Stability of ZrO2 Phases in Ultrafine ZrO2-Al2O3 Mixtures

Mixtures of ultrafine monoclinic zirconia and aluminum hydroxide were prepared by adding NH₄OH to hydrolyzed zirconia sols containing varied amounts of aluminum sulfate. The mixtures were heat-treated at 500° to 1300°C. The relative stability of monoclinic and tetragonal ZrO₂ in these ultrafine particles was studied by X-ray diffractometry. Growth of ZrO₂ crystallites at elevated temperatures was strongly inhibited by Al₂O₃ derived from aluminum hydroxide. The monoclinic-to-tetragonal phase transformation temperature was lowered to ∼500°C in the mixture containing 10 vol% Al₂O₃, and the tetragonal phase was retained on cooling to room temperature. This behavior may be explained on the basis of Garvie's hypothesis that the surface free energy of tetragonal ZrO₂ is lower than that of the monoclinic form. With increasing A1₂O₃ content, however, the transformation temperature gradually increased, although the growth of ZrO₂ particles was inhibited; this was found to be affected by water vapor formed from aluminum hydroxide on heating. The presence of atmospheric water vapor elevates the transformation temperature for ultrafine ZrO₂. The reverse tetragonal-to-monoclinic transformation is promoted by water vapor at lower temperatures. Accordingly, it was concluded that the monoclinic phase in fine ZrO₂ particles was stabilized by the presence of water vapor, which probably decreases the surface energy.     

Phase Transformation of Hydrous-Zirconia Fine Particles Containing Cerium Hydroxide

Monoclinic hydrous-zirconia fine particles that contained cerium(IV) hydroxide (Ce(OH)₄) were heated from 200°C to 600°C, to investigate the phase transformation to CeO₂-doped tetragonal ZrO₂. Both ZrOCl₂·8H₂O and CeCl₃·7H₂O were dissolved in aqueous solutions and then boiled to prepare the hydrous-zirconia particles. The Ce(OH)₄-containing hydrous-zirconia particles were prepared by adding aqueous ammonia into the boiled solutions. The monoclinic-to-tetragonal ( m right arrow t ) phase transformation of the Ce(OH)₄-containing hydrous zirconias was observed at 300°C using X-ray diffraction (XRD). XRD and Brunauer-Emmett-Teller (BET) specific surface area measurements revealed that the Ce(OH)₄-containing hydrous zirconias had a tendency to transform from the monoclinic phase to the tetragonal phase at lower temperatures as the primary particle size of the hydrous zirconia decreased and the Ce(OH)₄ content increased. These tendencies for the m right arrow t phase transformation agree with the conclusions that have been derived from thermodynamic and kinetic considerations.     

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.     

At-Temperature Neutron Diffraction Investigation of the Aging Process in Magnesia-Partially-Stabilized Zirconia

A time-resolved neutron powder diffraction technique has been used to follow the changes occurring during the aging of magnesia-partially-stabilized zirconia at 1100°C. Through quantitative phase analyses it has been possible to follow the development with aging time of tetragonal zirconia and of the δ-phase (Mg₂Zr₅O₁₂, related to cubic, but with ordered anion vacancies), both at the expense of cubic zirconia. Changes in lattice parameters have been attributed to the expulsion of MgO stabilizer from the tetragonal zirconia precipitates as the aging proceeds. The broadening of peaks in the neutron diffraction pattern suggests there is considerable strain in the tetragonal precipitates in the c -direction, which is the short dimension in these lenticular precipitates. On cooling, there is some transformation of tetragonal zirconia to the monoclinic and orthorhombic phases.     

