Adhesive strength of new thermal barrier coatings of rare earth zirconates

La₂Zr₂O₇ (LZ) and La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) as novel candidate materials for thermal barrier coatings (TBCs) were prepared by electron beam-physical vapor deposition (EB-PVD). The adhesive strength of the as-deposited LZ and LZ7C3 coatings were evaluated by transverse scratch test. Meanwhile, the factors affecting the critical load value were also investigated. The critical load value of LZ7C3 coating is larger than that of LZ coating, whereas both values of these two coatings are lower than that of the traditional coating material, i.e. 8 wt% yttria stabilized zirconia (8YSZ). The micro-cracks formed in the scratch channel can partially release the stress in the coating and then enhance the adhesive strength of the coating. The width of the scratch channel and the surface spallation after transverse scratch test are effective factors to evaluate the adhesive strength of LZ and LZ7C3 coatings.     

Electrical conductivity of 5 mol.% Yb2O3 and 5 mol.% Gd2O3 co-doped Sm2Zr2O7

Sm₂Zr₂O₇ co-doped with and without 5 mol.% Yb₂O₃ and 5 mol.% Gd₂O₃ were prepared by a pressureless-sintering method at 1973 K for 10 h in air. The relative density, structure and electrical conductivity were investigated by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance spectra measurements. Both Sm₂Zr₂O₇ and (Sm_0.9Gd_0.05Yb_0.05)₂Zr₂O₇ ceramics exhibit a single phase of pyrochlore-type structure. The grain conductivity, grain-boundary conductivity and total conductivity obey the Arrhenius relation, respectively, and gradually increase with increasing temperature from 723 to 1173 K. (Sm_0.9Gd_0.05Yb_0.05)₂Zr₂O₇ ceramic is the oxide-ion conductor in an oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The grain conductivity, grain-boundary conductivity and total conductivity of (Sm_0.9Gd_0.05Yb_0.05)₂Zr₂O₇ with dual Yb³⁺ + Gd³⁺ doping are higher than those of undoped Sm₂Zr₂O₇ at identical temperature levels.     

Electrical properties of Pb0.97La0.02(Zr0.95Ti0.05)O3 antiferroelectric thin films on TiO2 buffer layer

Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ antiferroelectric thin films with thickness of 500 nm were successfully deposited on TiO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates via sol-gel process. Microstructure of Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was studied by X-ray diffraction analyses. The antiferroelectric nature of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was confirmed by the double hysteresis behaviors of polarization and double buffer fly response of dielectric constant versus applied voltage at room temperature. The capacitance-voltage behaviors of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films with and without TiO₂ buffer layer were studied, as a function of temperature. The temperature dependence of dielectric constant displayed a similar behavior and the Curie temperature (T_c) was 193 °C for films on both substrates. The current caused by the polarization and depolarization of polar in the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films was detected by current density-electric field measurement.     

Pressureless sintering of negative thermal expansion ZrW2O8/Zr2WP2O12 composites

Negative thermal expansion material ZrW₂O₈/Zr₂WP₂O₁₂ composite was prepared by liquid phase sintering. The apparent density of ZrW₂O₈ without any sintering additive was about 3.7 g/cm³, corresponding to about 73% of its theoretical density. However, the relative density of the samples, sintered with more than 5 mol% P₂O₅ was about 90%. The identified phases were mainly ZrW₂O₈ with small amounts of WO₃, ZrO₂ and Zr₂WP₂O₁₂ by XRD. The intensity of Zr₂WP₂O₁₂ peaks increased with increasing P₂O₅ content. It was surmised that the melting of ZrO₂-P₂O₅ resulted in liquid phase formation, which is then converted to Zr₂WP₂O₁₂ on the final stage of sintering. Therefore, Zr₂WP₂O₁₂ phase was observed at the gap between the ZrW₂O₈ grains and at the triple junctions. The ceramics sintered with 20 mol% P₂O₅ showed a negative thermal expansion coefficient of − 4.0 × 10^− 6 °C^− 1.     

