducting powder was derived from the calcination of nitrated Y₂O₃, CuO, and BaCO₃ powder. The powder was HIPed using pressures of 69, 138, and 207 MPa at 820°C. BaO₂ was used as an oxygen donor during HIPing. The density, hardness, and Young's modulus of HIPed samples were higher than those of sintered control samples. Superconducting transition temperatures > 92 K were achieved without post-HIP annealing of the samples in oxygen.     

Properties of Modified Lead Zirconate Titanate Ceramics Prepared at Low Temperature (800°C) by Hot Isostatic Pressing

High-density lead zirconate titanate (PZT) ceramics were fabricated for the first time at a temperature as low as 800°C via the hot isostatic pressing (HIP) of a PZT powder with a modified composition of 0.92Pb(Zr_0.53Ti_0.47)O₃—0.05BiFeO₃—0.03Ba(Cu_0.5W_0.5)O₃ that contained 0.5 mass% MnO₂. The resultant PZT ceramics exhibited a microstructure that was denser and finer than that of PZT sintered at 935°C, which is the lowest temperature for the densification of the same composition via normal sintering. The relevant dielectric and piezoelectric properties of the HIPed PZT ceramics were as follows: coefficient of electromechanical coupling ( K ₃₁), 31.8%; mechanical quality factor ( Q _m), 1364; piezoelectric constant ( d ₃₁), −73.7 × 10⁻¹² C/N; relative dielectric constant (ɛ₃₃^T/ɛ₀), 633; dielectric loss factor (tan δ), 0.5%; Curie temperature ( T _c), 285°C; and density (ρ), 8.06 g/cm³. In addition to these reasonably good piezoelectric properties, the HIPed PZT exhibited better mechanical properties—particularly, higher fracture strength—than the normally sintered PZT.     

Hot Isostatic Pressing of Reactive SnO2 Powder

Tin(IV) oxide (SnO₂) crystallizes at room temperature by adding hydrazine monohydrate ((NH₂)₂· H₂O) to a hydrochloric acid solution of tin, followed by washing and drying. Well-densified SnO₂ ceramics (99.8% of theoretical) with an average grain size of 0.9 μm have been fabricated by hot isostatic pressing for 2 h at 900°C and 196 MPa. Their Vickers hardness and bending strength are 14.4 GPa and 200 MPa, respectively. They exhibit an electrical conductivity of 2 × 10⁻³−9 × 10⁻³ S·cm⁻¹ at room temperature.     

Hot Isostatic Press Sintering and Properties of Silicon Nitride without Additives

Fully densified silicon nitride without additives was fabricated by means of hot isostatic pressing. The sintering process of highly pure powder was investigated with special interest in the evolution of α–β phase transformation, densification, and microstructure development. It was observed that the transformation occurred without a liquid phase below 1730°C, which corresponds to the melting point of SiO₂. Above 1730°C, the densification and β-grain elongation accelerated concurrently because of the appearance of liquid SiO₂. However, full densification was attained at 1950°C together with marked grain growth. Flexural strength, microhardness, fracture toughness, and Young's modulus of sintered bodies were measured as a function of temperature. In the sintered body started from highly pure powder, excellent MOR behavior was found up to 1400°C. Impurity content of a few hundred ppm was found to be sufficient to make densification easy and to degrade high-temperature strength.     

Porous Ceramic Filters Produced by Hot Isostatic Pressing

Porous TiO₂ ceramics were produced by capsule-free hot isostatic pressing (HIPing) and were evaluated by measuring gas permeability and pore size distribution. In comparison to conventionally sintered TiO₂, the HIPed TiO₂ has a higher permeability and narrower pore size distribution. The differences are caused by the effects of high-pressure gas during sintering.     

Self-Reinforced Nitrogen-Rich Calcium–α-SiAlON Ceramics

Nitrogen-rich Ca–α-SiAlON ceramics with nominal compositions Ca _x Si_{12−2 x} Al_{2 x} N₁₆ and 0.2≤ x ≤2.6, extending along the Si₃N₄–1/2Ca₃N₂:3AlN tie line, were prepared from Si₃N₄, AlN, and CaH₂ precursors by hot pressing at 1800°C. The x values attained were determined by energy-dispersive X-ray (EDX) microanalysis and X-ray powder diffraction (XRPD) data using the Rietveld method. The results show that Ca–α-SiAlONs form continuously within the compositional range x =0 to at least x =1.82. Phase assemblages, lattice parameters, Vickers hardness, and fracture toughness were determined and correlated to the calcium content, x . Owing to a high sintering temperature and the use of CaH₂ as a precursor, grain growth was kinetically enhanced, resulting in self-reinforced microstructures with elongated grains. The obtained Ca–α-SiAlON ceramics demonstrate a combination of both high hardness ∼21 GPa, and high fracture toughness ∼5.5 MPa·m^1/2.     