Crystallization and Phase Transformation Process in Zirconia: An in situ High-Temperature X-ray Diffraction Study

Amorphous zirconia precursors were made by the precipitation of a zirconium tetrachloride solution with either slow (8 h) or rapid additions of ammonium hydroxide at a pH of 10.5. Following calcination at 500°C for 4 h, the rapidly precipitated precursor exhibited predominantly monoclinic ZrO₂ phase, while the slowly precipitated precursor produced the tetragonal ZrO₂ phase. The crystallization and phase transformations were followed by in situ high-temperature X-ray diffraction (HTXRD) for both specimens in helium and in air. Each amorphous precursor first crystallizes as the tetragonal phase at about 450°C. A tetragonal-to-monoclinic phase transformation of the rapidly precipitated material was observed on cooling at about 275°C. Surface impregnation of sulfate ions following precipitation inhibited the tetragonal-to-monoclinic transformation for the rapidly precipitated ZrO₂ sample. The crystallite size for the t -ZrO₂ of all samples, irrespective of whether they transform to monoclinic, was approximately 11 nm, indicating that the t → m transformation in these materials is not controlled by differences in crystallite size. It is therefore suggested that anionic vacancies control the tetragonal-to-monoclinic phase transformation on cooling, and that oxygen adsorption triggers this phase transformation.     

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.     

Cyclic Fatigue of Ce-TZP/AI2O3 Composites: Role of the Degradation of Transformation Zone Shielding

The origin of cyclic fatigue in two Ce-TZP/Al₂O₃ composites was investigated by (a) measurements of residual stresses in the transformation zones and crack-tip stress intensities in in situ loaded compact specimens using microprobe Raman spectroscopy, (b) examination of the crack-tip transformation zones by transmission electron microscopy, and (c) measurements of crack-growth rates in cyclic fatigue and in sustained loading at 400°C, a temperature at which stress-induced transformation of the tetragonal zirconia to the monoclinic polymorph was suppressed. Transformation zones formed during cyclic fatigue consistently showed lower compressive residual stresses and higher crack-tip stress intensities than the zones formed in sustained loading. Transmission electron microscopy revealed monoclinic laths of smaller average twin spacing and of multiple types of lattice correspondence in the transformation zones of the fatigue specimens as compared to the sustained-load specimens. Crack-growth measurements at 400°C indicated a significant suppression of the cyclic fatigue effect in the absence of transformation plasticity. These results in combination pointed to degradation of transformation-zone shielding as an important contributing cause of cyclic fatigue in Ce-TZP/Al₂O, composites. A more efficient accommodation of the transformation strains within the zones appears to be the underlying mechanism of the degradation of zone shielding in cyclic fatigue.     

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.     

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.     

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.     

Energy Crossovers in Nanocrystalline Zirconia

The synthesis of nanocrystalline powders of zirconia often produces the tetragonal phase, which for coarse-grained powders is stable only at high temperatures and transforms into the monoclinic form on cooling. This stability reversal has been suggested to be due to differences in the surface energies of the monoclinic and tetragonal polymorphs. In the present study, we have used high-temperature oxide melt solution calorimetry to test this hypothesis directly. We measured the excess enthalpies of nanocrystalline tetragonal, monoclinic, and amorphous zirconia. Monoclinic ZrO₂ was found to have the largest surface enthalpy and amorphous zirconia the smallest. Stability crossovers with increasing surface area between monoclinic, tetragonal, and amorphous zirconia were confirmed. The surface enthalpy of amorphous zirconia was estimated to be 0.5 J/m². The linear fit of excess enthalpies for nanocrystalline zirconia, as a function of area from nitrogen adsorption (BET) gave apparent surface enthalpies of 6.4 and 2.1 J/m², for the monoclinic and tetragonal polymorphs, respectively. Due to aggregation, the surface areas calculated from crystallite size are larger than those measured by BET. The fit of enthalpy versus calculated total interface/surface area gave surface enthalpies of 4.2 J/m² for the monoclinic form and 0.9 J/m² for the tetragonal polymorph. From solution calorimetry, the enthalpy of the monoclinic to tetragonal phase transition for ZrO₂ was estimated to be 10±1 kJ/mol and amorphization enthalpy to be 34±2 kJ/mol.     

Significance of Internal Stresses for the Martensitic Transformation in Yttria-Stabilized Tetragonal Zirconia Polycrystals During Degradation

Various aspects of the tetragonal ( t ) to monoclinic ( m ) transformation during degradation have been studied experimentally and theoretically in yttria-stabilized tetragonal zirconia polycrystals (Y-TZP), i.e., polycrystalline t -ZrO₂ containing Y₂O₃ in solution. Transmission electron microscopy (TEM) revealed that protruding grains at the surface of Y-TZP specimens do not transform under corrosive conditions (250°C, humid atmosphere) even after an annealing time of 168 h. Eigenstresses due to anistropic thermal expansion In and around protruding and bulk grains have been calculated for Y-TZP containing 2 and 3 mol% Y₂O₃. The prominent role of these stresses on subsequent transformation nucleation during degradation is shown to agree qualitatively with an established free energy concept. The lack of complete transformation of m -ZrO₂ is attributed to characteristics of the nucleation- and growth-controlled transformation process.     

