Chemical synthesis and structural characterization of nanocrystalline powders of pure zirconia and yttria stabilized zirconia (YSZ)

Nanocrystals of pure zirconia and yttria stabilized zirconia (YSZ) are obtained by a simple chemical synthesis route using sucrose, polyvinyl alcohol (PVA) and metal nitrates. The reaction mixture on pyrolysis and calcination gives nanocrystals. These are characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The size of the nanocrystallites for pure zirconia is in the range of about 7.0–45.0 nm and for yttria stabilized zirconia, is in the range of about 5.0–24.0 nm at 200°C and above, according to the preparative condition. At 200°C, pure zirconia forms cubic phase and this cubic phase is stable up to 600°C and then slowly transformed into monoclinic form. For yttria stabilized zirconia, the crystals are tetragonal in the temperature range from 200 to 1200°C.     

Phase stability,microstructural evolution and room temperature mechanical properties of TiO2 doped 8 mol% Y2O3 stabilized ZrO2 (8Y-CSZ)

The effect of TiO₂ dopant on phase stability, microstructural evolution and room temperature mechanical properties of 8 mol% yttria-stabilized cubic zirconia (8Y-CSZ) was studied. The results show that TiO₂ (up to 10 wt%) can be dissolved in solid solution in the zirconia matrix. When the dopant amount is less than 5 wt%, TiO₂ doped 8Y-CSZ remains single phase cubic zirconia. Increased additions of TiO₂ destabilize the cubic phase and cause the formation of tetragonal zirconia with a resultant microstructure consisting of large cubic zirconia grains and small tetragonal zirconia grains. EDS analyses show that yttria is partitioned between these two types of grains. The solubility of TiO₂ is the highest for cubic grains which also have higher yttria concentrations. Room temperature mechanical property measurements show that hardness does not change significantly with additions of TiO₂, but fracture toughness is more than doubled for 10 wt% TiO₂ doped 8Y-CSZ.     

Phase Distribution and Residual Stresses in Melt-Grown Al2O3-ZrO2(Y2O3) Eutectics

Al₂O₃-ZrO₂ eutectics containing 0 to 12.2 mol% Y₂O₃ (with respect to zirconia) were produced by directional solidification using the laser floating zone (LFZ) method. Processing variables were chosen to obtain homogeneous, colony-free, interpenetrating microstructure for all of the compositional range, optimum from the viewpoint of mechanical properties. The amount of cubic, tetragonal, or monoclinic zirconia phases was determined using a combination of Raman and X-ray diffraction techniques. Monoclinic zirconia was present up to concentrations of 3 mol% Y₂O₃, while the amount of tetragonal zirconia gradually increased with yttria content up to 3 mol%. Cubic zirconia was the only phase detected when the yttria content reached 12 mol%. The residual stresses in alumina were measured using the shift of the ruby R lines. Compressive stresses were isotropic when measured in the samples containing tetragonal and cubic zirconia, while higher tensile, anisotropic stresses were found when monoclinic zirconia was present. They were partially relieved in the eutectic sample without yttria. These results were compared with a thermoelastic analysis based on the self-consistent model.     

Subsolidus Phase Equilibria and Ordering in the System ZrO2-Y2O3

The subsolidus phase relations in the entire system ZrO₂-Y₂O₃ were established using DTA, expansion measurements, and room- and high-temperature X-ray diffraction. Three eutectoid reactions were found in the system: ( a ) tetragonal zirconia solid solution→monoclinic zirconia solid solution+cubic zirconia solid solution at 4.5 mol% Y₂O₃ and ∼490°C, ( b ) cubic zirconia solid solutiow→δ-phase Y₄Zr₃O₁₂+hexagonalphase Y₆ZrO₁₁ at 45 mol% Y₂O₃ and ∼1325°±25°C, and ( c ) yttria C -type solid solution→wcubic zirconia solid solution+ hexagonal phase Y₆ZrO₁₁ at ∼72 mol% Y₂O₃ and 1650°±50°C. Two ordered phases were also found in the system, one at 40 mol% Y₂O₃ with ideal formula Y₄Zr₃O₁₂, and another, a new hexagonal phase, at 75 mol% Y₂O₃ with formula Y₆ZrO₁₁. They decompose at 1375° and >1750°C into cubic zirconia solid solution and yttria C -type solid solution, respectively. The extent of the cubic zirconia and yttria C -type solid solution fields was also redetermined. By incorporating the known tetragonal-cubic zirconia transition temperature and the liquidus temperatures in the system, a new tentative phase diagram is given for the system ZrO₂-Y₂O₃.     

