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.     

Fracture toughness,strength and Vickers hardness of yttria-ceria-doped tetragonal zirconia/alumina composites fabricated by hot isostatic pressing

Yttria-ceria-doped tetragonal zirconia ((Y, Ce)-TZP)/alumina (Al₂O₃) composites were fabricated by hot isostatic pressing (HIP) at 1400–1600 °C and 147 MPa for 30 min in Ar gas using fine powders prepared by hydrolysis of ZrOCl₂ solution. The mechanical properties of these ceramic composites were evaluated. The fracture toughness and bending strength of the composites consisting of 25 wt% Al₂O₃ and tetragonal zirconia with compositions 4 mol% YO_1.5-4 mol% CeO₂-ZrO₂, 2.5 mol% YO_1.5-4 mol% CeO₂-ZrO₂ and 2.5 mol% YO_1.5-5.5 mol% CeO₂-ZrO₂ fabricated by HIP at 1400 °C were 6–7 MPa m^1/2 and 1700–1800 MPa. Fracture toughness, strength and hardness of (Y, Ce)-TZP/Al₂O₃ composites were strongly dependent on HIP temperature. The fracture strength and hardness were increased, and grain growth of zirconia grains and phase transformation from the tetragonal to the monoclinic structure of (Y, Ce)-TZP during HIP in Ar at high temperature (1600 °C) were suppressed by the dispersion of Al₂O₃ into (Y, Ce)-TZP.     

Formation and hot isostatic pressing of ZrO2 solid solution in the system ZrO2-Al2O3

In the system of ZrO₂-Al₂O₃, cubic ZrO₂ solid solutions containing up to 40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials prepared by the simultaneous hydrolysis of zirconium and aluminium alkoxides. At higher temperatures, they transform into tetragonal solid solutions. Metastable ZrO₂ solid solution powders containing 25 mol% Al₂O₃ have been sintered at 1000–1150 °C under 196 M Pausing the hot isostatic pressing technique. The solid solution ceramics consisting of homogeneous microstructure with an average grain size of 50 nm exhibited a very high fracture toughness of 23 MN m ^–1.5. They have been characterized by X-ray diffraction and electron probe surface analyses.     

Thermal stability and mechanical properties of yttria-doped tetragonal zirconia polycrystals with dispersed alumina and silicon carbide particles

Yttria-doped tetragonal zirconia polycrystals in which were dispersed various amounts of Al₂O₃ and SiC particles were sintered at 1500° C for 3 h, and the mechanical properties and the thermal stability of the sintered bodies were evaluated. Dispersion of Al₂O₃ caused no significant effect on sinterability, and increased the hardness and elasticity of the composites. Dispersion of SiC particles decreased the relative density and the grain size of composites. Elasticity and hardness increased by dispersing less than 10 vol% SiC, but decreased above 10 vol% SiC due to the decrease of relative density. Dispersion of both Al₂O₃ and SiC particles slightly increased the fracture toughness of ZrO₂-3 mol% Y₂O₃ ceramics but significantly decreased that of ZrO₂-2 mol% Y₂O₃ ceramics. The rate of the tetragonal-to-monoclinic phase transformation decreased by dispersing both Al₂O₃ and SiC particles. The transformation depth increased rapidly and then slowly with increasing the annealing time. The rate of increase in the transformation depth greatly decreased by dispersing Al₂O₃ particles.     

Control of the tetragonal-to-monoclinic phase transformation of yttria partially stabilized zirconia in hot water

The tetragonal-to-monoclinic phase transformation of yttria partially stabilized zirconia caused by annealing in hot water was investigated in the temperature range 80 to 200° C using sintered bodies in zirconia containing 2, 3 and 4 mol % Y₂O₃. Three approaches, alloying ZrO₂(Y₂O₃) with 0 to 20wt% CeO₂, dispersing 0 to 40 wt % Al₂O₃ into ZrO₂(Y₂O₃) ceramics and decreasing the grain size of zirconia, were examined to inhibit the tetragonal-to-monoclinic phase transformation. The amount of monoclinic phase formed decreased with increasing concentrations of CeO₂ alloyed and Al₂O₃ dispersed, and with decreasing grain size of zirconia.     

