The ZrO2-rich region of the ZrO2-MgO system

The solubility limits of MgO in tetragonal zirconia were studied by combining the differential thermal analysis data and X-ray disappearing phase method. From these experiments a eutectoid reaction, tetragonal ZrO₂ solid solution monoclinic ZrO₂ solid solution + MgO, at 1120±10 °C and 1.6±0.2 mol% MgO was established. The solubility of MgO in tetragonal ZrO₂ diminished as the temperature increased, and at 1700 °C the solubility was less than 0.5 mol% MgO. The extent of the cubic zirconia solid solution single field was determined by using precise lattice parameter measurements and SEM observations. In this way an invariant eutectoid point, cubic ZrO₂ solid solution tetragonal ZrO₂ solid solution + MgO, was located at 1420±10 °C and 14.8±0.5 mol% MgO.     

Low temperature phase equilibria and ordering in the ZrO2-rich region of the system ZrO2-CaO

From co-precipitated powder samples, the solid state reactions occurring between room temperature and 1500° C in the ZrO₂-CaO system have been studied. At low temperatures, compositions containing < 25 mol% CaO show a complex picture of phase transformation and ordering in the system. From the obtained results the following singular reactions have been established. (i) Tetragonal zirconia solid solution decomposes eutectoidally at 7 mol% CaO and 1048 ± 4° C into monoclinic zirconia solid solution and calcium zirconate (CZ). (ii) Cubic zirconia solid solution undergoes a eutectoidal decomposition at 17.5 mol% Cao and 1080 ±20° C into tetragonal solid solution + calcium zirconate. (iii) The monoclinic ordered phase, CaZr₄O₉ (₁), ), undergoes an order-disorder transformation into cubic zirconia solid solution at 1232 ± 5° C. (iv) Cubic zirconia solid solution undergoes a eutectoidal decomposition into two ordered phases, ₁ + ₂ at 21 mol% CaO and 1200 ± 10°C. (v) Hexagonal ordered phase Ca₆Zr₁₉O₄₄ (₂) decomposes peritectoidally into cubic zirconia solid solution + calcium zirconate at 1360 ± 10° C. The two ordered phases ₁ and ₂ seem to be unstable below 1100° C. By using DTA, X-ray diffraction and SEM techniques, the extent of the tetragonal and cubic zirconia solid solution fields have been established. From the above experimental results a new tentative phase diagram is given for the ZrO₂-rich region of the system, ZrO₂-CaO.     

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.     

Phase equilibria and ordering in the system HfO2-Yb2O3

The system HfO₂-Yb₂O₃ was investigated in the 0 to 100 mol % Yb₂O₃ range using X-ray diffraction analysis, linear thermal expansion measurements and melting point studies. At high temperatures, the system is dominated by wide regions of solid solutions based on HfO₂ and Yb₂O₃ separated by a two-phase field which appears to extend to the solidus. The extent of the cubic hafnia and ytterbia C-type solid solution fields was established using the precision lattice parameter method. At low temperature (< 1800° C) two ordered phases were found in the system, one at 40 mol % ytterbia with ideal formula Yb₄Hf₃O₁₂, and another at 70 mol % ytterbia with formula Yb₆HfO₁₁. Four eutectoid reactions and a peritectic reaction cubic ytterbia solid solution cubic hafnia solid solution + liquid at 67 mol % and 2380° C have been established in the system. By incorporating the known tetragonal-cubic hafnia and C-type-hexagonal ytterbia transition temperatures, and the melting points data in the system, a tentative phase diagram is given for the system HfO₂-Yb₂O₃.     

The modulated structure formed by isothermal ageing in ZrO2-5.2 mol % Y2O3 alloy

The modulated structure produced by isothermal ageing of ZrO₂-5.2 mol % Y₂O₃ alloy was examined mainly by electron microscopy. It was found that the modulated structure was formed at ageing temperatures between 1400 and 1600° C, but not at 1700° C. The structure is developed by spinodal decomposition, which produces compositional fluctuation in the elastically soft 111 direction in cubic zirconia. The hardness increase caused by the development of modulated structure during ageing is larger than the hardening by precipitation of tetragonal phase in the cubic matrix.Graduate Student, Tohoku Univerisy, Sendai, Japan.     

