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.     

Strengthening of Ceria-Doped Tetragonal Zirconia Polycrystals by Reduction-Induced Phase Transformation

Phase-transformation-induced compressive surface stresses were introduced into ceria-doped tetragonal zirconia polycrystals by reduction of CeO₂. Four-point-bending strength of sintered ZrO₂ containing 12 mol% CeO₂ increased from 240 to 545 MPa after it was annealed at 1400°C for 2 h in nitrogen. The strength of the same material hot isostatically pressed in oxygen increased after it was annealed in nitrogen for 2 h at 1500°C from 430 to 595 MPa.     

氧化锆陶瓷低温老化研究进展

氧化锆陶瓷具有优异的力学性能、化学稳定性和白色美学特性,已广泛用于与牙齿相关的修复体中,如牙冠、牙桥、基台以及最近的种植体。然而,氧化锆陶瓷的生物安全性受到低温老化(LTD)的威胁。LTD现象发生在低温潮湿环境中,例如在人体环境中,氧化锆陶瓷的强度在短期内迅速降低,进而导致早期失效。本文从表征方法、影响因素以及老化理论模型等角度,对近年来各国学者对氧化锆陶瓷LTD现象开展的相研究进行了综述,并对相关研究结果进行梳理了及归纳。     

On the Thermoelastic Martensitic Transformation in Tetragonal Zirconia

Recent evidence is summarized showing that the tetragonal ( t ) → monoclinic ( m ) martensitic transformation in ZrO₂ can occur thermoelastically in certain ZrO₂-containing ceramics, and that microcracking accompanying the transformation is more common than had previously been recognized. The implications of these new data for the conditions under which the stress-induced transformation is irreversible, and for the particle size dependence of the transformation start ( M _s), temperature, are discussed.     

Neutron Diffraction Studies of Phase Transformations between Tetragonal and Orthorhombic Zirconia in Magnesia-Partially-Stabilized Zirconia

Neutron powder diffraction and conventional dilatometry have been used to investigate the tetragonal-to-orthorhombic phase transformation and the orthorhombic-to-tetragonal reversion in a high-toughness magnesia-partially-stabilized zirconia. For this material, the onset temperature on cooling for the tetragonal-to-orthorhombic transformation (determined by dilatometry) was 192 K, and the reversion on subsequent heating occurred between 500 and 620 K. Neutron diffraction patterns were recorded at temperatures down to 19 K then up to 664 K, and analyzed by the multiphase Rietveld method to determine the amounts of different phases as well as their lattice parameters and unit-cell volumes. It is notable that, at its maximum, the orthorhombic phase amounted to 45% of the sample by weight. Length changes were measured, using pushrod dilatometers, in the temperature range 80 to 700 K. Length changes calculated from the neutron diffraction determinations of the proportions and unit-cell volumes of the different phases are in very good agreement with the directly measured values.     

Enhanced Phase Stability for Tetragonal Zirconia in Precipitation Synthesis

Tetragonal ZrO₂ nanocrystallites—with or without yttria (3 mol%) doping—have been synthesized via a precipitation process in which the hydrous oxide precipitate reacts with hexamethyldisilazane (HMDS) vapor before calcination. The nanocrystallites are formed and retain a tetragonal structure for hours after calcination at temperatures of 300°–1100°C. The enhanced structural metastability has been attributed to the combined effect of suppressed grain growth and reduced surface energy that results from the HMDS treatment.     

Ferroelastic Domain Switching in Polydomain Tetragonal Zirconia Single Crystals

As-received, yttria-doped (4.2 wt% Y₂O₃) single crystals of zirconia were heated to ≥2100°C in air. Cube-shaped samples with faces perpendicular to 〈100〉 axes on the basis of the pseudocubic symmetry were cut from the crystals. X-ray and electron diffraction indicated that the crystals are polydomain with [001] axes, on the basis of the tetragonal symmetry, in three mutually orthogonal directions (perpendicular to the cube faces). The cube-shaped crystals were tested in compression at temperatures as high as 1400°C. X-ray diffraction indicated that ferroelastic domains underwent reorientation (switching) in compression. Subsequently, notched samples with the long direction of the beams along 〈100〉 on the basis of the pseudocubic symmetry were fractured in three-point bending at temperatures as high as 1000°C. X-ray diffraction from fracture surfaces showed that domain reorientation had occurred and that no monoclinic phase was observed on fracture or ground surfaces. The fracture toughness at room temperature and at 1000°C was ∼12 and ∼8 MPa · m^1/2, respectively. Preliminary experiments on polycrystalline tetragonal zirconia samples containing 5.4 wt% Y₂O₃ and sintered at ≥2100°C also showed no evidence of the monoclinic phase on fracture or ground surfaces. The toughness of the polycrystalline samples was typically 7.7 MPa · m^1/2. These results indicate that ferroelastic domain switching can occur during fracture and may contribute to toughness.     

