Opportunities for TBCs in the ZrO2-YO1.5-TaO2.5 system

An examination of the ZrO₂-YO_1.5-TaO_2.5 system reveals several promising attributes for use in thermal barrier coating applications. The rather unique presence of a stable, non-transformable tetragonal region in this ternary oxide system allows for phase stability to high temperatures (1500 °C). Selected compositions with high levels of yttria and tantala have also shown superior resistance to vanadate corrosion than the commercially utilized 7YSZ. In addition, Y + Ta stabilized zirconia compositions within the non-transformable tetragonal phase field exhibit toughness values comparable or somewhat higher than those of 7YSZ, which bodes well for their durability as TBCs. These promising attributes are discussed in this paper in the context of recent experimental work.     

Thermodynamic study of CVD–ZrO2 phase diagrams

Chemical vapor deposition (CVD) of zirconium oxide (ZrO₂) from zirconium acetylacetonate Zr(acac)₄ has been thermodynamically investigated using the Gibbs’ free energy minimization method and the FACTSAGE program. Thermodynamic data Cp°, ΔH° and S° for Zr(acac)₄ have been estimated using the Meghreblian–Crawford–Parr and Benson methods because they are not available in the literature. The effect of deposition parameters, such as temperature and pressure, on the extension of the region where pure ZrO₂ can be deposited was analyzed. The results are presented as calculated CVD stability diagrams. The phase diagrams showed two zones, one of them corresponds to pure monoclinic phase of ZrO₂ and the other one corresponds to a mix of monoclinic phase of ZrO₂ and graphite carbon.     

On the wide range of mechanical properties of ZTA and ATZ based dental ceramic composites by varying the Al2O3 and ZrO2 content

In this work the influence of pressureless sintering on the Vickers hardness and fracture toughness of ZrO₂ reinforced with Al₂O₃ particles (ATZ) and Al₂O₃ reinforced with ZrO₂ particles (ZTA) has been investigated. The ceramic composites were produced by means of uniaxial compacting at 50 MPa and the green compacts were heated to 1250 °C using a heating rate of 10 °C min⁻¹, then to 1500 °C at 6 °C min⁻¹ and maintained at this temperature during 2 h. After sintering, relative density over 94%, hardness values between 9.5 and 21.9 GPa, and fracture toughness as high as 3.6 MPa m^1/2 were obtained. The presence of TZ-3Y particles on the grain boundaries suggests that they inhibit notably the alumina grain growth. The grain sizes of pure Al₂O₃ and TZ-3Y as well as Al₂O₃ and TZ-3Y in the 20 wt% Al₂O₃+80 wt% TZ-3Y composite were 1.27 ± 0.51 μm, 0.57 ± 0.12 μm, 0.65 ± 0.19 μm and 0.41 ± 0.14 μm, respectively. The 20 wt% Al₂O₃ + 80 wt% ZrO₂ + 3 mol% Y₂O₃ (TZ-3Y) composite showed a hardness of 16.05 GPa and the maximum fracture toughness (7.44 MPa m^1/2) with an average grain size of 0.53 ± 0.17 μm. On the other side, the submicron grain size and residual porosity seem to be responsible for the high hardness and fracture toughness obtained. The reported values were higher than those obtained by other authors and are in concordance with international standards that could be suitable for dental applications.     

Formation of zirconium diboride (ZrB2) by room temperature mechanochemical reaction between ZrO2, B2O3 and Mg

A mixture of magnesium, boric oxide and zirconium dioxide were mechanically milled under argon for up to 15 h in a laboratory scale ball mill. X-ray diffraction showed that there was an increasing conversion of ZrO₂ to ZrB₂ with milling time with >98% reaction after 15 h. Differential thermal analysis revealed there were multiple, overlapping reactions all of which seemed to be formation of ZrB₂. The energy evolved decreased with milling time and the sample after 15 h milling showed no thermal reaction. After milling, separation of the ZrB₂ from the coproduct MgO was easily achieved by a mild acid leaching leaving essentially pure ZrB₂ with a crystallite size of 75 nm.     

