Preparation of YSZ/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite coatings via electrophoretic deposition of nanopowders

Using electrophoretic deposition (EPD), we have produced YSZ individual ceramic coatings and YSZ/Al₂O₃ composite coatings for a wide range of applications in modern materials research. YSZ and Al₂O₃ nanopowders were prepared by high-energy physical dispersion techniques, namely, by a laser evaporation–condensation process and electroexplosion of wire, respectively. Stable nonaqueous suspensions for the EPD process have been prepared using YSZ and Al₂O₃ nanopowders with an average particle size of 11 and 22 nm, respectively. The YSZ/Al₂O₃ composite coating produced by sintering at 1200°C has been shown to have higher density in comparison with the YSZ individual coating produced at the same temperature. X-ray diffraction characterization showed that the YSZ/Al₂O₃ composite coating consisted of two crystalline phases: α-Al₂O₃ (corundum) (42 wt %) and cubic ZrO₂〈Y₂O₃〉 (58 wt %). Quantitative analysis of electron micrographs of the surface of the films showed that the YSZ individual coating produced by sintering at 1200°C had a loose structure and contained pores (9%), as distinct from the composite coating, which had a dense, porefree grain structure.     

Properties of nanocrystalline ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>-CoO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders

We have studied the properties of nanocrystalline ZrO₂-Y₂O₃-CeO₂-CoO-Al₂O₃ powders prepared via hydrothermal treatment of a mixture of coprecipitated hydroxides at 210°C. A number of general trends are identified in the variation of the properties of the synthesized powders during heat treatment at temperatures from 500 to 1200°C. Our results demonstrate that the addition of 0.3 mol % CoO to nanocrystalline ZrO₂-based powders containing 1 to 5 mol % Al₂O₃ allows one to obtain composites with good sinterability at a reduced temperature (1200°C).     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> on the properties of nanocrystalline ZrO<Subscript>2</Subscript> + 3 mol % Y<Subscript>2</Subscript>O<Subscript>3</Subscript> powder

We have studied the properties of nanocrystalline ZrO₂〈3 mol % Y₂O₃〉 and 90 wt % ZrO₂〈3 mol % Y₂O₃〉-10 wt % Al₂O₃ powders prepared via hydrothermal treatment of coprecipitated hydroxides at 210°C. The results demonstrate that Al₂O₃ doping raises the phase transition temperatures of the metastable low-temperature ZrO₂ polymorphs and that the structural transformations of the ZrO₂ and Al₂O₃ in the doped material inhibit each other.     

A novel method for producing open-cell Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> ceramic foams with controlled cell structure

A novel method was introduced to prepare open-cell Al₂O₃–ZrO₂ ceramic foams with controlled cell structure. This method used epispastic polystyrene (EPS) spheres to array ordered templates and centrifugal slip casting in the interstitial spaces of the EPS template to obtain cell struts with high packing density. Aqueous Al₂O₃–ZrO₂ slurries with up to 50 vol.% solid contents were prepared and centrifuged at acceleration of 2,860g. The effect of the solid contents of slurries on segregation phenomena of different particles and green compact uniformity were investigated. In multiphase system, the settling velocities of Al₂O₃ and ZrO₂ particles were calculated. Theory analysis and calculated results both indicated segregation phenomenon was hindered for slurries with 50 vol.% solid content. The cell struts of sintered products had high green density (61.5%TD), sintered density (99.1%TD) and homogeneous microstructures after sintered at 1,550 °C for 2 h. The cell size and porosity of Al₂O₃–ZrO₂ ceramic foams can be adjusted by changing the size of EPS spheres and the load applied on them during packing, respectively. When the porosity increased from 75.3% to 83.1%, the compressive strength decreases from 3.82 to 2.07 MPa.     

