Cubic-Formation and Grain-Growth Mechanisms in Tetragonal Zirconia Polycrystal

The microstructure in Y₂O₃-stabilized tetragonal zirconia polycrystal (Y-TZP) sintered at 1300°–1500°C was examined to clarify the role of Y³⁺ ions on grain growth and the formation of cubic phase. The grain size and the fraction of the cubic phase in Y-TZP increased as the sintering temperature increased. Both the fraction of the tetragonal phase and the Y₂O₃ concentration within the tetragonal phase decreased with increasing fraction of the cubic phase. Scanning transmission electron microscopy (SEM) and X-ray energy dispersive spectroscopy (EDS) measurements revealed that cubic phase regions in grain interiors in Y-TZP generated as the sintering temperature increased. High-resolution electron microscopy and nanoprobe EDS measurements revealed that no amorphous layer or second phase existed along the grain-boundary faces in Y-TZP and Y³⁺ ions segregated at their grain boundaries over a width of ∼10 nm. Taking into account these results, it was clarified that cubic phase regions in grain interiors started to form from grain boundaries and the triple junctions in which Y³⁺ ions segregated. The cubic-formation and grain-growth mechanisms in Y-TZP can be explained using the grain boundary segregation-induced phase transformation model and the solute drag effect of Y³⁺ ions segregating along the grain boundary, respectively.     

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.     

Crystal Structure of Metastable Tetragonal Zirconia up to 1473 K

The crystal structure of metastable tetragonal zirconia prepared via the alkoxide method has been investigated at temperatures up to 1473 K, to clarify the similarity between this metastable phase and the tetragonal phase at high temperature. The lattice constants, tetragonality, oxygen shift parameter, and equivalent isotropic thermal parameter of the metastable tetragonal phase are proportional to the temperature. These parameters, when extrapolated to the high-temperature range, are very similar to those of the high-temperature tetragonal phase. Present results indicate that the structure of the metastable tetragonal phase is the same as that of the high-temperature tetragonal phase.     

Macrochanneled Tetragonal Zirconia Polycrystals Coated by a Calcium Phosphate Layer

A coextrusion process was used to fabricate three-directionally macrochanneled tetragonal zirconia polycrystals (TZP) with a calcium phosphate coating layer. The three-directionally connected structure was built by a unique alignment and a lamination of the TZP surrounded by calcium phosphate and carbon black filaments. After a thermal treatment (binder burnout and sintering), a 52 vol% array of 290 μm, three-directionally connected macrochannels, which were clad on the inside with bioactive calcium phosphate, had formed on the sintered TZP body. For a comparison, porous calcium phosphate with a similar structure was also fabricated. The compressive strength (96 MPa) of the three-directionally macrochanneled TZP with a bioactive calcium phosphate layer was much higher than that (24 MPa) of the three-directionally macrochanneled calcium phosphate.     

Superplastic Bulging of Fine-Grained Zirconia

A tetragonal zirconia containing 2 mol% Y₂O₃, with 0.3 mol% CuO addition as a grain-boundary phase, was superplastically stretched at 1150°C using a hemispherical punch. Mechanical analyses were performed to establish that a biaxial tensile stress/strain state was achieved in the process with a maximal strain of 0.5 in the thinned hemispherical shell. The material was damage tolerant up to a critical strain rate, approximately 10⁻³ s⁻¹.     

