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.     

Thermal conductivity and phase evolution of plasma-sprayed multilayer coatings

Multilayer coatings were prepared using small-particle plasma spray to investigate the effect of interfaces on thermal conductivity and phase stability. Monolithic and multilayer alumina and yttria partially-stabilized zirconia coatings, with 0, 3, 20, and 40 interfaces in 200–380 m thick coatings were studied. Thermal conductivity was determined for the temperature range 25 °C to 1200 °C using the laser flash method and differential scanning calorimetry. Thermal conductivity of the multilayer coatings was accurately modeled by a series heat transfer equation, indicating that interfacial resistance plays a negligible role in heat transfer in the direction perpendicular to the coating plane. Powder X-ray diffraction results indicate that identical phase transitions occur in all the coatings. Independent of coating microstructure (i.e. layer thickness), as-sprayed -Al₂O₃ transforms to -Al₂O₃ after 100 hours at 1200°C; as-sprayed metastable t–ZrO₂ converts to a mixture of t–ZrO₂ and c–ZrO₂ after 100 hours at 1300 °C. Thus, the results indicate that the interfaces do not aid in stabilizing the as-sprayed phases after prolonged severe heat treatments.     

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.     

Solid-state reaction,microstructure and phase relations in the ZrO2-rich region of the ZrO2-Yb2O3 system

Phase relations below 1700°C in the ZrO₂-rich region of the zirconia-ytterbia system have been established using thermal expansion, room-temperature X-ray diffraction, precision lattice parameter measurements and microscopic observations. The solubility limits of ytterbia in both monoclinic and tetragonal zirconia were determined. A eutectoid reaction, tetragonal zirconia solid solution monoclinic + cubic zirconia solid solutions at 400 ± 20°C and 2.4 mol % ytterbia was found. The left-hand boundary of the cubic zirconia solid-solution field was redetermined between room temperature and about 1700°C. Long-range ordering was present at 40 mol % ytterbia and the formation of an ordered phase, Zr₃Yb₄O₁₂, isostructural with M₇O₁₂-type compounds was found. Its thermal stability was established between room temperature and 1630 ± 10°C, in which it decomposes into cubic zirconia solid solution by an order-disorder reaction.     

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.     

Crystallization process of cubic ZrO2 in calcium acetate solution

Ultrafine powders of cubic ZrO₂ were obtained at about 270° C by heating hydrated amorphous ZrO₂ in greater than 0.2 molal calcium acetate solutions. Ca²⁺ ions played a role as nucleii for crystallization and were introduced into distinct sites of the crystalline phases, that is, substituted for Zr⁴⁺ ions. Mn²⁺ ions produced almost the same effects on the crystallization of ZrO₂·EPR spectra for powder samples containing Mn²⁺ ions apparently showed two types as follows: for tetragonal ZrO₂ with a trace of monoclinic ZrO₂, the central fine structure transitions (M=+1/2–1/2) showed a well-resolved hyperfine structure. In addition to the m=0 transition, forbidden m=±1 transitions were observed. For cubic ZrO₂, the broad underlying response was observed as well as the hyperfine structure composed of six main peaks.     

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.     

Dispersion of ZrO2 particles in aqueous suspensions by ammonium polyacrylate

The effects of poly anionic-electrolyte (ammonium polyacrylate, PAA) as a dispersant on two kinds of ZrO₂ (monoclinic and yttria-doped tetragonal zirconia) aqueous suspensions were examined by the measurements of-potential and viscosity, the sedimentation test and the determination of the wet point and flow point of the powders. Additions above 2.5 wt% PAA to zirconia gave a negative high-potential above –30 mV, and then –45 and –30 mV were obtained for monoclinic and tetragonal zirconia above 5 wt% PAA, respectively. A high negative-potential above –30 mV was retained with 5 wt% PAA for a change in pH over a wider range (pH 6 to 10 for monoclinic ZrO₂, 7 to 9 for tetragonal ZrO₂) in comparison to that of ZrO₂ without dispersant. The increase of the-potential resulted in a decrease in the viscosity. The evaluation of dispersion by the sedimentation test was correlated well with the value of-potential and the viscosity of the suspensions. The presence of native positive charge of monoclinic and tetragonal zirconia powders required an excess amount of PAA to attain dispersion of the suspension. There was a small difference in the least amount of PAA required to attain good dispersion between monoclinic and tetragonal ZrO₂. The difference was also indicated by changes of the flow point on PAA addition. Addition of 0.1% PAA to monoclinic ZrO₂ and 0.25 wt% to tetragonal ZrO₂ gave a maximum value of the flow point, whereas the positive-potential fell to zero. Measurement of the flow point was a simple and useful technique for rapid evaluation of a required amount of dispersant for ZrO₂ suspensions.     