Phase Separation in 12 mol% Ceria-Doped Zirconia Induced by Heat Treatment in H2 and Ar

The phase separation in 12 mol% CeO₂─ZrO₂ ceramic heattreated in a mixture of H₂ and Ar was investigated by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy, and Raman scattering. After heat treatment at temperatures above 1200°C, the tetragonal solid-solution phase separated into Zr₂Ce₂O₇ and the monoclinic phase. Raman scattering measurements also provided supplementary evidence for the phase separation. XPS showed that the valence change from Ce⁴⁺ to Ce³⁺ predominantly occurred, whereas the reduction from Zr⁴⁺ to Zr³⁺ took place above 1200°C. It is concluded, that in the highly reduced sample, where the valence changes from Ce⁴⁺ (Zr⁴⁺) to Ce³⁺ (Zr³⁺), the phase separation is noticeably promoted. Below 1000°C the phase separation was suppressed because of no appreciable valence change to trigger the phase separation, and the single tetragonal phase was retained.     

Phase Relations and Ordering in the System ZrO2-MgO

The Phase relationships in the system ZrO₂-MgO were reinvestigated over a wide range of temperatures and compositions. The extent of the cubic solid solution field was determined with precise lattice parameter measurements and a high-temperature X-ray furnace using analyzed samples. DTA results show that the addition of MgO to ZrO₂ decreases the transition temperature for monoclinic ⇌ tetragonal ZrO₂ and 1 mol% of MgO is soluble in the monoclinic zirconia at ∼1070°C.The invariant eutectiod point is at 13.5 ± 0.3 mol% MgO at 1406°± 7°C, which is in fair agreement with previous results by Grain. The ordered phase Mg₂Zr₅O₁₂ (δ-phase) can form metastably in cubic solid solutions at temperatures as low as 800°C after prolonged annealing. Evidence for the existence of the ordered phase MgZr₆O₁₃(γ-phase) was obtained by electron diffraction technique. Conditions for the formation of this phase are described. The ordered phases in this system are metastable and their formation is an intermediate step in the eutectoid decomposition of the cubic phase.     

ZrO2-Transformation-Toughened Glass-Ceramics Prepared by the Sol-Gel Process from Metal Alkoxides

Glasses of composition 3ZrO₂O · 2SiO₂ were prepared by the sol-gel process from metal alkoxides. Tetragonal ZrO₂ was precipitated by appropriate heat treatment at 1000° to 1200°C. The fracture toughness of these glass-ceramics increased with increasing crystallite size of the tetragonal ZrO₂, reaching ∼5.0 MN/m^3/2 at a size of ∼40 nm. The higher fracture toughness was attributed to tetragonal → monoclinic ZrO₂ transformation toughening.     

Polymorphic Behavior of Thin Evaporated Films of Zirconium and Hafnium Oxides

Polymorphism in thin evaporated films of zirconium and hafnium oxides was investigated from 100° to 1500°C by electron diffraction and transmission electron microscopy. The films have metastable cubic structures at room temperature and at moderate temperatures. Zirconium oxide, depending on temperature, exists in cubic, tetragonal, and monoclinic forms, whereas hafnium oxide transforms directly from the cubic to the monoclinic structure. The transformation temperatures depend on the oxygen partial pressure. Air annealing of thin films of ZrO₂ and HfO₂ lowered the temperature of transformation of the tetragonal and the cubic structure into the monoclinic structure by about 150° and 100°C, respectively. The cubic/tetragonal transformation of ZrO₂ is monotropic, whereas the tetragonal monoclinic transformation occurs by the typical nucleation and growth mechanism. Determination of grain size in ZrO₂ at the tetragonal/monoclinic transformation temperature showed that the transformation occurs when a constant grain size of about 800 Å is reached. The oxygen partial pressure, grain size, and temperatures at which the metastable phases exist were correlated. The rate of grain growth is enhanced by increase in oxygen partial pressure. The accelerated transformation in air is attributed to rapid attainment of the critical size; grain boundary energy is an important controlling factor in transformation.     