Preparation and thermal evolution of sol-gel derived transparent ZrO2 and MgO-ZrO2 gel monolith

Transparent gel monoliths of pure and MgO-doped zirconia having dopant concentrations in the range 0 to 15 mol % were prepared by chemical polymerization of zirconium n-propoxide and magnesium acetate tetrahydrate using 2-methoxy ethanol as solvent. The thermal evolution of amorphous gels was studied by differential thermal analysis, X-ray diffraction and transmission electron microscopy. The crystallization of pure and doped zirconia gels occurred in the temperature range 360 to 450° C. The first crystalline phase to appear is tetragonal for pure and 2 mol % doped zirconia, and cubic for 3 to 15 mol % doped samples. Both crystallization and decomposition temperatures are found to increase with increasing dopant concentration, approaching a saturation value for 10 mol % doped samples. It has been established that the transformation of the cubic to the monoclinic phase takes place via a metastable tetragonal phase. A linear relationship between the lattice parameter of cubic zirconia and MgO concentration has been established. X-ray diffraction studies have also revealed that the entire amount of MgO used in preparing doped zirconia gels remains in a single MgO-ZrO₂ crystalline phase formed initially by thermal treatment.[/p]     

Synthesis and characterization of vanadium-containing ZrO2 solid solutions pigmenting system from gels

A procedure is reported for the synthesis of vanadium-doped zirconia pigmenting system with different vanadium loadings which permitted their complete formation and further characterization. Monoclinic vanadium-zirconia solid solutions were prepared by gelling mixtures of zirconium n-propoxide and vanadyl acetylacetonate and studied over the range of temperature up to 1300 °C. Succesive steps of the reactions leading to the final monoclinic vanadium-zirconia solid solution phase were investigated by X-ray powder diffraction. It was found that the formation of the monoclinic solid solution took place by a phase transformation from a phase with the structure of tetragonal zirconia. The transformation temperature of metastable tetragonal to monoclinic phase was found to be governed by the nominal vanadium amount. Measurements of lattice parameters of monoclinic vanadium-zirconia solid solutions as a function of the nominal vanadium amount revealed that vanadium was dissolved in the zirconia lattice. Energy dispersive X-ray microanalysis and lattice parameters variation indicates that the maximum amount of vanadium into the monoclinic zirconia lattice was about 5 mol % of vanadium (3.7 wt % as V₂O₅). UV-Vis diffuse reflectance of monoclinic V-ZrO₂ solid solutions indicated that vanadium was dissolved as V⁺⁴ and that the color of vanadium-zirconia yellow pigments was produced by the dissolved vanadium.     

Acoustic emission study of phase relations in low-Y2O3 portion of ZrO2-Y2O3 system

The (metastable) tetragonal phase in 3–4 mol% Y₂O₃-ZrO₂ alloys undergoes a transition to the monoclinic form in the 200–300 °C temperature range. Microcracking due to the volume change at this transition has been detected in these compositions by sharp acoustic emission during heating. The phase change was confirmed by X-ray diffraction, dilatometry and scanning electron microscopy. The monoclinic tetragonal transition in ZrO₂-1 mol% Y₂O₃ alloy at 850–750 °C and the same phase change in 2, 3, 4 and 6 mol% Y₂O₃ compositions at the eutectoid temperature of about 560 °C was also clearly signalled by the acoustic emission counts during heating and cooling. There was no significant acoustic emission activity on heating and cooling the 9 and 12 mol% Y₂O₃ compositions, which are cubic. The acoustic emission data thus confirm the phase relations in the 1–12 mol% Y₂O₃ region, established by conventional methods such as differential thermal analysis, dilatometry and X-ray diffraction.     