Accelerated Reaction Bonding of Mullite

A suitable way to process mullite ceramics and mullite-matrix composites with low dimensional changes ("near-net-shape processing") is reaction bonding, using silicon metal and corundum (α-Al₂O₃) as starting materials, be-cause sintering-induced shrinkage is compensated by vol-ume expansion caused by the silicon-oxidation-induced vol-ume expansion. This work describes a new reaction-bonded mullite (RBM) processing route that proceeds at much lower temperatures (≤1350°C) than in "normal" RBM systems (≥1550°C). Accelerated silicon oxidation and mullite formation are effected by adding low amounts of yttria (Y₂O₃) or ceria (CeO₂) to the green powder mixtures, which causes the formation of transient, metastable, and low-viscosity Y-Al-Si-O and Ce-Al-Si-O partial melts. After long-term heat treatments at ≤1350°C, however, the intermediate liquids recrystallize and leave behind RBM ceramics that are homogeneous, substantially glass-free, and relatively dense. These two RBM materials consist of mullite, α-Al₂O₃, and Y₂Si₂O₇ or CeO₂, respectively.     

Reaction Between Titanium and Zirconia Powders During Sintering at 1500°C

Zirconia–titanium (ZrO₂–Ti) composites have been considered potential thermal barrier graded materials for applications in the aerospace industry. Powder mixtures of Ti and 3 mol% Y₂O₃ partially stabilized ZrO₂ in various ratios were sintered at 1500°C for 1 h in argon. The microstructures of the as-sintered composites were characterized by X-ray diffraction and transmission electron microscopy/energy-dispersive spectroscopy. Ti reacted with and was mutually soluble in ZrO₂, resulting in the formation of α-Ti(O, Zr), Ti₂ZrO, and/or TiO. These oxygen-containing phases extracted oxygen ions from ZrO₂, whereby oxygen-deficient ZrO₂ was generated. For relatively small Ti/ZrO₂ ratios, specimens with ≤30 mol% Ti, TiO were formed as oxygen could be sufficiently supplied by excess ZrO₂. For the specimens with ≥50 mol% Ti, lamellar Ti₂ZrO was precipitated in α-Ti(Zr, O), with no TiO being found. Both m -ZrO_{2− x} and t -ZrO_{2− x} were found in specimens with ≤50 mol% Ti; however, only c -ZrO_{2− x} was formed in the specimen with 70 mol% Ti. As ZrO₂ was gradually dissolved into Ti, yttria was retained in ZrO₂ because of the very limited solubility of yttria in α-Ti(O, Zr) or TiO. The concentration of retained yttria and the degree of oxygen deficiency in ZrO₂ increased with the Ti content. The complete dissolution of ZrO₂ into Ti was followed by the precipitation of Y₂Ti₂O₇ in the specimen with 90 mol% Ti.     

Postsintering Hot Isostatic Pressing of Ceria-Doped Tetragonal Zirconia/Alumina Composites in an Argon–Oxygen Gas Atmosphere

Ceria-doped tetragonal zirconia (Ce-TZP)/alumina (Al₂O₃) composites were fabricated by sintering at 1450° to 1600°C in air, followed by hot isostatic pressing (postsintering hot isostatic pressing) at 1450°C and 100 MPa in an 80 vol% Ar–20 vol% O₂ gas atmosphere. Dispersion of Al₂O₃ particles into Ce-TZP was useful in increasing the relative density and suppressing the grain growth of Ce-TZP before hot isostatic pressing, but improvement of the fracture strength and fracture toughness was limited. Postsintering hot isostatic pressing was useful to densify Ce-TZP/Al₂O₃ composites without grain growth and to improve the fracture strength and thermal shock resistance.     

High Q Microwave Dielectric Ceramics in (Ni1−x Znx)Nb2O6 System

(Ni_{1− x} Zn _x )Nb₂O₆, 0≤ x ≤1.0, ceramics with >97% density were prepared by a conventional solid-state reaction, followed by sintering at 1200°–1300°C (depending on the value of x ). The XRD patterns of the sintered samples (0≤ x ≤1.0) revealed single-phase formation with a columbite ( Pbcn ) structure. The unit cell volume slightly increased with increasing Zn content ( x ). All the compositions showed high electrical resistivity (ρ_dc=1.6±0.3 × 10¹¹Ω·cm). The microwave (4–5 GHz) dielectric properties of (Ni_{1− x} Zn _x )Nb₂O₆ ceramics exhibited a significant dependence on the Zn content and to some extent on the morphology of the grains. As x was increased from 0 to 1, the average grain size monotonically increased from 7.6 to 21.2 μm and the microwave dielectric constant (ɛ'_r) increased from 23.6 to 26.1, while the quality factors ( Q _u× f ) increased from 18 900 to 103 730 GHz and the temperature coefficient of resonant frequency (τ_f) increased from −62 to −73 ppm/°C. In the present work, we report the highest observed values of Q _u× f =103 730 GHz, and ɛ'_r=26.1 for the ZnNb₂O₆-sintered ceramics.