Strengthening of Porous Mullite and Zirconia CMC Matrices by Evaporation/Condensation

A processing method using evaporation/condensation sintering in an HCl atmosphere was developed for strengthening porous materials without shrinkage. Strengthening without shrinkage is useful in preventing voids and cracks that might be formed during constrained densification, e.g., a porous matrix in a continuous fiber reinforced ceramic composite. Mixtures of mullite and zirconia (monoclinic, tetragonal (3 mol% Y₂O₃), and cubic (8 mol% Y₂O₃)) were studied and exposed to HCl vapor at temperatures up to 1300°C. It was observed that the evaporation–condensation mass transport process produced a porous material with minimal shrinkage. As the crystal structure of the starting tetragonal and cubic zirconia powders did not change after extensive coarsening, it appeared that zirconium and yttrium were transported in the same proportion via evaporation/condensation. The process produced significant coarsening of the zirconia grains, which made the material resistant to densification when heated to 1200°C in air. Because the sintering produced coarsening without shrinkage, the pores also coarsened and a porous microstructure was retained. Mixtures of mullite and zirconia were used because mullite does not densify under the processing conditions used here, namely, heat treatments up to 1300°C. The mullite particles acted as a non-densifying second phase to further inhibit shrinkage when the mullite/zirconia composite was heated up to 1200°C in air. The coarsened cubic zirconia plus mullite mixture had the least densification after heat treatments in air of 100 h at 1200°C.     

Synthesis of the Orthorhombic Phase of 2Y˙ZrO2

A mixture of tetragonal and monoclinic 2Y˙ZrO₂ (2 mol% Y₂O₃–ZrO₂) powder was treated from 400° to 800°C and from 4 to 7 GPa for 30 min. The products were identified by powder XRD, Raman spectroscopy, and TEM. Results indicated that an orthorhombic phase was synthesized at T=400° to 600°C and P>4 GPa. The lattice parameters were obtained as a=0.505, b=0.525, and c=0.509 nm; the density was 6.17 Mg/m³. The orthorhombic phase always coexisted with the tetragonal phase in the products. The amounts of the tetragonal phase before and after treatment remained largely unchanged, whereas the amount of new orthorhombic phase was nearly the same as the decreased amount of the monoclinic phase. It was assumed, therefore, that only the monoclinic phase transformed into the orthorhombic phase.     

Tetragonal Zirconia Polycrystals Reinforced with SiC Whiskers

The microstructure and the mechanical properties of hot-pressed tetragonal ZrO₂ polycrystals (TZP) reinforced with up to 30 vol% SiC whiskers were studied. The SiC whisker-TZP composites were stable under the hot-pressing conditions at 1450°C. Annealing in an oxidizing atmosphere at ∼1000°C resulted in glass formation and microcracking caused by whisker oxidation and transformation of the ZrO₂ grains near the whiskers to monoclinic symmetry. The fracture toughness was markedly improved by the dispersed whiskers (∼12 Mpa·m^1/2 at 30 vol% SiC) compared to the values measured for the matrix (∼6 Mpa·m^1/2). The flexural strength of the hot-pressed TZP-30 vol% SiC whisker composite at 1000°C (∼400 MPa) was twice that of the TZP matrix.     

Sol–Gel Processed Y-PSZ Ceramics with 5 wt% Al2O3

Y-PSZ ceramics with 5 wt% Al₂O₃ were synthesized by a sol–gel route. Experimental results show that powders of metastable tetragonal zirconia with 2.7 mol% Y₂O₃ and 5 wt% Al₂O₃ can be fabricated by decomposing the dry gel powder at 500°C. Materials sintered in an air atmosphere at 1500°C for 3 have high density (5.685 g/cm³), high content of metastable tetragonal zirconia (>96%), and high fracture toughness (8.67 MPa.m^1/2). Compared with the Y-PSZ ceramics, significant toughening was achieved by adding 5 wt% Al₂O₃.