Thermal conductivity of nanoporous ZrO2-4 mol% Y2O3 multilayer coatings fabricated by EB-PVD

The effect of multilayer configurations on the thermal conductivity of 4 mol% Y₂O₃⁻ stabilized ZrO₂ coatings fabricated by EB-PVD has been investigated. The deposited coating layers consist of columnar grains containing nano-sized pores. Multilayer specimens are found to contain many pores at the interfaces between layers. The density and thermal conductivity of the multilayer coatings decreases with increasing number of coating layers for one to six layers. The thermal conductivities of coatings deposited onto rotating substrates are lower than those of coatings deposited on stationary substrates. The decreased thermal conductivity of multilayer coatings is ascribed to the increased total porosity resulting from an increase in the number of interface pores concomitant with the formation of non-uniform interfaces between layers, which causes increased phonon scattering.     

Thermal cycle behavior of plasma sprayed La2O3, Y2O3 stabilized ZrO2 coatings

The effects of La₂O₃ addition on thermal conductivity, phase stability and thermal cycle life of Y₂O₃ stabilized ZrO₂ plasma sprayed coatings were investigated. Although low thermal conductivity as well as high resistance to sintering was achieved by La₂O₃ addition, it tended to also result in lower phase stability and thermal cycle life of the coatings. Optimization of the composition and structure of the coatings improved these properties, and the optimized coatings showed prolonged thermal cycle life.     

A new high-pressure polymorph of NiSb2

A new polymorph of NiSb₂ was obtained under high-pressure/temperature condition of 6 GPa and 550–650°C. The crystal structure is orthorhombic with the space group Pbca (No. 61), isostructural with the low-temperature form of NiAs₂ (pararammelsbergite). The crystallographic parameters were refined by the Rietveld analysis of the powder X-ray diffraction data (a=0.62866(2) nm, b=0.63643(2) nm, c=1.23670(3) nm, Z=8). The structure can be regarded as an intermediate structure between the marcasite-type and the pyrite-type. The pararammelsbergite-type NiSb₂ is a high-pressure form of NiSb₂ and the density is slightly higher than that of ambient pressure form with the marcasite-type structure.     

Temporal evolution of the nanostructure of Al(Sc,Zr) alloys: Part II-coarsening of Al3(Sc1−xZrx) precipitates

The coarsening behavior of four Al(Sc,Zr) alloys containing small volume fractions (<0.01) of Al₃(Sc_1−xZr_x) (L1₂) precipitates was investigated employing conventional transmission electron microscopy (CTEM) and high-resolution electron microscopy (HREM). The activation energies for diffusion-limited coarsening were obtained employing the Umantsev–Olson–Kuehmann–Voorhees (UOKV) model for multi-component alloys. The addition of Zr is shown to retard significantly the coarsening rate and stabilize precipitate morphologies. HREM of Al(Sc,Zr) alloys aged at 300 °C reveals Al₃(Sc_1−xZr_x) precipitates with sharp facets parallel to {1 0 0} and {1 1 0} planes. Coarsening of Al-0.07 Sc-0.019 Zr at.%, Al-0.06 Sc-0.005 Zr at.% and Al-0.09 Sc-0.047 Zr at.% alloys is shown to be controlled by volume diffusion of Zr atoms, while coarsening of Al-0.14 Sc-0.012 Zr at.% is controlled by volume diffusion of Sc atoms.     

The temperature-dependent electrical properties of Bi0.5Na0.5TiO3-BaTiO3-Bi0.5K0.5TiO3 near the morphotropic phase boundary

Bi_0.5Na_0.5TiO₃-BaTiO₃-Bi_0.5K_0.5TiO₃ (BNT-BT-BKT) lead-free piezoceramics with compositions near the rhombohedral-tetragonal morphotropic phase boundary (MPB) were prepared and investigated. At room temperature, all ceramics show excellent electrical properties. In this study, the best properties were observed in 0.884BNT-0.036BT-0.08BKT, with the remnant polarization, bipolar total strain, unipolar strain, piezoelectric constant, and planar electromechanical coupling factor being 34.4 μC cm⁻², 0.25%, 0.15%, 122 pC N⁻¹, and 0.30, respectively. Detailed analysis of the temperature dependence of polarization-electric field (P-E) loops and bipolar/unipolar strain-electric field (S-E) curves of this composition revealed a ferroelectric-antiferroelectric phase transition around 100 °C. Around this temperature, there is a significant shape change in both P-E and S-E curves, accompanied by enhanced strain and decreased polarization; the largest recoverable strain reaches 0.42%. These results can be explained by the formation of antiferroelectric order and the contribution of field-induced antiferroelectric-ferroelectric phase transition to piezoelectric response. Our results indicate that BNT-BT-BKT lead-free piezoceramics can have excellent electrical properties in compositions near the MPB and also reveal some insight into the temperature dependence of the electrical performance with the MPB composition.     