Production and characterization of ZrO<Subscript>2</Subscript> ceramics and composites to be used for hip prosthesis

Tetragonal ZrO₂ polycrystalline (TZP) ceramics with varying yttria and ceria content (2–3 mol%) and distribution (coated or co-precipitated), and varying second phase content Al₂O₃ were prepared and investigated by means of microstructural analysis, mechanical properties, and hydrothermal stability, and ZrO₂-based composites with 35–60 vol% of electrical conductive TiN particles were developed. The effects of stabilizer content and means of addition, powder preparation, sintering conditions, and grain size have been systematically investigated. Fully dense Y-TZP ceramics, stabilized with 2–3 mol% Y₂O₃, 2 wt% Al₂O₃ can be achieved by hot pressing at 1,450 °C for 1 h. The hydrothermal stability increased with increasing overall yttria content. The jet-milled TiN powder was used to investigate the ZrO₂–TiN composites as function of the TiN content. The experimental work revealed that fully dense ZrO₂–TiN composites, stabilized with 1.75 mol% Y₂O₃, 0.75 wt% Al₂O₃, and a jet-milled TiN content ranging from 35 to 60 vol% could be achieved by hot pressing at 1,550 °C for 1 h. Transformation toughening was found as the primary toughening mechanism. The decreasing hardness and strength could be attributed to an increasing TiN grain size with increasing TiN content, whereas the decreasing toughness might be due to the decreasing contribution of transformation toughening from the tetragonal to monoclinic ZrO₂ phase transformation. The E modulus increases linearly with increasing TiN content, whereas the hydrothermal stability increases with addition of TiN content.     

Mechanical properties of Al2O3 and Al2O3 + ZrO2 ceramics reinforced by SiC whiskers

The effect of the SiC whisker content on the mechanical properties of Al₂O₃ and Al₂O₃ + 20 vol% ZrO₂ (2 mol% Y₂O₃) ceramic composites has been investigated. It is shown that the strength and fracture toughness of the composites are increased by the addition of 0–30 vol% SiC whiskers with only one exception that 30 vol% SiC whisker leads to a decrease in the flexure strength. The addition of 20 vol% ZrO₂ (2 mol% Y₂O₃) significantly improves the mechanical properties of the Al₂O₃ + SiC whisker (SiC_w) composites and the t-m phase transformation of ZrO₂ is enhanced by the residual stresses caused by the thermal incompatibility between the SiC_w and the matrix. The toughening effect of both SiC whiskers and the t-m phase transformation of ZrO₂ (2 mol% Y₂O₃) is shown to be additive, but the addition of ZrO₂ decreases the strengthening effect of the SiC whiskers.     

Sintering and compensation effect of donor- and acceptor-codoped 3mol% Y2O3-ZrO2

Addition of 0.15–0.5 mol% acceptor oxide, Al₂O₃, to 3 mol% Y₂O₃-ZrO₂ results in enhanced densification at 1350 °C. The enhancement is accounted for by a liquid phase sintering mechanism. The addition of donor oxide, Ta₂O₅, of 0.15–2.5 mol % at 1300–1600 °C results in the destabilization of tetragonal (t-) phase and the decrease of final density in 3 mol% Y₂O₃-TZP (tetragonal ZrO₂ polycrystals). X-ray diffractometry (XRD) reveals that the Ta₂O₅-added 3 mol% Y₂O₃-ZrO₂ contains monoclinic (m-) ZrO₂ and a second phase of Ta₂Zr₆O₁₇. The decreasing in final density is attributed to the increase of m-ZrO₂ content. Complete destabilization of t-ZrO₂ to m-ZrO₂ in samples added with 2.5 mol% Ta₂O₅ is interpreted by the compensation effect based on donor- and acceptor-codoping defect chemistry.     