Improved Low-Temperature Environmental Degradation of Yttria-Stabilized Tetragonal Zirconia Polycrystals by Surface Encapsulation

An encapsulating layer was deposited on the surface of tetragonal zirconia polycrystals doped with 3 mol% of yttria (3Y-TZP), to prevent low-temperature environmental degradation (aging) of the material. The layer, which was composed of silica and zircon, was formed on the surface by exposing the specimens next to a bed of silicon carbide powder in a flowing hydrogen atmosphere that contained ∼0.1% water vapor at 1450°C. The layer was ∼0.5 µm thick and is expected to be under strong residual compressive stress. This encapsulation process remarkably improved the low-temperature degradation of the material. The strength of the specimens also was improved by this process.     

Grain-Size-Dependent Transformation Behavior in Polycrystalline Tetragonal Zirconia

Experimental observations of the tetragonal phase transformation behavior in polycrystalline zirconias and the related toughening contribution are presented. An analysis which considers transformation thermodynamics and residual stresses is developed to describe the influence of grain size on tetragonal-to-monoclinic transformation temperature. The model is based on the promotion of the transformation by local internal tensile stress concentrations whose effects scale with grain size. The analysis is supported by observations of the martensite start temperature–grain size behavior in polycrystalline tetragonal zirconia containing 12 mol% ceria (12CeTZP). Next, the analysis considers the grain-size-dependent behavior of the transformation-toughening contribution, Δ K ^T, and the transformation zone size, r _T. The tetragonal-to-monoclinic ( t -to- m ) formation temperature, M _s, increases with increase in tetragonal grain size, d . Experimental results for zirconia-12 mol% ceria (12CeTZP) and 2YTZP ceramics illustrate the predicted forms of the grain size dependencies for Δ K ^T and r _T. The analytical model also describes the temperature dependence of the transformation-toughening contribution Δ K ^T observed in 2 mol% yttriadoped polycrystalline tetragonal zirconias (2YTZP).     

Water Incorporation in Tetragonal Zirconia

Samples of 3 mol% Y₂O₃-stabilized tetragonal ZrO₂ ceramics were annealed at 250°C in atmospheres of water vapor pressures of 1 bar and 26 mbar. As demonstrated by the water uptake and the lattice expansion, water molecules were incorporated into the ZrO₂ lattice during annealing, and the amount of the incorporated water is determined by the water vapor pressure. Owing to the filling of oxygen vacancies by the incorporated water molecules, part of the tetragonal ZrO₂ transformed to the monoclinic structure, and protonic defects were induced. The expected proton conduction was confirmed by the polarity of the water vapor concentration cells.     

Low-Temperature Aging of Zirconia Ferrules for Optical Connectors

Zirconia ferrules for optical connectors were examined after aging at 85°C and 95% relative humidity. Two degradation mechanisms were the roughening and the deformation of the zirconia ferrule surface. Raman microscopy revealed that this relatively low-temperature degradation of zirconia ferrules is caused by the tetragonal to monoclinic transformation of zirconia, and is accelerated by stress relief during polishing. The surface upheavals associated with low-temperature aging may significantly degrade the performance of optical connectors over time.     

Sintering and Characterization of Polycrystalline Monoclinic, Tetragonal, and Cubic Zirconia

Polycrystalline monoclinic ( m ), tetragonal ( t ), and cubic ( c ) ZrO₂, sintered at 1500°C, were annealed in the cubic stability field and rapidly cooled to permit the displacive c → t ' transformation to occur in compositions containing 0–6 mol% Y₂O₃. The bulk fracture toughness of coarse-grained (> 25 μm) m , t ', and c zirconias were compared with conventionally sintered, fine-grained (typically less than 1 μm) materials. The ferroelastic monoclinic and tetragonal zirconias were more than twice as tough as paraelastic cubic zirconia.     

Crack-Tip Transformation Zones in Toughened Zirconia

Transformation zones surrounding cracks in several toughened magnesia-partially-stabilized zirconia ceramics are characterized by optical interference measurements of surface uplift and by Raman microprobe spectroscopy. The measurements demonstrate that the volume fraction of transformation is nonuniform within the zone and that the extent of the frontal zone is approximately the same as that of the wake. Results are used to evaluate the crack-tip shielding stress intensity factor and to compare with the measured fracture toughness.     