Thermal conductivity of EB-PVD ZrO2-4 mol% Y2O3 films using the laser flash method

The variation in thermal conductivity and thermal diffusivity of ZrO₂-4 mol% Y₂O₃ coatings deposited onto Inconel substrates by EB-PVD is examined as a function of coating thickness using the laser flash method. The coatings are found to consist of columnar grains with a feather-like microstructure. The thermal conductivities of the coatings are calculated using two methods: the first involves separating the coating from the substrate and measuring the thermal diffusivity directly; the second uses thermal diffusion results from coatings still attached to the substrate and is based on the response function method. The results of both methods are in excellent agreement, and show that the thermal conductivities of the coatings increase with increasing coating thickness. The results also confirm that the double layer method can be used successfully to calculate the thermal conductivities of thin film coatings.     

Strain effect on phase transitions of BaTiO3 nanowires

The effects of strain on the phase transitions of BaTiO₃ nanowires taking into account three components of polarization are studied by thermodynamic analysis based on the Landau theory. Similar to the strain effect on phase transitions in thin films, the mismatch strain between the nanowire and substrate governs the Curie temperature. The complete misfit strain–temperature phase diagram shows six stable ferroelectric phases for BaTiO₃ nanowires under different strain and temperature conditions.     

Correlation between the surface state and optical properties of S6 site and C2 site in nanocrystalline Eu:Y2O3

Eu³⁺ doped Y₂O₃ nanocrystals are synthesized via precipitation and hydrothermal methods. With the increase of hydrothermal temperature, the number of surface states decreases when nanorods are formed. The decrease of surface states induces the increase in the ratio of S₆ site to C₂ site, and meanwhile results in the spectral red-shift of charge transfer band as well as the enhancement of red emission. The results indicate that the surface states and optical properties have close correlations.     

Investigation of changes in band gap and density of localized states on phase transition for Ge2Sb2Te5 and Si3.5Sb2Te3 materials

Upon phase transition, the resistivity changes of Ge₂Sb₂Te₅ (GST) and Si_3.5Sb₂Te₃ (SST) are proved to be closely related to the variations of band gap and density of localized states. Amorphous SST has a slightly more localized state than amorphous GST; however, the larger band gap of SST material causes relatively difficult phase transition processes. Therefore, the phase change memory (PCM) cell based on the SST film shows larger threshold voltages for both set and reset operations than that of the GST-based PCM cell. The formation of amorphous Si-rich segregated areas in the SST film during phase transitions increases the randomness of the whole film microstructure, which leads to a different Urbach tail absorption result to that of the GST film.     

Thermodynamic properties and phase diagrams of the binary systems B2O3–Ga2O3, B2O3–Al2O3 and B2O3–In2O3

We calculated the binary phase diagrams B₂O₃–Ga₂O₃, B₂O₃–In₂O₃ and B₂O₃–Al₂O₃, and the Gibbs energy of formation of the binary compounds, using experimental liquidus data. The B₂O₃–Ga₂O₃ system is of industrial importance, because liquid B₂O₃, in which Ga₂O₃ is not very soluble, is used to protect GaAs during growth of single crystals of GaAs. During recovery of noble metals B₂O₃ is added to slags containing Al₂O₃ to lower the melting point and the viscosity. The B₂O₃–In₂O₃ system is of much less importance to industry. In all three systems we have a liquid miscibility gap, and also solid binary compounds, none of which melt congruently. The miscibility gaps are not surprising, because even in the B₂O₃–Bi₂O₃ system where four congruently melting compounds are present, a liquid miscibility gap exists close to B₂O₃.     

Polymorphism of PrIr2Si2 – In situ XRPD experiments and theoretical calculations

We have confirmed polymorphism of PrIr₂Si₂ and performed the in situ high-temperature X-ray powder diffraction (XRPD) experiments focused on the dynamics of the crystallographic phase transition from the high-temperature CaBe₂Ge₂-type phase to the low-temperature ThCr₂Si₂ phase above 250 °C. A double-exponential time evolution of this phase transformation has been observed at 325 °C. We have also performed density functional calculations to analyze why the low-temperature crystallographic modification becomes the ground state crystal structure. The important role of the c/a ratio in this process can be argued from results of calculations.     