Duplex spinel-ZrO2 ceramics

Duplex spinel-ZrO₂ ceramic composites were produced by an emulsion-hot kerosene drying technique. The sintered duplex spinel-ZrO₂ ceramics which had the composition of 55 wt% Al₂O₃-20 wt% ZrO₂-25 wt% MgO, consisted of a spinel matrix, whose grain size was in the range of 1.5 to 2.0 m, and uniformly dispersed zirconia agglomerates having grain sizes ranging from 1.0 to 2.0 m. Zirconia agglomerates began to appear at a temperature of 1500 °C and the duplex spinel-ZrO₂ structure was formed with the weight ratio of Al₂O₃/MgO being within 1.67 to 2.20 and the amount of ZrO₂ addition being within 5 to 25 wt %. The relative density, fracture toughness, flexural strength, and critical temperature difference of the spinel-ZrO₂ composite were 97.8%, 1.98 MPam^0.5, 390 MPa, and 275 °C, respectively.     

Sintering and compensation effect of donor and acceptor codoped 3 mol% Y2O3-ZrO2

Addition of 0.15–0.5 mol% acceptor oxide, Al₂O₃, to 3 mol% Y₂O₃-ZrO₂ results in enhanced densification at 1350°C. The enhancement is accounted for by a liquid phase sintering mechanism. While the addition of donor oxide, Ta₂O₅, of 0.15–2.5 mol% at 1300–1600°C results in the decrease of final density and in the destabilization of the tetragonal (t) phase of the 3 mol% Y₂O₃-t-ZrO₂ (TZP). X-ray diffractometry (XRD) reveals that the Ta₂O₅-added 3 mol% Y₂O₃-ZrO₂ contains monoclinic (m) ZrO₂ phase and a second Ta₂Zr₆O₁₇ phase. The decrease is attributed to the increase of m-ZrO₂ content in these samples. Complete phase transformation from t-ZrO₂ to m-ZrO₂ observed in samples added with 2.5 mol% Ta₂O₅ is interpreted by the compensation effect based on donor and acceptor codoping defect chemistry.     

Electrical conductivity of tetragonal stabilized zirconia

The electrical conductivity change on annealing for tetragonal stabilized zirconia (TZP) was studied with the help of a.c. impedance dispersion analysis techniques. The dependences of the conductivity on annealing time at 1000 ° C and on temperature cycling between room temperature and 1000 ° C were investigated. A decrease in conductivity of about 30% at 1000 ° C of TZP with 3 mol% Y₂O₃ was observed during the first 200 h of annealing at 1000 ° C, and no change was observed during further annealing. A similar result was observed for TZP with 2.9 mol% Sc₂O₃. For TZP with 3.0mol% Yb₂O₃, the conductivity decreased gradually during an annealing time of over 2000 h. The impedance dispersion analysis at lower temperature suggested that the decrease in electrical conductivity by annealing at 1000 ° C could be attributed to the increases of both grain boundary and intragrain resistance. No monoclinic phase was observed for the samples annealed at 1000 ° C for 2000 h. On the other hand, a trace of a monoclinic phase was found for TZP with 3mol% Y₂O₃ after the 50th temperature cycling, but no significant decrease in conductivity was observed with the cycling.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript> and Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> co-stabilized ZrO<Subscript>2</Subscript>-WC composites

Y₂O₃ + Nd₂O₃ co-stabilized ZrO₂-based composites with 40 vol% WC were fully densified by pulsed electric current sintering (PECS) at 1350 °C and 1450 °C. The influence of the PECS temperature and Nd₂O₃ co-stabilizer content on the densification, hardness, fracture toughness and bending strength of the composites was investigated. The best combination of properties was obtained for a 1 mol% Y₂O₃ and 0.75 mol% Nd₂O₃ co-stabilized composite densified for 2 min at 1450 °C under a pressure of 62 MPa, resulting in a hardness of 15.5 ± 0.2 GPa, an excellent toughness of 9.6 ± 0.4 MPa.m^0.5 and an impressive 3-point bending strength of 2.04 ± 0.08 GPa. The hydrothermal stability of the 1 mol% Y₂O₃ + 1 mol% Nd₂O₃ co-stabilized ZrO₂-WC (60/40) composites was compared with that of the equivalent 2 mol% Y₂O₃ stabilized ceramic. The double stabilized composite did not degrade in 1.5 MPa steam at 200 °C after 4000 min, whereas the yttria stabilized composite degraded after less than 2000 min. Moreover, the (1Y,1Nd) ZrO₂-WC composites have a substantially higher toughness (~9 MPa.m^0.5) than their 2Y stabilized equivalents (~7 MPa.m^0.5).     