Improved thermal shock resistant refractories from plasma-dissociated zircon

Dissociated zircon (DZ), produced in a plasma furnace recombined and sintered to about 92% of the theoretical density in the range 1300 to 1500° C The work-of-fracture of DZ increased from 20J m^–2 to 73 J m^–2 with additions of 10 wt% monoclinic zirconia particles which had a mean diameter of about 13m. Thermal shock data showed that crack propagation in DZ/ZrO₂ composites was stable.     

Sol-emulsion-gel synthesis of hollow mullite microspheres

Hollow mullite microspheres were obtained from emulsified diphasic sols by an ion extraction method. The surfactant concentration and viscosity of the sols were found to affect the characteristics of the derived microspheres. The gel and calcined microspheres were investigated by using thermogravimetry analysis (TGA), differential thermal analysis (DTA), Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), optical and scanning electron microscopy (SEM) and particle size analysis. TGA indicated the removal of most of the volatiles, i.e. 30.77 wt% up to about 500°C. Crystallization of the Si-Al spinel at 900°–970°C in gel microspheres was confirmed by DTA and XRD. XRD results also showed the formation of orthorhombic mullite at 1200°C. FTIR indicated the sequence of transformations taking place during heat-treatment of gel microspheres at different temperatures. The optical and scanning electron microscopy confirmed the spherical morphology of the gel and calcined particles. Formation of hollow microspheres with a single cavity was identified by SEM. The particle size distribution of the mullite microspheres calcined at 1300°C/1h exhibited a size range of 6–100 m with an average particle size (d ₅₀) of 22.5 m.     

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.     

Si3N4-ZrO2 composites with small Al2O3 and Y2O3 additions prepared by HIP

Si₃N₄-ZrO₂ composites have been prepared by hot isostatic pressing at 1550 and 1750 °C, using both unstabilized ZrO₂ and ZrO₂ stabilized with 3 mol% Y₂O₃. The composites were formed with a zirconia addition of 0, 5, 10, 15 and 20 wt%, with respect to the silicon nitride, together with 0–4 wt% Al₂O₃ and 0–6 wt% Y₂O₃. Composites prepared at 1550 °C contained substantial amounts of unreacted -Si₃N₄, and full density was achieved only when 1 wt% Al₂O₃ or 4 wt % Y₂O₃ had been added. These materials were generally harder and more brittle than those densified at the higher temperature. When the ZrO₂ starting powder was stabilized by Y₂O₃, fully dense Si₃N₄-ZrO₂ composites could be prepared at 1750 °C even without other oxide additives. Densification at 1750 °C resulted in the highest fracture toughness values. Several groups of materials densified at 1750 °C showed a good combination of Vickers hardness (HV10) and indentation fracture toughness; around 1450 kg mm^–2 and 4.5 MPam^1/2, respectively. Examples of such materials were either Si₃N₄ formed with an addition of 2–6 wt% Y₂O₃ or Si₃N₄-ZrO₂ composites with a simultaneous addition of 2–6 wt%Y₂O₃ and 2–4 wt% Al₂O₃.     

Toughened glass-ceramics in the ZrO2-Al2O3-SiO2 system prepared by the sol-gel process

Monolithic glass-ceramics containing Al₂O₃ or TiO₂ were prepared in the ZrO₂-SiO₂ system by the sol-gel process from metal alkoxides. Tetragonal ZrO₂ was precipitated by heat treatment at 900–1200 °C and its crystal growth was increased by adding TiO₂ or Al₂O₃. Further heating at higher temperature resulted in the precipitation of zircon and monoclinic ZrO₂ which was transformed from tetragonal ZrO₂. The addition of Al₂O₃ had less effect on both the tetragonal-to-monoclinic ZrO₂ transformation and the precipitation of zircon. The fracture toughness increased as the size of tetragonal ZrO₂ particles increased and then decreased with the appearance of monoclinic ZrO₂ or zircon. The fracture toughness of the glass-ceramics was measured in the glass-forming regions of the ZrO₂-Al₂O₃-SiO₂ system. The fracture toughness was sensitively dependent on both Al₂O₃ and ZrO₂ content, of which the highest value achieved was 9 MPa m^1/2 for the 50ZrO₂·10Al₂O₃·40SiO₂ composition.     