High temperature phase relation in the system La2O3WO3

The system La₂O₃WO₃, especially the La₂O₃-rich portion was studied by a thermal analysis, high temperature X-ray diffraction, annealing of fused samples, solid state reaction and DTA methods up to the liquidus. Eight intermediate phases, La₂O₃:WO₃ = 3:1, 5:2, 3:2, 1:1, 7:8, 1:2, 1:3 and 2:9, were found and characterized. In addition, two unquenchable solid solution phases based upon La₂O₃X and H, have been found. A phase diagram is presented.     

Preparation and properties of some phases in the system Nd2O3−CeO2−ZrO2−RuO2

Compound formation relevant to the calcination of radiocative waste was studied by heating Nd₂Ce₂O₇?Nd₂Zr₂O₇?Nd₂Ru₂O₇ compositions in air at 1200 – 1400°C and determining the phase distributions by X-ray diffraction and the phase compositions by analytical electron microscopy. Nd₂Zr₂O₇ and Nd₂Ru₂O₇ both have the pyrochlore structure, but do not form complete solid solutions. The equilibria between Ce-rich fluorite and the pyrochlore phase(s) are complicated by the appearance of a new phase shown to be (Nd,Ce)₂(Ru,Ce)O₅. Indexed powder data (59 reflections) are given for the Ce-free composition, Nd₂RuO₅.     

Rapid preparation and characterization of Dy2Zr2O7 nanocrystals

Ultrafine fluorite type Dy₂Zr₂O₇ nanocrystals with cubic structure were fabricated at relatively low temperature by stearic acid method (SAM) using zirconium(IV) butoxide and dysprosium nitrate as raw materials, stearic acid as solvent and dispersant. The fabrication process was monitored by thermogravimetric analysis and differential thermal analysis (TG-DTA) and Fourier transform infrared spectroscopy (FT-IR). The obtained products were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectrometer (EDS) and UV-vis absorption spectroscopy. A single phase of Dy₂Zr₂O₇ with high crystallinity was formed at 800 °C. The interplanar distances measured from the HRTEM image were 0.284 and 0.256 nm, respectively, coinciding with the theoretical values.     

Formation and thermal properties of fluorite-pyrochlore composite structure in La2(ZrxCe1 − x)2O7 oxide system

Rare-earth oxides of La₂(Zr_xCe_1 ? x)₂O₇ for thermal barrier coatings (TBCs) are fabricated via a solid-state reaction at 1600 °C. As the phase formation, microstructure, and thermal properties of these oxides are examined, a fluorite–pyrochlore composite structure is found in the La₂(Zr_xCe_1 ? x)₂O₇ system. This composite structure is composed of coarse Ce-rich fluorite and fine Zr-rich pyrochlore grains. From XRD and microstructural analysis, the lattice parameter and volume fraction of each phase are evaluated in order to obtain the intrinsic thermal conductivity value of composite-structured oxide with porosity calibration. The thermal conductivity of the composite structure is similar to that of pyrochlore La₂Zr₂O₇, which is attributed to phonon scattering by phase boundaries.     

无机固体电解质Li7La3Zr2O12的制备及掺杂改性研究进展

无机固体电解质由于其安全性能高、能量密度大等特点备受研究者的青睐。其中Garnet型锂离子无机固体电解质Li_7La_3Zr_2O_(12)具有较高的离子导电率,较低的界面电阻,优良的稳定性能和电化学性能,在未来的全固态锂离子电池、锂空气电池等领域有着广阔的应用前景。主要从Li_7La_3Zr_2O_(12)的晶体结构、制备工艺和掺杂改性等方面详细阐述无机固态电解质Li_7La_3Zr_2O_(12)的研究进展。     

(La_(0.2)Ce_(0.2)Nd_(0.2)Sm_(0.2)Eu_(0.2))_2Zr_2O_7:A novel high-entropy ceramic with low thermal conductivity and sluggish grain growth rate