Preparation of porous ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> macrobeads from ion-exchange resin templates

In this work, we will report a method to prepare porous ZrO₂ and ZrO₂/Al₂O₃ macrobeads using cation-exchange resins with sulfonate groups as templates. The preparation process involves metal ion-loading, ammonia-precipitation, and calcination at an appropriate temperature. Several characterization methods, such as TGA, XRD, SEM with EDX, TEM and N₂ adsorption and desorption, were used to characterize the ZrO₂ and ZrO₂/Al₂O₃ macrobeads. The results showed that the porous structures of the resin templates were negatively duplicated in the two kinds of macrobeads. We found the following interesting results: (1) The ZrO₂/Al₂O₃ macrobeads are composed of tetragonal zirconia nanocrystals that are more technologically important, while the pure ZrO₂ macrobeads consist of a mixture of tetragonal and monoclinic zirconia. (2) In the ZrO₂/Al₂O₃ macrobeads, the size of ZrO₂ nanocrystals is about 5 nm smaller than that (about 19 nm) found in the pure ZrO₂ macrobeads. (3) The ZrO₂/Al₂O₃ macrobeads have more mesopores and, therefore, have a larger surface area than the pure ZrO₂ macrobeads. These oxide macrobeads will have potential applications in catalysis by taking advantage of their macrobeads shape and pores structure.     

Mechanical properties of bovine hydroxyapatite (BHA) composites doped with SiO<Subscript>2</Subscript>, MgO,Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and ZrO<Subscript>2</Subscript>

Biologically derived hydroxyapatite from calcinated (at 850 °C) bovine bones (BHA) was doped with 5 wt% and 10 wt% of SiO₂, MgO, Al₂O₃ and ZrO₂ (stabilized with 8% Y₂O₃). The aim was to improve the sintering ability and the mechanical properties (compression strength and hardness) of the resultant BHA-composites. Cylindrical samples were sintered at several temperatures between 1,000 and 1,300 °C for 4 h in air. The experimental results showed that sintering generally occurs at 1,200 °C. The BHA–MgO composites showed the best sintering performance. In the BHA–SiO₂ composites, extended formation of glassy phase occurred at 1,300 °C, resulting in structural degradation of the resultant samples. No sound reinforcement was achieved in the case of doping with Al₂O₃ and zirconia probably due to the big gap between the optimum sintering temperatures of BHA and these two oxides.     

The ZrO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> phase diagram

The ZrO₂-TiO₂ phase diagram was determined experimentally between 800 and 1200°C, 1 atm, extending our knowledge of this system to temperatures previously inaccessible for equilibrium experiments due to sluggish kinetics. The crystallization of the ordered (Zr,Ti)₂O₄ phase from the oxides was facilitated by the addition of flux (CuO or Li₂MoO₄/MoO₃), and seeds. Two ordered (Zr,Ti)₂O₄ phases with different compositions were identified, and their phase relationships with TiO₂ and ZrO₂ solid solutions investigated. Structure data, superstructure reflections and composition were used to locate the ordering phase transition of (Zr,Ti)₂O₄ in equilibrium with ZrO₂ and TiO₂. At the onset of ordering between 1130 and 1080°C, (Zr,Ti)₂O₄ is of composition X_Ti = 0.495 ± 0.02, and displays a dramatic change in b-dimension. At 1060°C and below, the composition of (Zr,Ti)₂O₄ is significantly more Ti-rich and dependent on temperature, ranging from X_Ti = 0.576 at 1060°C to 0.658 at 800°C. This variability in composition of the ordered phase contrasts with previous studies that suggested the composition to be constant at either X_Ti = 0.667 [ZrTi₂O₆] or 0.583 [Zr₅Ti₇O₂₄]. When grown at low temperatures and with lithium molybdate, the crystals of ordered (Zr,Ti)₂O₄ are acicular to needle shape, and develop distinct square cross-sections and end facets.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript> and Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> co-stabilized ZrO<Subscript>2</Subscript>-WC composites

Y₂O₃ + Nd₂O₃ co-stabilized ZrO₂-based composites with 40 vol% WC were fully densified by pulsed electric current sintering (PECS) at 1350 °C and 1450 °C. The influence of the PECS temperature and Nd₂O₃ co-stabilizer content on the densification, hardness, fracture toughness and bending strength of the composites was investigated. The best combination of properties was obtained for a 1 mol% Y₂O₃ and 0.75 mol% Nd₂O₃ co-stabilized composite densified for 2 min at 1450 °C under a pressure of 62 MPa, resulting in a hardness of 15.5 ± 0.2 GPa, an excellent toughness of 9.6 ± 0.4 MPa.m^0.5 and an impressive 3-point bending strength of 2.04 ± 0.08 GPa. The hydrothermal stability of the 1 mol% Y₂O₃ + 1 mol% Nd₂O₃ co-stabilized ZrO₂-WC (60/40) composites was compared with that of the equivalent 2 mol% Y₂O₃ stabilized ceramic. The double stabilized composite did not degrade in 1.5 MPa steam at 200 °C after 4000 min, whereas the yttria stabilized composite degraded after less than 2000 min. Moreover, the (1Y,1Nd) ZrO₂-WC composites have a substantially higher toughness (~9 MPa.m^0.5) than their 2Y stabilized equivalents (~7 MPa.m^0.5).     