Acoustic emission study of phase relations in low-Y2O3 portion of ZrO2-Y2O3 system

The (metastable) tetragonal phase in 3–4 mol% Y₂O₃-ZrO₂ alloys undergoes a transition to the monoclinic form in the 200–300 °C temperature range. Microcracking due to the volume change at this transition has been detected in these compositions by sharp acoustic emission during heating. The phase change was confirmed by X-ray diffraction, dilatometry and scanning electron microscopy. The monoclinic tetragonal transition in ZrO₂-1 mol% Y₂O₃ alloy at 850–750 °C and the same phase change in 2, 3, 4 and 6 mol% Y₂O₃ compositions at the eutectoid temperature of about 560 °C was also clearly signalled by the acoustic emission counts during heating and cooling. There was no significant acoustic emission activity on heating and cooling the 9 and 12 mol% Y₂O₃ compositions, which are cubic. The acoustic emission data thus confirm the phase relations in the 1–12 mol% Y₂O₃ region, established by conventional methods such as differential thermal analysis, dilatometry and X-ray diffraction.     

Microstructure and properties of a composite system for dental applications composed of glass-ceramics in the SiO2–Li2O–ZrO2–P2O5 system and ZrO2-ceramic (TZP)

The objective of the study was to develop a biocompatible composite system which was composed of TZP-ceramic (tetragonal zirconia polycrystals, ZrO₂ stabilized with 3 mol% Y₂O₃) and two glass-ceramics of the SiO₂–Li₂O–ZrO₂–P₂O₅ type. The metal-free composite system would satisfy the translucency, the biocompatibility and the strength requirements of dentistry. The two glass-ceramics of the SiO₂–Li₂O–ZrO₂–P₂O₅ type with a content of 15 and 20 wt% ZrO₂ respectively, were chemically and physically adapted to TZP-ceramic. The glass-ceramics were used as a dentin buildup material. The TZP-ceramic had the function of a root post. The shape of the post was cylindrical with a conical tip. The composite system was easy to process through viscous flow of the glass-ceramic at 900 and 1000°C, respectively. The microstructure and the mechanical properties of two glass-ceramics of the SiO₂–Li₂O–ZrO₂–P₂O₅ type were examined therefore.     

The microstructure and mechanical properties of yttria-stabilized zirconia prepared by arc-melting

The microstructure of ZrO₂-Y₂O₃ alloys prepared by arc-melting was examined mainly by electron microscopy. It was found that the microstructure changed markedly with yttria content between 0 and 8·7 mol%. Pure zirconia was a single monoclinic phase, while ZrO₂-8·7 mol% Y₂O₃ alloy was single cubic phase as expected from ZrO₂-Y₂O₃ phase diagram. Tetragonal phase was found in alloys with 1 to 6 mol% Y₂O₃ together with monoclinic or cubic phase. The tetragonal phase found in present alloys normally had a lenticular shape with a length 1 to 5m and a width 0.1 to 0.3m, which is much larger than that formed by annealing. The phase with a herring-bone appearance was found in alloys with Y₂O₃ between 2 and 3 mol%, which was recognized to be a metastable rhombohedral phase. The structure of the present alloys is likely to be formed by martensitic or bainitic transformation during fairly rapid cooling from the melt temperature. The change in hardness and toughness with yttria content of the alloys is discussed on the basis of microstructural observations.     