Fine grains and slow grain growth rate are beneficial to preventing the thermal stress-induced cracking and thermal conductivity increase of thermal barrier coatings.Inspired by the sluggish diffusion effect of high-entropy materials,a novel high-entropy(HE) rare-earth zirconate solid solution(La_(0.2)Ce_(0.2)Nd_(0.2)Sm_(0.2)Eu_(0.2))2 Zr_2 O_7 was designed and successfully synthesized in this work.The as-synthesized(La_(0.2)Ce_(0.2)Nd_(0.2)Sm_(0.2)Eu_(0.2))_2 Zr_2 O_7 is phase-pure with homogeneous rare-earth element distribution.The thermal conductivity of as-synthesized(La_(0.2)Ce_(0.2)Nd_(0.2)Sm_(0.2)Eu_(0.2))_2 Zr_2 O_7 at room temperature is as low as 0.76 W m-1 K-1.Moreover,after being heated at 1500 ℃ for 1-18 h,the average grain size of(La_(0.2)Ce_(0.2)Nd_(0.2)Sm_(0.2)Eu_(0.2))_2 Zr_2 O_7 only increases from 1.69 μm to 3.92 μm,while the average grain size of La_2Zr_2O_7 increases from 1.96 μm to 8.89 μm.Low thermal conductivity and sluggish grain growth rate indicate that high-entropy(La_(0.2)Ce_(0.2)Nd_(0.2)Sm_(0.2)Eu_(0.2))_2Zr_2O_7 is suitable for application as a thermal barrier coating material and it may possess good thermal stress-induced cracking resistance.     

Synthesis, crystal structure and thermal decomposition of [La2(CH3CH2COO)6·(H2O)3]·3.5H2O precursor for high-k La2O3 thin films deposition

Lanthanum acetylacetonate La(C₅H₇O₂)₃·xH₂O has been used in the preparation of the precursor solution for the deposition of polycrystalline La₂O₃ thin films on Si(1 1 1) single crystalline substrates. The precursor chemistry of the as-prepared coating solution, precursor powder and precursor single crystal have been investigated by Fourier Transformed Infrared Spectroscopy (FTIR), differential thermal analysis coupled with quadrupole mass spectrometry (TG-DTA-QMS) and X-ray diffraction. The FTIR and X-ray diffraction analyses have revealed the complex nature of the coating solution due to the formation of a lanthanum propionate complex. The La₂O₃ thin films deposited by spin coating on Si(1 1 1) substrate exhibit good morphological and structural properties. The films heat treated at 800 °C crystallize in a hexagonal phase with the lattice parameters a = 3,89 Å and c = 6.33 Å, while at 900 °C the films contain both the hexagonal and cubic La₂O₃ phase.     

Finite element simulation of residual stress of double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings using birth and death element technique

In this paper, the residual stress of double-ceramic-layer (DCL) La₂Zr₂O₇/8YSZ thermal barrier coatings (TBCs) fabricated by atmospheric plasma spraying (APS) was calculated by finite element simulation using birth and death element technique. The residual stress was composed of two parts, i.e. the quenching stress and the thermal stress. The simulation results indicated that the surface and the edge of interface are often the positions of stress concentration. The DCL La₂Zr₂O₇/8YSZ has lower residual stress compared with that of the single-ceramic-layer (SCL) 8YSZ TBCs with the same thickness. In addition, the influence of defects on the residual stress has been calculated and discussed using finite element method combined with Computational Micro-Mechanics (CMM). As the DCL TBCs has better thermal insulation effect, sintering resistance ability and lower residual stress compared with that of the SCL 8YSZ at the same time, it was expected to be an ideal candidate material for the application in the future.     