Effects of particle size of 8 mol% Y2O3 stabilized ZrO2 (YSZ) and additive Ta2O5 on the phase composition and the microstructure of sintered YSZ electrolyte

The chemical stability and sinterability of nano- and micro-sized yttria stabilized zirconia (YSZ) powders were investigated, and the effect of Ta₂O₅ additive on the sinterability of YSZ electrolyte was also studied. Addition of Ta₂O₅ easily causes phase transformation of YSZ from cubic to monoclinic, and thus unfavorable for the improvement of ionic conductivity of YSZ electrolyte. Nano-sized YSZ easily causes abnormal grain growth and hence readily results in inhomogeneous microstructure of YSZ matrix, while micro-sized YSZ displays relatively low sinterability. Comparatively, mixture with 50 wt.% nano-sized and 50 wt.% micro-sized YSZ powders exhibits high sinterability and could be sintered to homogeneous microstructure, which can be used as starting materials to prepare dense YSZ electrolyte at low temperatures.     

载体中ZrO2/Al2O3比对Pt/ZrO2-Al2O3催化剂性能的影响

相比汽油车而言,柴油车具有高效、低油耗的优势已得到广泛应用。本实验以ZrO₂作为改性剂,探究了ZrO₂与Al₂O₃的质量比对催化剂的影响。研究结果表明：随着ZrO₂的加入,Pt粒子先减小后增大;Pt粒子与载体的交互作用先增大后减小。活性实验数据分析表明,ZrO₂的最佳添加量为40 wt%,CO和C₃H₆完全氧化温度分别降低20 _oC 、25 _oC。贵金属在催化剂的分散度以及贵金属与载体的相互作用随着ZrO₂与Al₂O₃质量比的变化而变化。Pt粒子越小,其与载体的交互作用越强,这表明催化剂性能越强。     

Self-organized porous TiO2 and ZrO2 produced by anodization

The present work investigates the electrochemical formation of self-organized high aspect ratio TiO₂ and ZrO₂ nanotube layers. The formation and growth of a self-organized porous layer can be achieved directly by anodization without any templates in fluoride containing electrolytes. The morphology of the porous layers is affected by the electrochemical conditions such as the electrolyte composition, the pH and the exact polarization treatment (such as the potential sweep rate from the open-circuit potential to the anodizing potential). For Ti, nanotube layers are formed with diameters varying from approx. 20 nm to 100 nm and lengths from approx. 0.25 μm to 2.5 μm depending on the electrolytes and pH. On the other hand, for Zr, tubes of 50 nm in diameter and up to approx. 17 μm in length can be grown—a key parameter in this case is the potential sweep rate. The large difference between Ti and Zr in the achievable thickness of nanotube layers indicates a difference in the growth mechanism which may be based on the different chemical dissolution rates of electrochemically formed oxides.     

Modelling and analysis of pulsed Nd:YAG laser machining characteristics during micro-drilling of zirconia (ZrO2)

Pulsed Nd: YAG laser beam has great ability for micro-machining of ceramic materials because of high laser beam intensity at low mean beam power, good focusing characteristics due to very small pulse duration, small kerf widths and narrow heat effected zones. In the paper, experimental investigations into CNC pulsed Nd:YAG laser micro-drilling of zirconium oxide (ZrO₂) have been carried out. Influence of laser machining parameters on the HAZ thickness and phenomena of tapering of the machined micro-holes has been experimentally investigated. Response Surface Methodology-based optimal parametric analysis has been performed to determine the optimal setting of process parameters such as pulse frequency and pulse width, lamp current, assist air pressure for achieving minimum HAZ thickness and taper of the micro-hole machined by pulsed Nd:YAG laser. Minimum HAZ thickness has been obtained as 0.0675 mm when the lamp current, pulse frequency, assisted air pressure and pulse width are set at optimal parametric setting i.e. 17 amp, 2.0 kHz, 2.0 kg/cm² and 2% of the duty cycle, respectively. Minimum taper has been achieved as 0.0319 at optimal parametric setting i.e. the lamp current of 17 amp, pulse frequency of 2.0 kHz, assisted air pressure of 0.6 kg/cm² and pulse width of 2% of the duty cycle. Analysis has also been carried out for multi-optimisation of both the responses i.e. HAZ thickness and taper during pulsed Nd:YAG laser micro-drilling on ZrO₂.