Thermodynamic Model of the Cubic → Tetragonal Transition in Nonstoichiometric Zirconia

Nonstoichiometric zirconia is described with a model recently developed for ZrO₂—Y₂O₃ alloys. It is thus possible to rationalize the experimental information on the cubic/tetragonal phase boundaries in zirconia.     

Tensile Strength of Yttria-Stabilized Tetragonal Zirconia Polycrystals

Tensile strengths of 2.0 to 5.0 mol% Y₂O₃-stabilized ZrO₂ polycrystals were described using the newly developed tensile testing method. The tensile test was conducted by attaching three strain gauges on both sides of a rectangular bar that was 10 mm by 1 mm by 200 mm. The tensile strength of tetragonal ZrO₂ polycrystals (TZP) containing 2.0 mol% Y₂O₃ showed 745 MPa, whereas the bend strength of this material was 1630 MPa. Inelastic behavior of the stress-strain curve was observed at critical stresses and strains of 500 to 700 MPa and 0.25% to 0.35%, respectively. Although deviation from proportionality was observed to be small, it increased with the increase of temperature from −100° to 200°C.     

Grain-Size Dependence of Thermal-Shock Resistance of Yttria-Doped Tetragonal Zirconia Polycrystals

Thermal-shock fracture behavior of yttria-doped tetragonal zirconia polycrystals (Y-TZP) of various grain sizes was evaluated by the quenching method using water as the quenching solvent. The tetragonal-to-monoclinic phase transformation behavior of Y-TZP around cracks introduced by thermal stress was investigated by using Raman microprobe spectroscopy. The critical quenching temperature difference (Δ T _c ) of Y-TZP ceramics increased from 250° to 425°C with increasing grain size of zirconia from 0.4 to 3.0 μm, while the fracture strength decreased from 900 to 680 MPa. The improvement of Δ T _c of Y-TZP with increasing grain size of zirconia corresponded with the quantity of tetragonal-to-monoclinic phase transformation around cracks introduced by thermal stress.     

Crystal Structure of Orthorhombic Zirconia in Partially Stabilized Zirconia

A neutron powder diffraction investigation confirms that, in tough magnesiapartially-stabilized zirconia cooled to 30 K, most of the tetragonal zirconia transforms to an orthorhombic phase. This phase is retained on heating to room temperature; the lattice parameters at 295 K are a = 0.5068, b = 0.5260, and c = 0.5077 nm. The room-temperature crystal structure (space group Pbc2₁) is determined by multiphase Rietveld refinement from the neutron diffraction pattern. This orthorhombic structure is compared with the parent tetragonal structure and with the structure of monoclinic zirconia, which it closely resembles.     

Growth of Tetragonal Zirconia Coatings by Reactive Sputter Deposition

Zirconia coatings were produced by reactive dc magnetron sputter deposition, using a system with multiple sputter sources and a biased substrate stage. Tetragonal zirconia with either a random orientation or a highly (111) preferred orientation was formed by applying a substrate bias. Coating grown with no substrate bias had the equilibrium monoclinic structure. X-ray diffraction and transmission electron microscopy analyses revealed that bias sputtering could effectively decrease crystalline size in the as-deposited coating, which resulted in room-temperature stabilization of the tetragonal phase. The fraction of tetragonal phase, the desired phase for transformation-toughening behavior, was strongly dependent on the substrate bias and post-deposition annealing temperature.     

Surface Nitridation of Yttria-Doped Tetragonal Zirconia Polycrystals (Y-TZP): Microstructural Evolution and Kinetics

Sintered tetragonal-zirconia polycrystals (TZP) were embedded in a zirconium nitride powder bed and heat-treated at various temperatures. Surface layers of the TZP specimens were transformed to a stabilized cubic-zirconia by nitrogen incorporation, and their thickness was observed to increase by a parabolic rate law. The nitrogen diffusivity was evaluated from the temperature dependence of the nitridation rate. The microstructure of the nitrided layer was composed of different zones of equiaxed and columnar grains. The columnar grains were developed along the nitrogen flux lines. The observed microstructural evolution was explained in terms of nucleation and growth kinetics of nitridation.     

Entrapped Gas Effect in the Fast Firing of Yttria-Doped Zirconia

Compared to conventional sintering of Y₂O₃-doped ZrO₂ using a slow heating rate of 10°C/min, microwave sintering and fast firing using a rapid heating rate of about 500°C/min resulted in lower final sintered densities. It is attributed to the residual chlorine in commerical zirconia powders manufactured by the chloride process. By calcining at 1100°C for 1 h to remove residual chlorines from the powder compacts, near full densities (>99% of theoretical) could be obtained by both fast firing and microwave sintering.