Crystallite and Grain-Size-Dependent Phase Transformations in Yttria-Doped Zirconia

In pure zirconia, ultrafine powders are often observed to take on the high-temperature tetragonal phase instead of the "equilibrium" monoclinic phase. The present experiments and analysis show that this observation is one manifestation of a much more general phenomenon in which phase transformation temperatures shift with crystallite/grain size. In the present study, the effect of crystallite (for powders) and grain (for solids) size on the tetragonal → monoclinic phase transformation is examined more broadly across the yttria–zirconia system. Using dilatometry and high-temperature differential scanning calorimetry on zirconia samples with varying crystallite/grain sizes and yttria content, we are able to show that the tetragonal → monoclinic phase transformation temperature varies linearly with inverse crystallite/grain size. This experimental behavior is consistent with thermodynamic predictions that incorporate a surface energy difference term in the calculation of free-energy equilibrium between two phases.     

Dehydration and Crystallization Kinetics of Zirconia-Yttria Gels

Zirconia and zirconia-yttria gels containing 4 and 8 mol % yttria were obtained by coprecipitation and drying at 373 K. The dehydration and crystallization behavior of the dried gels was studied by DSC, TG, and XRD. The gels undergo elimination of water over a wide temperature range of 373–673 K. The peak temperature of the endotherm corresponding to dehydration and the kinetic constants for the process were not influenced by the yttria content of the gel. The enthalpy of dehydration observed was in good agreement with the heat of vaporization data. The dehydration was followed by a sharp exothermic crystallization process. The peak temperature of the exotherm and the activation energy of the process increased with an increase in yttria content, while the enthalpy of crystallization showed a decrease. The "glow effect" reduced with increasing yttria content. Pure zirconia crystallizes in the tetragonal form while the zirconia containing 4 and 8 mol% yttria appears to crystallize in the cubic form.     

Twin-Related Tetragonal Variants in Yttria Partially Stabilized Zirconia

Crystals of yttria partially stabilized zirconia were grown by the arc-image floating-zone technique and studied by transmission electron microscopy. Crystals annealed at 1700°C consist of tetragonal precipitates and a cubic matrix. The platelike domains in a precipitate are twin-related tetragonal variants stacked alternately parallel to the (011) twin plane. The axial relations between the tetragonal precipitate and the cubic matrix are [100]_tetragonal|[100]_cubic, [011]_tetragonal|[011]_cubic.     

Polymorphic Mixes of Zirconia from a Borate Glass Melt

Yttria-stabilized zirconia crystals were produced by devitrification within a sodium borate glass containing zirconia and yttria. Yttria (3, 6, or 10 mol%) in zirconia was added as part of the starting material of the glass batch. Phase separation and crystallization occurred during the cooling and subsequent heat treatment of the glasses. The zirconia powders obtained after leaching away the sodium borate had surface areas between 16 and 48 m²/g. X-ray diffraction traces revealed a mixture of monoclinic, tetragonal, and cubic phases, the phase ratios of which depended on the composition of the glass.     

Low temperature degradation resistant nanostructured yttria-stabilized zirconia for dental applications

When used in prosthetic dentistry, zirconia encounters severe durability issues due to low temperature degradation: exposure to humidity results in a transition from tetragonal to monoclinic phase, associated to disruptive integrity loss. Recently it has been shown that size-induced stabilization helps maintaining zirconia in tetragonal form, when the grain size is reduced to the nano-range. Objective of this work is to demonstrate the applicability of High Pressure Field Assisted Sintering (HP-FAST) to the preparation of dense, nanostructured samples of tetragonal yttria stabilized zirconia, with yttria content between 0.5 and 3 mol% and showing resistance to low temperature degradation. The yttria stabilized zirconia nanopowders were prepared by a hydrothermal method. Sintering by HP-FAST was performed at 900 °C in 5 min, under a pressure of 620 MPa. Resistance to low temperature degradation was tested at 134 °C, under vapor pressure, for up to 40 h. Both pristine and aged samples were characterized by X-ray diffraction, high-resolution scanning electron microscopy and nanoindentation tests in continuous stiffness measurement mode. The sintered samples presented a grain size between 20 and 30 nm and low or null monoclinic content. Both parameters resulted unaffected by ageing. The best results in terms of phase composition and mechanical properties have been obtained with the material containing 1.5 mol% of yttria. These results induce to reconsider the use of yttria stabilized zirconia as material for dental prosthetic systems requiring long-term durability.     