Thermal expansion of Li2O-ZnO-Al2O3-SiO2 glasses and corresponding glass-ceramics

The thermal expansion behaviour of some glasses and glass-ceramics within the system Li₂ZnSiO₄-LiAlSi₂O₆ is described. The effect of TiO₂ and ZrO₂ additions is also evaluated. The expansion coefficient () of the glasses increases with an increase of the Li₂ZnSiO₄ component in the glass composition. TiO₂ and ZrO₂ were found to decrease the thermal expansion of the glasses investigated. The dilatometric transition and softening points of the glasses showed the reverse behaviour. The thermal expansion of the glass-ceramics exhibited a wide range, depending upon the type and relative proportions of the crystalline phases present. The values of the glasses ranged between 73.6 and 97.4×10^–7C^–1 in the temperature range 20–450C and those for the crystalline products ranged from 36.1 and 102.6 × 10^–7 in the temperature range 20–450C.     

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.     

Sintering and compensation effect of donor- and acceptor-codoped 3mol% Y2O3-ZrO2

Addition of 0.15–0.5 mol% acceptor oxide, Al₂O₃, to 3 mol% Y₂O₃-ZrO₂ results in enhanced densification at 1350 °C. The enhancement is accounted for by a liquid phase sintering mechanism. The addition of donor oxide, Ta₂O₅, of 0.15–2.5 mol % at 1300–1600 °C results in the destabilization of tetragonal (t-) phase and the decrease of final density in 3 mol% Y₂O₃-TZP (tetragonal ZrO₂ polycrystals). X-ray diffractometry (XRD) reveals that the Ta₂O₅-added 3 mol% Y₂O₃-ZrO₂ contains monoclinic (m-) ZrO₂ and a second phase of Ta₂Zr₆O₁₇. The decreasing in final density is attributed to the increase of m-ZrO₂ content. Complete destabilization of t-ZrO₂ to m-ZrO₂ in samples added with 2.5 mol% Ta₂O₅ is interpreted by the compensation effect based on donor- and acceptor-codoping defect chemistry.     

Nano-crystallization and surface analysis of electrolytic ZrO2 coatings on Co-Cr alloy

Zirconia coatings were formed on Co-Cr substrates by electrolytic deposition. The microstructure of electrolytic zirconia-coated films on Co-Cr substrates was examined. According to the results of ESCA, the bonding energies of ZrO₂ coating surface layer which changed with the annealing temperature from 400 °C, 500 °C to 600 °C are attributed to amorphous (a), tetragonal (t) and monoclinic (m) structure, respectively. The X-ray diffraction (XRD) of the coatings on the Co-Cr substrates annealed at 400, 500 and 600 °C revealed the major crystallization from m through t and then to m+t. However, TEM observations clearly showed that the interface layer of the coatings were nanosize crystallites, first the formation of tetragonal and monoclinic ZrO₂ structures. These different phase transformations are mainly due to the different surface energy of ZrO₂ coating in air, in bulk or on Co-Cr alloy. © 2001 Kluwer Academic Publishers     

Nanocomposites in mullite-ZrO2 and mullite-TiO2 systems synthesised through alkoxide hydrolysis gel routes: microstructure and fractography

The sol-gel process allows preparation of very homogeneous and reactive monolithic, optically clear gels. Low-temperature thermal treatments (700–1000 °C) lead to amorphous optically clear samples (glass). Amorphous mullite compositions (0.4Al₂O₃-0.6SiO₂ to 0.8Al₂O₃-0.2SiO₂) retain large amounts of Ti and Zr elements. The crystallization has been studied by differential thermal analysis, dilatometry, X-ray and electron diffraction and Raman scattering. The nucleation begins above 1000 °C with the departure of the last protonic species, the amorphous matrix being completely crystallized only above 1400 °C. The addition of Zr and Ti elements leads to a homogeneous nucleation of phases with a composition close to ZrO₂ and Al₂Ti₃O₉ (EDX analysis) above the solubility limit. TEM and SEM analyses show that the precipitate size remains submicrometric over a wide temperature range (1000–1400 °C) and consequently glass-like mechanical properties, as well as toughening effects, caused by the presence of nanoprecipitates, are observed.     

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.     

Sol gel preparation,structure and thermal stability of crystalline zirconium titanate microspheres

Very pure and crystalline ZrTiO₄ microspheres (15–50 m) were prepared by two sol gel methods using a zirconia sol and two types of titania sols and characterized by scanning electron microscopy, X-ray diffraction and simultaneous differential thermal and thermogravimetric analysis. On gelation of the mixed sols, microspheres of an amorphous material with Zr/Ti ratio of 1.0 were obtained by each route. The amorphous materials obtained by the two routes transformed to fully crystalline ZrTiO₄ at 500 and 600 °C, respectively. The high temperature thermal stabilities of these materials were also studied.