Electrochemical ZrO2 and Al2O3 coatings on SiC substrates

SiC was electrochemically coated with ZrO₂ and with Al₂O₃ from 0.1 m aqueous solutions of metal-nitrate-hydrates with ethanol added. Amorphous zirconia and alumina coatings were formed with current densities from 10 to 70 mA cm^–2, and deposition durations of 1–60 min. The as-deposited coatings contained microcracks caused by drying shrinkage. Sintering of zirconia at 900 °C for 1 h and of alumina at 1200 °C for 2 h in air was accompanied by crystallization to a mixture of tetragonal and monoclinic phases in the former and to -alumina in the latter. The absence of intermediate phases between the coatings and the substrates and the good adherence of the sintered coatings indicate the high-temperature stability of these coatings.     

The effect of Bi2O3 on the microstructure and electrical conductivity of ZrO2-Y2O3 ceramics

ZrO₂-Y₂O₃ ceramics with varying Bi₂O₃ contents were prepared and their microstructures and electrical conductivities investigated. The phase stability of cubic fluorite zirconia was disturbed by the introduction of Bi₂O₃ and tetragonal or monoclinic second phases appeared. The effect of the second phases on the intragrain and the grain boundary conductivities was investigated in the 300–550 C range using complex plane analysis in the frequency range of 5 Hz to 13 MHz. It showed that conductivity data could readily be interpreted in terms of possible physical models and electrical equivalent circuits. Tetragonal phases had a small positive influence on the intragrain conductivity. The grain 9boundary resistivity could be diminished by discrete monoclinic second phases which offered more conductive intergranular contacts.     

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.     

Formation and hot isostatic pressing of ZrO2 solid solution in the system ZrO2-Al2O3

In the system of ZrO₂-Al₂O₃, cubic ZrO₂ solid solutions containing up to 40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials prepared by the simultaneous hydrolysis of zirconium and aluminium alkoxides. At higher temperatures, they transform into tetragonal solid solutions. Metastable ZrO₂ solid solution powders containing 25 mol% Al₂O₃ have been sintered at 1000–1150 °C under 196 M Pausing the hot isostatic pressing technique. The solid solution ceramics consisting of homogeneous microstructure with an average grain size of 50 nm exhibited a very high fracture toughness of 23 MN m ^–1.5. They have been characterized by X-ray diffraction and electron probe surface analyses.     

Iron-stabilized nanocrystalline ZrO2 solid solutions: Synthesis by combustion and thermal stability

The synthesis of Fe³⁺-stabilized zirconia by the nitrate/urea combustion route was investigated. Using several characterization techniques, including X-ray diffraction, field-emission-gun scanning electron microscopy and notably Mössbauer spectroscopy, it was possible to determine the appropriate amount of urea that allows to obtain a totally stabilized Zr_0.9Fe_0.1O_1.95 solid solution. The nanocrystalline zirconia solid solution is mostly tetragonal, but the presence of the cubic phase could not be ruled out. An in-depth study of the thermal stability in air showed that the Fe³⁺ solubility in the stabilized solid solution starts to decrease at about 875 °C which results in the formation of hematite (possibly containing some Zr⁴⁺) at the surface of the zirconia grains and further provokes the progressive transformation into the monoclinic zirconia phase.     

Microstructure of Y-PSZ after ageing at high temperature

Partially stabilized zirconia (PSZ) materials containing 2.5 and 5.0 mol % Y₂O₃ were prepared by pressureless sintering and aged at 1200° C for 1000 IS, and their microstructures were analysed by transmission electron microscopy and electron diffraction methods. Tetragonal zirconia polycrystal (TZP) containing 2.5 mol % Y₂O₃ before ageing showed nearly 100% tetragonal microstructure and 0.5 m grain size, but after ageing the microstructure changed greatly, exhibiting no simple grain structure over wide areas. Repeated twin structures within the grains were observed. Y-PSZ material containing 5.0M01% Y₂O₃ before ageing showed a tetragonal (I structure within a cubic (c) stabilized ZrO₂ matrix, After ageing, structures of fine strip crystals crossed each other orthogonally within the cubic matrix and typical diffuse scattering in the diffraction pattern was observed. Repeated twins were found on the plane of (100)_m, and the orientational relationship between tetragonal (t) and monoclinic (m) crystal was determined to be (100)_m [(100)_t, [010]_m \tT [001b]_t.     

