Stability of metastable tetragonal ZrO2 in compound powders and nucleation arguments

ZrO₂-SiO₂ (11) mixtures and ZrO₂ particles were prepared by a sol-gel method from the solutions of ZrOCl₂·8H₂O (ZOC) + Si(OC₂H₅)₄ (TEOS) + C₂H₅OH and ZOC + C₂H₅OH + H₂O + NH₄Cl systems, respectively. Quantitative changes of phase crystallized by heating were compared with those of ZOC + TEOS + H₂O and/or ZrO(NO₃)₂ · 2H₂O + H₂O systems, respectively. The stability of metastable tetragonal (mt)-ZrO₂ particles depends on the Young's modulus of the SiO₂ matrix. Transition metal oxides existing on the interface assisted in stabilizing mt-ZrO₂. The order of the assistance agreed with that of the relative field strengths of their oxides. A relationship between the ionic radius and the volatility of anionic groups, and the difficulty of nucleation for the martensitic transformation accompanying a shear stress, is suggested.     

Preparation of ZrO2-CeO2 and HfO2-CeO2 nanopowders

We prepared weakly agglomerated powders of ZrO₂-CeO₂ and HfO₂-CeO₂ solid solutions 5–8 nm in particle size, consisting of monoclinic and tetragonal phases. After heat treatment at 1200°C, the crystallite size was 30 and 14 nm, respectively. We also examined the effect of precipitate freeze drying on the crystallization of hafnia-based solid solutions containing up to 20 mol % CeO₂.     

Hot isostatic pressing of tetragonal ZrO2 solid-solution powders prepared from acetylacetonates in the system ZrO2-Y2O3-Al2O3

In compositions having ZrO₂/Y₂O₃=(74.25–71.25)/(0.75–3.75) (mol% ratio) with 25 mol% Al₂O₃, metastable t-ZrO₂ solid solutions crystallize at 780° to 860°C from amorphous materials prepared by the simultaneous hydrolysis of zirconium, yttrium and aluminium acetylacetonates. Hot isostatic pressing has been performed for 1 h at 1130 and 1230°C under 196 MPa using their powders. Two kinds of material are fabricated: (i) perfect ZrO₂ solid-solution ceramics and (ii) composites of ZrO₂ solid solution and -Al₂O₃. Their mechanical properties are examined, in connection with microstructures and t/m ZrO₂ ratios. Composites with a homogeneous dispersed -Al₂O₃ derived from solid-solution ceramics result in a remarkable increase of strength.     

Preparation of tetragonal ZrO2-Gd2O3 powders

ZrO₂-Gd₂O₃ alloys containing 2,3,5 and 8 mol.% Gd₂O₃ have been prepared by mixed oxide (MO), hybrid sol-gel (SG), and co-precipitation (CP) routes. No tetragonal (t) phase is retained in the MO method, while 100% t phase is obtained in the calcined CP samples; the SG method leads to only partial stabilization of the t phase. Washing of the CP powders with propan-2-ol leads to unagglomerated powders with increased specific surface area (145 versus 89 m²g^–1) and sintered density (98% versus 79%). Cubic and t phase also appear on sintering the samples with >2 mol.% Gd₂O₃.     

The metastable two-phase region in the zirconia-rich part of the ZrO2-Y2O3 system

ZrO₂-Y₂O₃ alloys with yttria contents between 2.0 and 6.3 mol% were prepared by arcmelting. The microstructure of the alloys after isothermal ageing was examined by electron microscopy. It was found that a modulated structure was formed in alloys aged at appropriate temperatures. The modulated structure resembles the structure of spinodally decomposed metallic alloys and ceramics. The range in which the modulated structure is developed is inside the cubic-tetragonal two-phase region of the ZrO₂-Y₂O₃ system. The modulated structure is associated with metastable phase decomposition.     