Phase stability,microstructure and high-temperature properties of NbSi<Subscript>2</Subscript>- and TaSi<Subscript>2</Subscript>-oxide conducting ceramic composites

NbSi₂- and TaSi₂-based electroconductive ceramic composites with the addition of 40–70 vol% Al₂O₃ and ZrO₂ particles were fabricated by high-temperature sintering (1400–1600 °C) under argon. Their phase stability, microstructural evolution, oxidation kinetics and electrical properties were studied at high temperatures. The densification of the composites was improved by increasing the oxide phase content and sintering temperature. The interaction of the starting metal disilicides with residual oxygen sources resulted in the formation of the hexagonal-structured 5–3 metal silicide (Nb₅Si₃ and Ta₅Si₃) phases. The increasing sintering temperature and volume percentage of the oxide phase reduced the pest oxidation, particularly for the silicide–alumina composites, which exhibited lower oxidation-induced mass changes than their dense monolithic metal silicides. Depending on the silicide–oxide volume percentage, their electrical conductivities ranged from 5.3 to 111.3 S/cm at 900 °C. Their phase stability, reduced oxidation rates and high electrical conductivities at high temperatures show promise for future high-temperature applications in advanced sensing.     

Directional solidification and growth characteristics of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Er<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>/ZrO<Subscript>2</Subscript> ternary eutectic ceramic by laser floating zone melting

Directionally solidified Al₂O₃/Er₃Al₅O₁₂/ZrO₂ ternary eutectic ceramic in situ composite rods with length of 110 mm have been fabricated by laser floating zone melting. The microstructural characteristics of steady growth zone, initial growth zone and solid/liquid interface are investigated under high temperature gradient. In the steady growth zone, the eutectic spacing (λ) is rapidly decreased as increasing the growth rate (V), and the corresponding relationship between growth rate and eutectic spacing is determined to be λ = 11.14 × V ^?1/2. The temperature gradient has been measured to be about 5.3 × 10³ K/cm. In the initial growth zone, the melting process and temperature distribution are recorded by infrared thermal imager, and several unstable complex microstructures are observed. In the quenched zone, the regular eutectics with minimum eutectic spacing of 200 nm are obtained. Moreover, the solid/liquid interface during solidification shows convex interface morphology and the interface height is gradually decreased as increasing the growth rate. The eutectic growth behaviors at the center and edge of the as-grown rod are compared and discussed.     

Effect of the precipitation sequence on phase formation in the ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied phase formation processes during heat treatment of precipitates in the ZrO₂-Al₂O₃ and ZrO₂-CeO₂-Al₂O₃ systems. During heat treatment of powders prepared by coprecipitation of precursors to ZrO₂, CeO₂, and Al₂O₃, α-Al₂O₃ is formed at higher temperatures, which is due to the formation and decomposition of T-ZrO₂ and metastable Al₂O₃ phases. The precipitation sequence in the ZrO₂-CeO₂-Al₂O₃ system influences the lattice parameters of the forming T-ZrO₂-based solid solutions because of the different degrees of Ce⁴⁺ and Al³⁺ substitutions for Zr⁴⁺.     

Ultrasound velocity and absorption in BeO,Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, ZrO<Subscript>2</Subscript>, and SiO<Subscript>2</Subscript> ceramics

We have measured the ultrasound velocity and absorption in BeO, Al₂O₃, ZrO₂, and SiO₂ ceramics. The results indicate that the ultrasound velocity in oxide ceramics depends on the nature of the basic oxide component, the density of the material, and the preferential alignment of the grains. The ultrasound velocity in ceramics is shown to correlate with their thermal conductivity: with increasing thermal conductivity, the ultrasound velocity increases. The ultrasound absorption in oxide ceramics decreases with decreasing temperature, and vice versa, with increasing temperature, the ultrasound attenuation coefficient increases.     