Influence of composition on the T→M transformation in the systems ZrO2-Ln2O3 (Ln=La,Nd, Sm,Eu)

The systems ZrO₂-Ln₂O₃ have been studied on samples annealed at 600,1170,1450°C in the 0–15 mol % Ln₂O₃ (where Ln is the rare-earth La, Nd, Sm or Er) range using X-ray diffraction, thermal analysis and dilatometry. The microstructure of annealed samples was examined mainly by electron microscopy. It was found that rare-earth oxides-doped zirconia formed monoclinic, tetragonal, cubic and pyrochlore-type phases. The existing region of the tetragonal phase is 1–15 mol % Ln₂O₃, which is independent of the species but dependent on the dopant content and temperature. The equilibrium phase diagrams and non-equilibrium diagrams have been deduced. The temperature and composition of eutectoid ZrO_2,ss (T)→ZrO_2,ss (M) + Py, as well as interconnection between grain size, Ln₂O₃ content and the martensitic transformation temperature, (M _s), were determined.     

Effects of TiO2 addition on the sintering of ZrO2·TiO2 compositions and on the retention of the tetragonal phase of zirconia at room temperature

The production of tetragonal zirconia polycrystalline (TZP) ceramics and the identification of factors controlling retention of the tetragonal phase in the ZrO₂·TiO₂ system have been investigated. In this binary system, it was not possible to retain tetragonal zirconia polycrystals at room temperature for a range of compositions sintered above 1200 °C. A decrease in the martensitic transformation temperature of zirconia with titania addition was observed, but the effect was insufficient to retain the tetragonal phase at room temperature. In solid solution, the TiO₂ additions act to suppress ZrO₂ densification, this leading to grain growth when attempts are made to attain higher densities. The use of fine powders, fast firing or sintering in reducing conditions altered densification but was not able to generate a final grain size sufficiently small to avoid spontaneous tetragonalmonoclinic transformation on cooling. Based on the results obtained for ZrO₂·MO_x systems, the main factors involved in the retention of tetragonal zirconia at room temperature are discussed in an attempt to incorporate thermodynamical and the stress field effects.     

Phase equilibrium relations in the binary system Bi2O3-ZnO

Phase equilibria in the binary system Bi₂O₃-ZnO were studied by quenching technique. Heat-treated compositions were subjected to X-ray diffraction for phase identification, and differential thermal analysis, optical and scanning electron microscopy were used to determine the solid-liquid equilibria occurring in this system. The data thus obtained revealed that incorporation of a small amount of ZnO to the high-temperature face-centered cubic lattice of Bi₂O₃ leads to the formation of a body-centered cubic solid solution (-Bi₂O₃), which extends up to a composition of 2.2 mol% ZnO at a temperature near 750°C. On cooling, the -Bi₂O₃ solid solution undergoes a eutectoid transformation at a temperature of 710°C to yield the low-temperature monoclinic polymorph of Bi₂O₃ (-Bi₂O₃) and Bi₃₈ZnO₅₈. The eutectoid occurs at a composition of 1.8 mol% ZnO. The compound Bi₃₈ZnO₅₈ has a crystal structure analogous to the body-centered cubic -Bi₂O₃ solid solution and melts incongruently at a temperature near 753 ± 2°C to yield -Bi₂O₃ and liquid. A binary eutectic occurs between Bi₃₈ZnO₅₈ and ZnO at a composition near 25 ± 1.0 mol% ZnO with a melting temperature of 738 ±2°C. Based on the data obtained in this study, a revised phase diagram of the binary system Bi₂O₃-ZnO is proposed.     