Oxygen Vacancies in Pure Tetragonal Zirconia Powders: Dependence on the Presence of Chlorine during Processing

We have used several experimental methods to study how a large extrinsic oxygen vacancy density in pure tetragonal ZrO₂ powders depends on details of how those powders are made. Samples were made from oxychloride and nitrate precursor solutions. We used perturbed angular correlation spectroscopy to determine in situ phase structure and the density of oxygen vacancies at 1200°C, XRD and SEM to determine the grain size and morphology of samples annealed at temperatures ranging from 200°–1200°C, and neutron activation analysis (NAA) to investigate purity of samples. NAA results showed that samples contain cation impurities at levels <<100 ppm. The XRD and SEM measurements showed that grains were nanometer-size, had a broad distribution, and grew from ∼10 nm at 200°C to ∼1 μm at 1200°C. The most striking process dependence is on presence of chlorine during processing. The grain size and phase above 600°C, and both the morphology and the density of oxygen vacancies at 1200°C were strongly affected by presence of chlorine-containing vapor during annealing. Samples processed in a chlorine-free atmosphere had large well-sintered grains and large (>500 ppm) oxygen vacancy concentrations at 1200°C, whereas samples processed in flowing H₂O/HCl vapor had smaller grains, porous morphology, and small (<100 ppm) vacancy density. All samples were loose powders consisting of single grain particles at <1000°C and multiple-grain particles at 1200°C.     

Room-Temperature Aging of Laminate Composites of Alumina/3-mol%-Yttria-Stablilized Tetragonal Zirconia Polycrystals

The stresses of laminate structures obtained by joining single layers of pure alumina (A), pure yttria-stabilized tetragonal zirconia, 3Y-TZP (Z), and an intimate mixture of alumina and zirconia (AZ) have been determined by fluorescence (in alumina) and Raman (in zirconia) piezospectroscopy. Three symmetrical stacking sequences were examined, namely, A/Z/A, A/AZ/A, and AZ/Z/AZ, with the aim of designing structures where the higher coefficient of thermal expansion (CTE) of zirconia could be used to induce compressive stress in the external layers (and ensuing tensile stress in the central layer). Two experimental sessions, 6 years apart, were conducted on the same samples, also taking care to record the spectra from the same locations; during the time elapsed between the two sessions, the samples were kept at room temperature and humidity. The stress values in alumina obtained during the more recent session were markedly different from those observed in the first session. Monoclinic zirconia ( m -zirconia) was absent in all samples in the first session, whereas up to 25 vol% zirconia could be observed during the second session. m -Zirconia could only be observed in AZ layers and not in Z layers, irrespective of the position in the stacking sequence. It was concluded that 3Y-TZP underwent spontaneous tetragonal-to-monoclinic ( t – m ) transformation, that is, "aging," when mixed with alumina at the grain-size level. Aging occurred only where pristine t -zirconia was subject to tensile stresses larger than ∼400 MPa.     

Accelerated Aging in 3-mol%-Yttria-Stabilized Tetragonal Zirconia Ceramics Sintered in Reducing Conditions

The aging behavior of 3-mol%-yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics sintered in air and in reducing conditions was investigated at 140°C in water vapor. It was observed by X-ray diffraction (XRD) that 3Y-TZP samples sintered in reducing conditions exhibited significantly higher tetragonal-to-monoclinic transformation than samples with similar density and average grain size values but obtained by sintering in air. This fact is explained by the increase of the oxygen vacancy concentration and by the presence at the grain boundary region of a new aggregate phase formed because of the exolution of Fe²⁺ ions observed by X-ray photoelectron spectroscopy.     

Creep Deformation and the Grain-Boundary Resistivity of Tetragonal Zirconia Polycrystalline Materials

The grain-boundary resistivity of tetragonal zirconia polycrystals, which had undergone creep with different applied compressive loads and at different temperatures, has been measured with impedance spectroscopy. A stress exponent of unity was determined from strain rate versus stress data. The grain-boundary resistivity decreased significantly with increasing stress at a constant creep temperature indicating squeezing out of the glassy phase from interfaces between grains. This, however, had no effect on the activation energy for the grain-boundary resistivity.     