Surface reactivity and electrophoretic deposition of ZrO<Subscript>2</Subscript>–MgO mechanical mixture

Electrophoretic deposition (EPD) is a precision technique useful for obtaining high quality ceramic bodies with controlled dimensions and smooth coatings. The electrophoretic deposition rate is highly dependent on the surface chemistry of the powders, especially when dealing with multi-component systems. The objective of this work is to study the surface reactivity of both ZrO₂ and MgO in ethanol suspension to provide experimental benchmarks to control EPD of a ZrO₂–3 wt% MgO mechanical mixture (Z3M) in ethanol. Infrared spectroscopy (FTIR) showed that ZrO₂ surface spontaneously reacts with ethanol, generating negative electrophoretic mobility of the particles (−0.07 × 10⁻⁸ V⁻¹ s⁻¹) measured by Electroacoustic Sonic Amplitude (ESA). MgO surface also spontaneously reacted with ethanol, but a positive electrophoretic mobility was observed in this case (0.26 × 10⁻⁸ V⁻¹ s⁻¹). Scanning Electron Microscopy of Z3M dried from ethanol suspension showed that MgO particles were located around the ZrO₂ particles, forming composite agglomerates, probably due to the electrostatic attraction between MgO and ZrO₂ particles. Homogeneous deposits could be obtained from EPD of Z3M ethanol suspensions. Mercury intrusion porosimetry showed that the ZrO₂–MgO green deposited bodies using different voltages had similar pores diameters distributions, indicating that the ZrO₂–MgO agglomerates are not affected by the increasing deposition rates.     

Microstructure and high-temperature strength of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Er<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>/ZrO<Subscript>2</Subscript> ternary melt growth composite

A new Al₂O₃/Er₃Al₅O₁₂(EAG)/ZrO₂ ternary MGC (Melt Growth Composite) with a novel microstructure has been fabricated by unidirectional solidification. This ternary MGC has a microstructure consisting of continuous networks of single-crystal Al₂O₃, single-crystal EAG and fine cubic-ZrO₂ phases without grain boundaries. The ternary MGC has also characteristic dimensions of the microstructure of around 2–4 m for EAG phases, around 2–4 m for Al₂O₃ phases reinforced with around 0.4–0.8 m cubic-ZrO₂ phases. No amorphous phases are formed at interfaces between phases in the ternary MGC. The ternary MGCs flexural strength at 1873 K is approximately 700 MPa, more than twice the 330 MPa of the Al₂O₃/EAG binary MGC. The fracture manner of the Al₂O₃/EAG/ZrO₂ ternary MGC at 1873 K shows the same intergranular fracture as the Al₂O₃/EAG binary MGC, but is significantly different from the transgranular fracture of the sintered ceramic.     

Preparation of magnetic composites through SrO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass crystallization

Glasses with nominal compositions 11SrO · 5.5Fe₂O₃ · 4.5Al₂O₃ · 4B₂O₃ (1) and 15SrO · 5.5Fe₂O₃ · 4.5Al₂O₃ · 4B₂O₃ (2) were prepared by rapidly quenching oxide melts between counterrotating steel rollers. The glasses were then heat-treated in the range 650–950°C to produce glass-ceramic samples. The samples were characterized by X-ray diffraction, electron microscopy, and magnetic measurements. The phase composition of the glass-ceramics was determined, and their microstructure and magnetic properties were studied. The annealing temperature was shown to have a strong effect on the coercivity of the materials, which reaches 650 and 570 kA/m for compositions 1 and 2, respectively.     

ZrO<Subscript>2</Subscript> foams for porous radiant burners

In this work, Y₂O₃-stabilized ZrO₂ (YSZ) foams with low relative density were developed through the replication method, for application as porous radiant burners. The ceramic foams were produced by impregnation of open-cell polyurethane foams with aqueous suspensions and different fractions of raw materials: ZrO₂–8% Y₂O₃ (8YSZ) powder, and additives. The materials were milled for 10–40 min. The impregnated foams were dried and submitted to a heat treatment for polyurethane elimination at 1000 °C for 1 h, with subsequent sintering of the remaining ceramic structure at 1600 °C for 2 h, which resulted in YSZ foams with low relative density (0.07). The structural analysis revealed a cellular structure with an average mechanical strength of 95.6 kPa. The radiation efficiency (>19%) was obtained by tests with different air/fuel ratio. The ceramic matrixes exhibited high performance and structural integrity at high operation temperatures (1400 °C).     