A new tentative phase equilibrium diagram for the ZrO2-CeO2 system in air

The phase relationships over a wide range of temperature and compositions in the ZrO₂-CeO₂ system have been reinvestigated. From DTA results, thermal expansion measurements andK _IC determinations it was established that additions of CeO₂ to ZrO₂ decreases the monoclinic to tetragonal ZrO₂ transition temperature, from 990 ° C to 150 50 ° C, and an invariant eutectoid point at approximately 15 mol% CeO₂ exists. The extent of the different single- and two-phase fields were determined with precise lattice parameter measurements on quenched samples. Evidence for the existence of a binary compound Ce₂Zr₃O₁₀ (ø-phase) was obtained by X-ray diffraction. The ø-phase was stable below approximately 800 ° C, above which it decomposes into tetragonal zirconia + fluorite ceria solid solutions. Taking into account the polymorphic tetragonal-cubic transition and the narrowness of the two-phase tetragonal zirconia + fluorite ceria field above 2000 ° C, the existence of a new invariant eutectoid point was assumed, in which the metastable fluorite zirconia solid solution decomposes into tetragonal zirconia + fluorite ceria solid solutions. From the results obtained, the phase diagram also incorporates a eutectic point located at approximately 2300 ° C and 24 mol % CeO₂.     

Microstructure and mechanical properties of ZrO2-Gd2O3 tetragonal polycrystals

The phases, transformability, microstructure and mechanical properties of ZrO₂-Gd₂O₃ polycrystals containing 1.75–8 mol% Gd₂O₃ were studied. The samples were prepared by a coprecipitation route followed by sintering at 1400°C for 2 hours. The grain size was in the range of 0.1–0.2 m except for some large grains at high Gd₂O₃ contents. Only a tetragonal phase was observed between 2–4 mol% Gd₂O₃ and a cubic phase for compositions containing 9.6 mol% Gd₂O₃. A peak K _IC of 12 MPa m^1/2 and a strength of 800 MPa were obtained in the 2 mol% Gd₂O₃ alloy for which the t m transformation on the fracture surface was also found to be maximum. Transformation toughening is able to account for most of the toughness of the samples.     

Optical spectroscopy of Eu3+ ions in tetragonal ZrO2 nanocrystals

A facile solvothermal method was introduced to incorporate Eu3+ ions into the monodisperse tetragonal ZrO2 nanocrystals (NCs) with small size of approximately 4 nm. The optical properties for Eu3+ doped ZrO2 NCs were investigated in detail by using the photoluminescence (PL) spectroscopy at room and low temperatures. Intense red emissions from Eu3+ ions could be achieved via the host sensitization, which was found to be much more efficient than the direct excitation of lanthanide ions. Moreover, multiple sites of Eu3+ as well as the host-to-Eu3+ energy transfer were also revealed based on the PL analyses.     

Influence of some precipitation variables on thermal behavior of ZrO2-Y2O3 and ZrO2-CeO2 precipitated gels

The scope of this work consisted of producing pure zirconia powders, yttria stabilized zirconia powders and ceria stabilized zirconia powders from zirconium oxychloride and yttrium and cerium chlorides using urea as precipitating agent and polyacrylic acid as dispersing agent. A factorial analysis was designed to study the effects of some precipitation variables (precipitation temperature, precipitation time, urea concentration, yttria concentration, ceria concentration and polyacrylic acid concentration) on the thermal behavior of zirconia gels using differential scanning calorimeter (DSC). It was observed that the addition of yttrium and cerium in the solution raised the crystallization temperature of the gels, due to changes on the characteristics of the Zr–OH bonds caused by the substitution of zirconium by yttrium or cerium. For the ZrO₂-Y₂O₃ system, the presence of polyacrylic acid increased the crystallization temperature. It was suggested that polyacrylic acid promoted the formation of a random polymeric structure of zirconia gels that required higher temperatures to crystallize.     