Diffusion-Induced Grain-Boundary Migration in Ceria-Stabilized Tetragonal Zirconia Polycrystals

The microstructure and microchemistry of grain-boundary regions in (CeO₂+ La₂O₃)-stabilized tetragonal ZrO₂ polycrystals (Ce(La)-TZP) were studied by means of transmission electron microscopy (TEM). Evidence was found for the existence of crystalline and vitreous intergranular phases situated in small pockets at multiple grain junctions and in thin films along grain boundaries. In this ceramic system grain-boundary migration was observed in situ in the TEM in sample areas subjected to electron irradiation. Interfaces migrated away from their centers of curvature. Evidence was found for Ce de-alloying in the volume swept by the advancing boundaries. It is suggested that the coherency lattice strain brought about by a partial reduction of Ce, resulting in the diffusion of Ce³⁺ along grain boundaries to free surfaces, is the driving force for this phenomenon.     

Role of Grain-Boundary Glass Phase on the Superplastic Deformation of Tetragonal Zirconia Polycrystal

Superplastic deformation of tetragonal zirconia polycrystal (TZP) was investigated by compression test in the temperature range of 1000° to 1500°C. Special attention was paid to the role of the grain-boundary glass phase on hightemperature deformation behavior. A small addition of glass phase markedly improved the high-temperature deformability of TZP. Lithium silicate glass was much superior to aluminosilicate or lithium aluminum silicate glasses for lowering the high-temperature flow stress. The deformation mechanism was discussed on the basis of mechanical testing data and microstructural examinations.     

Grain Size Control of Tetragonal Zirconia Polycrystals Using the Space Charge Concept

Grain growth kinetics and grain-boundary segregation of 12Ce-TZP and 2Y-TZP, containing divalent to pentavalent cationic dopants, were studied. In all cases, normal grain growth follwing the parabolic growth relation was observed at higher temperatures. The mobility of grain boundaries was suppressed by the addition of divalent and trivalent cations, unchanged or enhanced by the addition of tetravalent and pentavalent cations. Larger cations have a stronger effect in suppressing grain growth. From ESCA, AES, and STEM analysis of the near grain-boundary regions, it is further concluded that only divalent and trivalent cations segregate. These observations can be satisfactorily rationalized using the space charge concept and the model of impurity drag.     

Subeutectoid Degradation of Yttria-Stabilized Tetragonal Zirconia Polycrystal and Ceria-Doped Yttria-Stabilized Tetragonal Zirconia Polycrystal Ceramics

Yttria-doped tetragonal zirconia containing 2 and 3 mol% Y₂O₃ (Y-TZP), and CeO₂-doped Y-TZP containing 0 to 12 mol% CeO₂ were sintered at 1350°C in a tetragonal single-phase field for 2 h in air, and the degradation behavior at low temperature in air and in hot water was observed. X-ray photoelectron spectroscopy studies on the surface of hydrothermally treated samples show evidence for the formation of a YO(OH) species, along with the simultaneous formation of purely tetragonal zirconia nuclei that retain their coherence in the Y-TZP matrix. Above a critical size, the tetragonal nuclei spontaneously transform to a monoclinic structure, giving rise to macro- and microcracking. The strong tetragonal grains degrade to produce a spalling phenomenon that facilitates further degradation. Y-TZP ceramics alloyed with adequate amounts of CeO₂ show no tetragonal-to-monoclinic transformation after hydrothermal treatment.     

Indirect Determination of the Piezospectroscopic Coefficients of Ceria-Stabilized Tetragonal Zirconia Polycrystals

A method is proposed for the indirect determination of the stress dependence (expressed as piezospectroscopic (PS) coefficients) of spectroscopic bands of ceramic materials/phases. This method is based on the intimate mixture (intimate at the microstructural, grain-size level) of two phases/materials when the stress in one is independently known; it is used to determine the PS coefficients of the most intense Raman bands in ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP). Different amounts of Ce-TZP were mixed with alumina and the composite pellets sintered; subsequently, the stress in alumina was determined through the PS coefficient of its R2 luminescence band and the stress in Ce-TZP derived from the static equilibrium condition. The frequency shifts of each Raman band of Ce-TZP have been plotted against the stress and the slopes provide the PS coefficients. The method has the advantage of not requiring any type of loading device (i.e., diamond anvil-cell, bending jig). Finally, the limits are also discussed, the most important one being the requirement of immiscibility of the two materials/phases.     