Effects of TiO<Subscript>2</Subscript>, ZrO<Subscript>2</Subscript> and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> dopants on the compressive strength of tricalcium phosphate

Tricalcium phosphate (TCP) powders synthesised using the Ca(NO₃)₂ and Ca(OH)₂ routes were doped with TiO₂, ZrO₂ and Al₂O₃ in order to increase their compressive strength. An ultimate compressive strength (UCS) of 255 ± 6 MPa was achieved for approximately 10 vol% TiO₂ doping compared to 30 ± 3 MPa for an un-doped control processed and tested in the same manner. Higher levels of TiO₂ doping resulted in smaller increases in UCS with 30 and 50 vol% achieving 213 ± 9 and 178 ± 15 MPa, respectively. Very small amounts of Al₂O₃ doping (< 0.5 vol%) also resulted in a stronger materials. However, under the processing conditions employed, higher levels of Al₂O₃ and ZrO₂ doping resulted in no beneficial effect on the UCS. Polyvinyl alcohol (PVA) was used as binding agent to facilitate processing. As expected, higher levels of PVA were associated with smaller increases in UCS. Powders synthesised using the Ca(OH)₂ route had smaller particle size and resulted in larger increases in UCS compared to the Ca(NO₃)₂-synthesised powders. Although some powders contained α and β-TCP phases, no other calcium phosphate, CaO, CaTiO₃ or CaZrO₃ phases were detected. In conclusion, a significant increase in the UCS of TCP was achieved by doping with approximately 10 vol% TiO₂ which is expected to have little or no effect on the bioactivity or bioresorbability of the material.     

Hollow biomorphic Al<Subscript>2</Subscript>O<Subscript>3</Subscript> fibers produced from sisal

Al₂O₃ fibers with a hollow morphology were produced by Al-vapor infiltration-reaction and subsequent oxidation from pyrolysed fibers of natural sisal. Following pyrolysis, the bio-fiber template was reacted with gaseous Al at 1,400 °C–1,600 °C in vacuum to form Al₄C₃. After an oxidation/sintering process at 1,550 °C, the biomorphic Al₄C₃ fibers were fully converted into Al₂O₃, maintaining the microstructural features of the native sisal. Phase and microstructural characterization during processing were evaluated by high temperature X-ray diffractometry and scanning electron microscopy, respectively. Thermo-analyses were performed in the Al₄C₃ samples in order to estimate the reactions and the weight change during the oxidation step.     

Structure of multilayer ZrO<Subscript>2</Subscript>/SrTiO<Subscript>3</Subscript>

Multilayered oxide heteroepitaxial systems, including that of a 1-nm-thick Y₂O₃-stabilised ZrO₂ (YSZ) sandwiched between layers of SrTiO₃ (STO) [1], have been a subject of much interest lately due to their significantly enhanced ionic conductivities as compared to the bulk materials. We aim to provide the foundation for understanding this increase in conductivity by considering the atomic configurations at the interfaces of such systems, specifically a ZrO₂/STO multilayer system. Possible stable lattice structures of pure ZrO₂ in the system are explored using a genetic algorithm in which the interatomic interactions are modelled by simple pair potentials. The energies of several of the more stable of these structures are then evaluated more accurately within density functional theory (DFT). We find that the fluorite ZrO₂ phase is unstable as a coherently strained epitaxial layer in the multilayer system. Instead, anatase-, columbite-, rutile-, and pyrite-like ZrO₂ epitaxies are found to be more stable, with the anatase-like epitaxy being the most stable structure over a wide range of chemical potential of the components. We also find a high energy metastable structure resembling the tetragonal fluorite structure which is predicted by DFT to be stabilised by SrO-terminated STO but not by TiO₂-terminated STO.     

Influences of ZrO<Subscript>2</Subscript> nanoparticles on the microstructure and mechanical behavior of Ce-TZP/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites

Influences of ZrO₂ nanoparticles on the mechanical properties and microstructure of hot-pressing Ce-TZP/Al₂O₃ ceramics were investigated. Meanwhile, t-ZrO₂ to m-ZrO₂ transformation toughening mechanism was investigated by X-ray diffractometry (XRD) method, and deflection of samples under applied stress were recorded too. The results show that when the percentage of ZrO₂ was 20%, the mechanical properties and microstructures of materials are optimum. Moreover, TEM observation show dislocation structures formation both in the Al₂O₃ and on the grain boundary. Because the dislocation agglomeration and fixation by ZrO₂ nanoparticles could deflect cracking or stop cracking development, a strengthening and toughening effect could be achieved.