Aluminum doped zirconia nanopowders: Wet-chemical synthesis and structural analysis by Rietveld refinement

Alumina/zirconia nanopowders, with up to 20 mol% Al₂O₃, were prepared by wet-chemical synthesis technique, using controlled hydrolysis of alkoxides. The as-synthesized powders are amorphous, have very high specific surface area and the corresponding particle size smaller than 4 nm. Amorphous powders with 0, 10 and 20 mol% Al₂O₃ crystallize at 460, 692 and 749 °C, respectively, as a single-phase tetragonal zirconia, without any traces of alumina phases. Rietvled refinement of X-ray diffraction data, used for the detailed structural analysis of annealed nanopowders, showed that the high-temperature zirconia phase is stabilized due to the formation of ZrO₂/Al₂O₃ solid solutions. High solubility of alumina in the tetragonal zirconia (up to 28.6 at% Al³⁺) and stabilization of tetragonal zirconia solid solution up to high temperature (as high as 1150 °C) were also confirmed.     

Formation and sintering of 75 mol% alumina/25 mol% zirconia (2–3.5 mol% yttria) composite powder prepared by the hydrazine method

Al₂O₃/Y₂O₃-doped ZrO₂ composite powders with 25 mol% ZrO₂ have been prepared by the hydrazine method. As-prepared powders are the mixtures of AlO (OH) gel solid solutions and amorphous ZrO₂. The formation process leading to -Al₂O₃/t-ZrO₂ composite powders is investigated. Hot isostatic pressing has been performed for 1 h at 1500 °C under 196 MPa. Dense ZrO₂-toughened Al₂O₃ (ZTA) ceramics with homogeneous-dispersed ZrO₂ particles show excellent mechanical properties. The toughening mechanism is discussed.     

Toughened glass-ceramics in the ZrO2-Al2O3-SiO2 system prepared by the sol-gel process

Monolithic glass-ceramics containing Al₂O₃ or TiO₂ were prepared in the ZrO₂-SiO₂ system by the sol-gel process from metal alkoxides. Tetragonal ZrO₂ was precipitated by heat treatment at 900–1200 °C and its crystal growth was increased by adding TiO₂ or Al₂O₃. Further heating at higher temperature resulted in the precipitation of zircon and monoclinic ZrO₂ which was transformed from tetragonal ZrO₂. The addition of Al₂O₃ had less effect on both the tetragonal-to-monoclinic ZrO₂ transformation and the precipitation of zircon. The fracture toughness increased as the size of tetragonal ZrO₂ particles increased and then decreased with the appearance of monoclinic ZrO₂ or zircon. The fracture toughness of the glass-ceramics was measured in the glass-forming regions of the ZrO₂-Al₂O₃-SiO₂ system. The fracture toughness was sensitively dependent on both Al₂O₃ and ZrO₂ content, of which the highest value achieved was 9 MPa m^1/2 for the 50ZrO₂·10Al₂O₃·40SiO₂ composition.     

Preparation of nanocrystalline YSZ powders by the plasma technique

A plasma synthesis method has been devised to produce nanosize YSZ powders with various yttria contents. The powders are synthesized by introducing a mixture of coarse-grained zirconia and yttria into an r.f. inductively coupled plasma flame. The average particle size of the as-prepared powders is in the range 20–40 nm and the specific surface area is 18–50 m²g^–1. The phase and granulometric composition of the produced powders depend on the degree of evaporation of raw powders, reagent concentration in the gas flow and quenching rate, and on the content of Y₂O₃. Up to 5.5 mol% yttria, the major phase of nanosize powders is tetragonal ZrO₂, mostly as the non-transformable (t) form. For yttria contents higher than 6 mol%, the major phase is cubic ZrO₂.     

The effect of ceria co-doping on chemical stability and fracture toughness of Y-TZP

The fracture toughness and ageing resistance of yttria, ceria-stabilized tetragonal zirconia polycrystals (Y, Ce-TZP) were evaluated as a function of grain size and ceria content. Very fine grained, fully dense materials could be produced by sinter forging at relatively low temperatures (1150–1200 °C). The ageing resistance in hot water (185 °C) of 2 mol% Y₂O₃-stabilized TZP is strongly enhanced by alloying with ceria. The ceria content necessary to avoid degradation completely, decreases with grain size. The toughness of fully dense Y, Ce-TZP is 7–9 MPa m^1/2 for grain sizes down to 0.2 m. No or very little transformation took place during fracturing and no clear variation with grain size was observed for the toughness at grain sizes up to 0.8 m. Reversible transformation and crack deflection may explain the observed toughness values.