Crystal growth of tetragonal ZrO2 in the glass system ZrO2-SiO2 prepared by the sol-gel process from metal alkoxides

Glasses in the system ZrO₂-SiO₂ containing 40 to 60 mol % ZrO₂ were prepared by the sol-gel process from metal alkoxides. Tetragonal ZrO₂ was precipitated by heat treatment at 800 and 1200° C, and its crystal growth was measured by differential thermal and X-ray diffraction analyses. At 800 to 900° C, tetragonal ZrO₂ crystals grew three-dimensionally and the activation energy for growth was calculated as about 680 kJ mol⁻¹. On the other hand, the secondary growth of tetragonal ZrO₂ at 1000 to 1200° C followed the cube-root-of-time law. The activation energy for secondary growth was about 380 kJ mol⁻¹. It is suggested that the diffusion of Zr⁴⁺ ions is the rate-limiting process for the secondary crystal growth of tetragonal ZrO₂.     

Microstructure and phase composition of ZrO2-CeO2 thermal barrier coatings

The microstructure and phase composition of zirconia plasma-sprayed thermal barrier coatings containing 12 to 25 wt% ceria addition have been investigated. Coatings containing less than 20 wt% CeO₂ are composed of a monoclinic and retained metastable transformable tetragonal phase due to the constraint developed by the small crystal size. This phase transforms readily under moderate thermal stresses. Compositions greater than 20 wt% CeO₂ are composed only of a metastable non-transformable tetragonal, tz′ structure, resistant to transformation under thermal or mechanical stresses. The microstructure of this phase shows microstructural similarities to the high-yttria t′-phase in the ZrO₂-Y₂O₃ system, such as transformation twins and anti-phase boundaries. This suggests that the phase observed in the ZrO₂-CeO₂ system forms by a similar mechanism.     

Microstructure and phase composition of ZrO2-CeO2-Al2O3 materials modified with MgO and Y2O3

This paper presents our findings on phase formation processes during heat treatment of sol-gel synthesis products with the composition (mol %) 65(88ZrO₂ + 12CeO₂) + 35Al₂O₃ modified with 1 mol % MgO or Y₂O₃. The composites modified with 1 mol % MgO have been shown to differ significantly in phase composition from the parent nanopowders. Sintering is accompanied by partial decomposition of the tetragonal zirconia (T-ZrO₂) based solid solution and the formation of a monoclinic zirconia (M-ZrO₂) based solid solution and two aluminum-containing phases: corundum and the mixed oxide MgAl₁₁CeO₁₉. The addition of 1 mol % Y₂O₃ leads to successive formation of T-ZrO₂ and corundum and improvement of their structural perfection. The observed differences in phase formation during heat treatment result in different grain size compositions in the microstructure of the composites.     

Cathodoluminescence from crystalline phases in a ZrO2-SiO2-CeO2 ceramic

The chemical composition of crystalline phases in a ZrO₂-SiO₂-CeO₂ ceramic was determined by electron probe x-ray microanalysis, and the luminescent properties of these phases were studied. The valence state of Ce in these phases was determined from cathodoluminescence data.     

A structural study of metastable tetragonal zirconia in an Al2O3-ZrO2-SiO2-Na2O glass ceramic system

The structural and microstructural properties (crystalline system at the beginning of crystallization, lattice disorder and crystallite size) of metastable zirconia have been studied by an X-ray line broadening analysis using simplified methods based on suitably assumed functions describing the diffraction profiles. Metastable tetragonal zirconia has been crystallized at 970, 1000 and 1050° C, respectively, starting from an Al₂O₃-ZrO₂-SiO₂Na₂O glassy system with a chemical composition very close to that of well known electromelted refractory materials. In the present work we have definitely shown the presence, inside the crystallized zirconia phase, of internal microstrains having values ranging approximately between 2 and 4×10^–3. Moreover, we have confirmed the peculiar smallness in size of precipitated zirconia crystallites ( 200 Å). Therefore, in the present system, the stabilization of the tetragonal form of ZrO₂ with respect to the stable monoclinic one can be explained in terms of a contribution to the amount of free energy due to strain energy, in addition to the previously hypothesized surface energy. The observed strong line broadening for some samples treated at lower temperatures (970 and 1000° C) gives rise to an apparent cubic lattice pattern; but the asymmetry of each apparent single line masks unequivocally a tetragonal doublet. This latter conclusion disagrees with some hypotheses on the existence of a cubic metastable form of ZrO₂ which could originate at the beginning of zirconia crystallization.