Dependence of La2O3 content on the nonlinear electrical behaviour of ZnO, CoO and Ta2O5 doped SnO2 varistors

The effects of La₂O₃ on the properties of (Zn, Co, Ta) doped SnO₂ varistors were investigated in this study. The samples with different La₂O₃ concentrations were sintered at 1400 °C for 2 h and their properties were characterized by XRD, SEM, I-V and impedance spectroscopy. The grain size was found to decrease from 13 μm to 9 μm with increasing La₂O₃ content. The addition of rare earth element leads to increase the nonlinear coefficient and the breakdown voltage. The enhancement was expected to arise from the possible segregation of lanthanide ion due to its larger ionic radius to the grain boundaries, thereby modifying its electrical characteristics. Furthermore, the dopants such as La may help in the adsorption of O′ to O″ at the grain boundaries characteristics.     

Structure and thermal conductivity of Gd2(TixZr1 − x)2O7 ceramics

The Gd₂(Ti_xZr_1 − x)₂O₇ (x = 0, 0.25, 0.50, 0.75, 1.00) ceramics were synthesized by solid state reaction at 1650 °C for 10 h in air. The relative density and structure of Gd₂(Ti_xZr_1 − x)₂O₇ were analyzed by the Archimedes method and X-ray diffraction. The thermal diffusivity of Gd₂(Ti_xZr_1 − x)₂O₇ from room temperature to 1400 °C was measured by a laser-flash method. The Gd₂Zr₂O₇ has a defect fluorite-type structure; however, Gd₂(Ti_xZr_1 − x)₂O₇ (0.25 ≤ x ≤ 1.00) compositions exhibit an ordered pyrochlore-type structure. Gd₂Zr₂O₇ and Gd₂Ti₂O₇ are infinitely soluable. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ increases with increasing Ti content under identical temperature conditions. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ first decreases gradually with the increase of temperature below 1000 °C and then increases slightly above 1000 °C. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ is within the range of 1.33 to 2.86 W m^− 1 K^− 1 from room temperature to 1400 °C.     

Synthesis and sintering of Ca0.5Zr2P3O12 -a low thermal expansion material

The single phase compound Ca_0.5Zr₂P₃O₁₂ (CZP) was prepared by solid state reaction technique. This material shows a negative thermal expansion in the temperature region of 30°–500°C. The effect of MgO and ZnO addition on the sintering behavior and thermal expansion characteristics of Ca_0.5Zr₂P₃O₁₂ was investigated. Mg₃(PO₄)₂ and Zn₃(PO₄)₂ were observed as minor phases responsible for improving the overall thermal expansion of CZP + MgO, ZnO systems. SEM studies and density data are also discussed. Observed sintering kinetics suggest that a liquid phase is promoting the sintering reaction. 98+% of theoretical density and near zero expansion behavior in certain compositions were observed.     

Electrical properties of La2Mo1.98Nb0.02O8.99 oxide ionic conductors prepared by tape casting

La₂Mo_2-xNb_xO_9-δ thick films have been successfully prepared by using a tape casting technique. Partial stabilization of the high temperature cubic phase is revealed in Nb doped La₂Mo₂O₉ (LMO) films. The sintering temperature is decreased to 925?°C as compared with that of 1150?°C in bulk ceramics. The grain exhibits an oxide ionic conductivity of 0.014?S?cm^?1 at 603?°C for La₂Mo_1.98Nb_0.02O_8.99, which is 39% higher than pure LMO. Additionally, the Nb doped LMO films present low grain boundary resistance showing the potential application as solid electrolytes.     

Structural properties of Al2O3-La2O3 binary oxides prepared by sol-gel

The structural properties of La₂O₃ and Al₂O₃-La₂O₃ binary oxides prepared by sol-gel were studied by XRD, HRTEM and UV-vis. The binary oxides with high lanthana contents show an amorphous structure after calcination at 650 °C. At calcination temperatures higher than 1000 °C there is a phase transformation from the amorphous state to the crystalline LaAlO₃ with a perovskite structure. The structure of La₂O₃ is consistent with the hexagonal system; however, some crystalline microdomains with a monoclinic structure were detected by HRTEM. Islands of La₂O₃ and LaAl₁₁O₁₈ phases were detected at high lanthana concentration in the binary oxide. The modification in the coordination shell of the Al³⁺ cations due to the interaction with La³⁺ cations confirms the formation of phases with a perovskite structure and the presence of islands of the LaAl₁₁O₁₈ phase.     