Morphology and Phase Stability of Nitrogen–Partially Stabilized Zirconia (N-PSZ)

The surface layer of yttria-doped tetragonal zirconia materials that have been heat-treated with zirconium nitride was observed to consist of a nitrogen-rich cubic matrix with nitrogen-poor tetragonal precipitates. The precipitates had a thin, oblate-lens shape, similar to those observed in magnesia–partially stabilized zirconia. Because of the fast diffusion of N⁴⁻ ions, the precipitates grew rather large, up to ∼5 μm in length, and remained stabilized in the tetragonal form at room temperature. Because the nitrided layer grew in the two-phase field, the size and distribution of the precipitates each was very irregular. The nitrogen content was observed to determine the proportion of cubic and tetragonal phases in the same way as in conventional cation-stabilized partially stabilized zirconia. A ternary phase diagram for the zirconium(yttrium)–nitrogen–oxygen system was suggested to explain the concentration gradient in the cubic matrix and the phase distribution of the nitrided layer.     

Analytical Electron Microscopy of Yttria Partitioning in the Yttria-Partially-Stabilized Zirconia Crystal

Yttria-partiaUy-stabilized zirconia was grown frcm the melt by the arc-image floating zone technique and annealed at 1700'C. The yttria concentration of the crystal was measured by analytical electron microscopy. The crystal, which contained 8.6 mol% YO_{1. 5}, consists of tetragonal and cubic phases with yttria concentrations of 3.9 and 9.7 mol% YO_1.5, respectively. There is a small difference between this result and the composition expected from the ZrO₂-Y₂O₃ phase diagram.     

Electrospinning of Y2O3- and MgO-stabilized zirconia nanofibers and characterization of the evolving phase composition and morphology during thermal treatment

The current paper focuses on the fabrication of yttria and magnesia stabilized zirconia nanofibers via electrospinning from zirconyl chloride octahydrate and polyvinylpyrrolidone precursors with minor additions of yttrium nitrate hexahydrate (3 mol.%) or magnesium nitrate hexahydrate (10 mol.%). The precursor materials were dissolved in an ethanol-water mixture in a ratio of 75:25. After successful fiber preparation, the thermal decomposition behavior of the starting materials and the subsequent phase evolution at elevated temperatures were studied. Pure tetragonal zirconia nanofibers were obtained for the composition stabilized with 3 mol.% yttria when the thermal treatment was conducted with a heating rate of 10 K/min up to 1100 °C. In future research work, these tetragonal zirconia nanofibers will be used as reinforcing material in metal matrix composites based on metastable austenitic steel. The combination of the TRIP/TWIP-effect in the steel matrix with the stress-assisted tetragonal to monoclinic phase transformation in the tetragonal stabilized zirconia will lead to a composite material with outstanding mechanical properties.     

Phase Evolution in Yttria-Stabilized Zirconia Thermal Barrier Coatings Studied by Rietveld Refinement of X-Ray Powder Diffraction Patterns

One failure mechanism of thermal barrier coatings composed of yttria-stabilized zirconia (YSZ) has been proposed to be caused, in part, by the transformation of the tetragonal phase of YSZ into its monoclinic phase. Normally, studies of phase evolution are performed by X-ray diffraction (XRD) and by evaluating the intensities of a few diffraction peaks for each phase. However, this method misses some important information that can be obtained with the Rietveld method. Using Rietveld's refinement of XRD patterns, we observed, upon annealing of YSZ coatings, an increase of cubic phase content, a reduction in as-deposited tetragonal phase content, and the appearance of a new tetragonal phase having a lower yttria content that coexists with the as-deposited tetragonal phase of YSZ.     

Fundamental Optical Absorption Edge of Sputter-Deposited Zirconia and Yttria

Zirconia and yttria films were sputter deposited onto unheated fused silica substrates using a metal target and rare gas-oxygen discharges. Double-beam spectrophotometry was used to measure the transmission and reflection as a function of incident photon energy, E , from which the absorption coefficient, α( E ), was calculated. An indirect interband transition at E _i= 4.70 eV and two direct interband transitions at E _g1= 5.17 eV and E _g2= 5.93 eV occur in monoclinic zirconia. Two direct interband transitions at E _g1= 5.07 eV and E _g2= 5.73 eV occur in cubic yttria. The absorption edge structure is modified when unusual phases, such as tetragonal zirconia, and zirconia and yttria with no longrange crystallographic order, are present.     