Sintering and microstructural studies in the system ZrO2 · TiO2 · CeO2

Tetragonal zirconia polycrystals (TZP) in the system ZrO₂ · TiO₂ · CeO₂ have been prepared from titanium and zirconium alkoxides and cerium nitrate precursors. The change in microstructure with sintering temperature in the range 1300 to 1600° C has been characterized. A fully tetragonal structure with theoretical final density has been achieved after liquid-phase sintering in the range 1350 to 1400° C for 2h. Sintering at temperatures above 1450° C resulted in a loss of stabilizer from the matrix, by the formation of zirconium titanate and to a cerium-, titanium-rich liquid. The loss of stabilizer was such that in the temperature range 1500 to 1600° C, extensive transformation to monoclinic zirconia occurred spontaneously on cooling. The tetragonal zirconia formed after sintering at 1350° C was found to be very stable. Thec/a ratio of the tetragonal phase in this system is higher than in any of the binary TZP systems reported in the literature. The stability of the tetragonal phase is believed to be associated with this highc/a ratio.     

Transformation of Sc2O3-doped tetragonal zirconia polycrystals by aging under hydrothermal conditions

The phase transformation of less than 6 mol% Sc2O3-doped tetragonal zirconia polycrystals consisting of fine grains has been investigated. Dense bodies with homogeneous microstructures doped with 3.5 to 5 mol% Sc2O3 sintered at 1300°C for 1 h consisted mostly of a tetragonal phase. Within 20 h of aging under hydrothermal conditions at 180°C, the amount of monoclinic ZrO2 on the surface of the 4 to 5 mol% Sc2O3-doped specimens sintered at 1400°C was saturated and reached a constant value, and the increase in the amount of monoclinic ZrO2 showed a sigmoidal type of kinetic transformation. The apparent activation energy for the phase transformation in Sc2O3-doped zirconia was 84–91 kJ/mol. Based on the hydrothermal aging results, the possible existence of a larger two-phase (cubic+tetragonal) region is suggested, and the phase boundary between the cubic+tetragonal and cubic phase in the ZrO2-Sc2O3 system is proposed.     

Effect of gadolinia on phase structure and thermal conductivity of ZrO2-4.5 mol%Y2O3 ceramics

This paper deals with the effect of gadolinia on the phase structure and thermal conductivity of ZrO₂-4.5 mol%Y₂O₃ (YSZ) ceramics for thermal barrier coatings. The YSZ-Gd₂O₃ ceramics were synthesized by solid state reaction at 1500 °C for 2 h in air. The relative density, structure of different YSZ-Gd₂O₃ ceramics and thermal diffusivity in a temperature range of room temperature to 1200 °C were investigated by the Archimedes method, X-ray diffraction and laser-flash method. The ZrO₂-4.5 mol%Y₂O₃ (YSZ) ceramics consist of tetragonal, cubic and a small amount of monoclinic phase, and the YSZ-1.5 mol%Gd₂O₃ ceramics consist of both tetragonal and cubic phases. However, the YSZ-3.0 mol%Gd₂O₃, YSZ-4.5 mol%Gd₂O₃ and YSZ-6.0 mol%Gd₂O₃ ceramics only exhibit a cubic structure. The thermal conductivity of YSZ-Gd₂O₃ ceramics decreases with the increase of gadolinia content under identical temperature conditions. The thermal conductivities of the YSZ and YSZ-1.5 mol%Gd₂O₃ ceramics first decrease gradually with the increase of temperature below 800 °C and then increase slightly above 800 °C. The thermal conductivities of the YSZ-3.0 mol%Gd₂O₃, YSZ-4.5 mol%Gd₂O₃ and YSZ-6.0 mol%Gd₂O₃ ceramics are almost constants from room temperature to 1200 °C.