Raman Investigation of the Nitridation of Yttria-Stabilized Tetragonal Zirconia

Raman spectroscopy has been used to obtain Raman spectra of yttria-stabilized tetragonal zirconia subject to surface nitridation induced by contact with zirconium nitride. Raman spectra recorded from regions at increasing distance from the source of nitridation have been used to obtain diffusion profiles from samples treated at different times and temperatures. The coupling of X-ray diffraction data previously taken and of the Raman spectra shows that in the samples there is a two-phase region (tetragonal + cubic) near the nitrided surface and that, at larger distance inside the samples, there is only one phase (tetragonal). Fitting of the diffusive profiles in the single-phase tetragonal region with an appropriate diffusion function allows the determination of the diffusion coefficient of nitrogen in tetragonal zirconia which is expressed in terms of the preexponential factor, D ₀= (3.98 ± 0.5) × 10⁻³ cm²/s, and the activation energy, Q = 170 ± 10 kJ/mol.     

加压辅助闪烧工艺制备四方相氧化锆

研究了加压辅助闪烧烧结工艺参数(温度、电压、电流、压力)对钇稳氧化锆致密度、微观组织结构和成分组成的影响,该工艺在热压烧结基础上叠加闪烧效应,利用高电场强度使高温导电氧化锆瞬间发生密实化烧结.结果表明:钇稳氧化锆的闪烧临界温度为880℃,在相同的电场强度条件下,闪烧临界温度处烧结可获得最大的闪烧收缩量.氧化锆在临界烧结...     

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.     

Strength Analysis of Yttria-Stabilized Tetragonal Zirconia Polycrystals

Tensile strength of Y₂O₃-stabilized ZrO₂ polycrystals (Y-TZP) was measured by a newly developed tensile testing method with a rectangular bar. The tensile strength of Y-TZP was lower than that of the three-point bend strength, and the shape of the tensile strength distribution was quite different from that of the three-point bend strength distribution. It was difficult to predict the distribution curve of the tensile strength using the data of the three-point bend strength by one-modal Weibull distribution. The distribution of the tensile strength was analyzed by two- or three-model Weibull distribution coupled with an analysis of fracture origins. The distribution curve of the three-point bend strength which was estimated by multimodal Weibull distribution agreed favorably with that of the measured three-point bend strength values. A two-modal Weibull distribution function was formulated approximately from the distributions of the tensile and three-point bend strengths, and the estimated two-modal Weibull distribution function for the four-point bend strength agreed well with the measured four-point bend strength.     

Grinding-Induced Texture in Ferroelastic Tetragonal Zirconia

Ceria- and yttria-doped tetragonal polycrystalline zirconia ceramics were ground at temperatures as high as 1100°C. X-ray diffraction revealed that the intensity ratio I ₍₀₀₂₎/ I ₍₂₀₀₎ increased (to as high as ∼4.5) compared with that from the as-sintered surfaces (∼0.55). The enhancement in I ₍₀₀₂₎/ I ₍₂₀₀₎ at temperatures well above the m → t transition temperature shows that it is not related to transformation, reversible or otherwise, but can be explained by ferroelastic domain switching.     

Effect of Cation Doping on the Superplastic Flow in Yttria-Stabilized Tetragonal Zirconia Polycrystals

The superplastic characteristics of various cation-doped yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) were examined. For 1 mol% cation doping the true stress of Y-TZP is very dependent on the ionic radii of the doped cations; for instance, smaller cation radii give rise to lower true stress when compared with the other compositions for the same grain size, strain rate, and testing temperature. The altered true stress level must be due to the change in diffusivity of the accommodation process for grain boundary sliding caused by the addition of cations in ZrO₂. The strain to failure of the doped zirconia is affected by both ionic radius and valence of the dopant cations.