Gelcast zirconia ceramics for dental applications combining high strength and high translucency

Tetragonal zirconia polycrystals (TZP) represent a favorite material for monolithic ceramic dental restorations. However, all approaches employed so far to improve the translucency of dental zirconia ceramics are accompanied by a significant decline in strength. In this investigation, we developed dental 3Y-TZP ceramics that can provide excellent strength combined with enhanced translucency. The machinable tetragonal zirconia discs and blocks were prepared from fine mesostructured zirconia particles stabilized with 3 mol% of yttria using the gelcasting method. Zirconia ceramics with an average biaxial strength of 1184 MPa and translucency of 41.1% for a 1 mm thick sample were obtained. Due to its unique microstructure, this tetragonal ceramic provided a favorable combination of high translucency comparable to the high-translucent, tetragonal/cubic 4Y-TZP and very high strength achievable only in the pure tetragonal 3Y-TZP. The applicability and resistance to low-temperature degradation of the new dental ceramics was demonstrated.     

Corrosion of zirconia ceramics in acidic solutions at high pressures and temperatures

Changes in microstructure and phase composition of ceria stabilized tetragonal zirconia polycrystals (Ce-TZP), magnesia and yttria partially stabilized zirconia [(Mg,Y)-PSZ] and magnesia partially stabilized zirconia (Mg-PSZ) were studied in diluted aqueous HCl, H₂SO₄ or H₃PO₄ solutions at a temperature of 390° C and a pressure of 27 MPa. Ce-TZP is corrosion resistant under these conditions in HCl, while Mg-PSZ is attacked severely and (Mg,Y)-PSZ undergoes a surface tetragonal to monoclinic phase transformation. All investigated zirconia ceramics suffer severe weight losses and transformation to the monoclinic phase on the surface in H₂SO₄. Only a small weight gain and a slight increase of m-phase on the surface of the ceramics is found in H₃PO₄.     

Phase Stability in Calcia‐Doped Zirconia Nanocrystals

Calcia‐doped zirconia exhibits all of the polymorphism seen in the yttria‐doped zirconia ceramics, but can be produced at lowered costs and in greater abundance due to the accessibility of Calcium precursors in comparison to Yttrium. Although with great challenges, there exists an opportunity to replace yttria with calcia in applications such as ionic conductors where phase stability is critical. There is a dearth of surface characterization to enable design and prediction of the polymorphism in nanoparticulate calcia–zirconia. With recent advances in water adsorption microcalorimetry, one can accurately probe surface energies of the four zirconia polymorphs: monoclinic, tetragonal, cubic, and amorphous. The surface energies can then be coupled with bulk enthalpies extracted from oxide melt drop solution calorimetry to create a nanocrystalline phase stability diagram similar to its bulk counterpart. We report here the surface and bulk thermodynamic data on polymorphs of calcia–zirconia with composition ranging from 0 to 20 mol% calcia and use it to build a nanophase diagram for this system. The effect of the humidity in the phase stability diagram trends is also addressed and demonstrated to minimize the effect of the surface energies in the overall polymorphism trends.     

Pressureless sintering of yttria-gadolinia co-stabilized zirconia

Zirconia ceramics partially stabilized with yttria and gadolinia [(3-x)Y,xGd-TZP; x = 0–2] were manufactured by intensive co-milling of zirconia and stabilizer oxides, spray granulation, axial pressing and pressureless sintering at 1300–1400 °C. Microstructure, phase composition and mechanical properties were determined. Stabilizer re-distribution in the materials at higher sintering temperatures was monitored by XRD. Substitution of yttria for gadolinia reduces the stabilizer content in the tetragonal phase, increases the tetragonality of the materials and induces higher transformability and toughness. The hardness is thereby reduced. In accordance with thermodynamic considerations the cubic content increases with increasing gadolinia content.     

Wetting and corrosion of yttria stabilized zirconia by molten slags

We present first results of a study dealing with the corrosion of yttria stabilized zirconia ceramics by molten slags. Good wetting of a typical metallurgical slag as a pre-requisite for an effective chemical interaction of melt and zirconia was found. Both the dissolution of Zirconia and the leaching of the stabilizing agent into the molten slag are observed corrosion mechanisms. The latter induces a phase transformation from tetragonal or cubic zirconia into the monoclinic modification. The transformation with its increase in volume by app. 5% induces cracks. Those act to give new pathways for the corrosive media, accelerating corrosion. Crucibles from Y-PSZ have been used as samples in experiments with various slags. We also demonstrate the use of cathodoluminescence microscopy as a powerful mapping tool for zirconia phase differentiation which was verified by Raman and XRD measurements.