H2S sensing properties of La-doped nanocrystalline In2O3

The nanocrystalline powders of pure and La³⁺-doped In₂O₃ with cubic structure were prepared by a simple hydrothermal decomposition route. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). All the compositions exhibited a single phase, suggesting a formation of solid solution in the concentration of doping investigated. Gas-sensing properties of the sensor elements were tested by mixing a gas in air at static state, as a function of concentration of dopant, operating temperature and concentrations of the test gases. The pure In₂O₃ exhibited high response towards H₂S gas at an operating temperature 150 °C. Doping of In₂O₃ with La³⁺ increases its response towards H₂S and La³⁺ (5.0 wt.% La₂O₃)-doped In₂O₃ showed the maximum response at 125 °C. The selectivity of the sensor elements for H₂S against different reducing gases was studied. The results on response and recovery time were also discussed.     

Microstructure, domain structures and ferroelectric properties in (Pb0.8,La0.1,Ca0.1)TiO3/Pb(Zr0.2,Ti0.8)O3 bilayered thin film

Ferroelectric (Pb_0.8,La_0.1,Ca_0.1)TiO₃/Pb(Zr_0.2,Ti_0.8)O₃ (PLCT/PZT) bilayered thin film was prepared on Pt(111)/Ti/SiO₂/Si(100) substrate by RF magnetron sputtering technique. Pure perovskite crystalline phase, determined by X-ray diffraction, was formed in the PLCT/PZT bilayer. The bilayered film exhibited a very dense and smooth surface morphology with a uniform grain size distribution. The ferroelectric domain structures were investigated by a combination of vertical and lateral piezoresponse force microscopy (VPFM and LPFM, respectively). It is demonstrated by both VPFM and LPFM observations that out-of-plane and in-plane lamellar ferroelectric domains coexist in the bilayered thin film. The PLCT/PZT bilayered film possesses good ferroelectric properties with relatively high spontaneous polarization (2P_s = 82 µC/cm²) and remnant polarization (2P_r = 26.2 µC/cm²).     

Structure and lithium ion conductivity of garnet-like Li5La3Sb2O12 and Li6SrLa2Sb2O12

Oxides with the nominal chemical compositions Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were prepared by solid-state reaction. The structures were refined by the Rietveld method using powder X-ray diffraction data. The synthesis of Li₅La₃Sb₂O₁₂ resulted in the well known garnet-related structure plus 5 wt.% of La₂LiSbO₆ in the bulk. In contrast to that, Li₆SrLa₂Sb₂O₁₂ could be synthesised in single garnet-related type phase. Lithium ion conductivities of Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were studied by the ac impedance method. The grain-boundary contribution to the total (bulk + grain-boundary) resistance is very small and about 5 and 3% for Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂, respectively, at 24 °C and decreases further with increase in temperature. Among the investigated compounds, Li₅La₃Sb₂O₁₂ exhibits the highest total (bulk + grain-boundary) and bulk ionic conductivity of 7.8 × 10⁻⁶ and 8.2 × 10⁻⁶ S cm⁻¹, respectively, at 24 °C. The structural data indicate that the coupled substitution Li + Sr ⇒ La leads to a closure of the bottle neck like O-O distances of the shared edges of neighbouring Li octahedra and therefore reduces the mobility of Li ions in Li₆SrLa₂Sb₂O₁₂. Scanning electron microscope (SEM) images of the Li₆SrLa₂Sb₂O₁₂ compound revealed well crystallised large homogeneous grains (∼4.8 μm) and the grains were in good contact with the neighbouring grain, which leads to a smaller grain-boundary contribution to the total resistance.