Fabrication and properties of Ba(Zr1−xCex)0.9Y0.1O2.95/NaCl composite electrolyte materials

Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95/NaCl (x = 0.1, 0.2 and 0.3) composite electrolyte materials were fabricated with ZnO as sintering aid. The effect of ZnO on the properties of Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 matrix were investigated. The phase composition and microstructure of samples were characterized by XRD and SEM, respectively. The electrochemical performances were studied by three-probe conductivity measurement and AC impedance spectroscopy. XRD results showed that Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 with 2 mol% of ZnO was perovskite structure. The relative density of this sample was above 95% when sintered at 1450 °C for 6 h. By adding 10 mol% of NaCl to Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 with 2 mol% of ZnO that was sintered at 1400 °C for 6 h, the conductivity was increased. The electrical conductivity of 1.26 × 10⁻² S/cm and activation energy of 0.23 eV were obtained when tested at 800 °C in wet hydrogen.     

Optical and thermal properties of P2O5-Na2O-CaO-Al2O3:CoO glasses doped with transition metals

The aim of this paper is to report the optical and thermal properties of V₂O₅ and CuO doped P₂O₅-Na₂O-CaO-Al₂O₃:CoO glasses so as to investigate their possible use in solar collection applications. The optical absorption spectra of the glasses at room temperature were in the spectral range of 200-1100 nm. The optical band gaps of the glass samples were determined for direct and indirect transitions. When transition metal ions doped to the base glass, the optical band gap decreased. Changes in the refractive indices vs. wavelength for all the specimens were also examined by spectroscopic ellipsometry. By measuring the heat capacities and thermal diffusion coefficients of the specimens at varying temperatures, their thermal conductivities were calculated to be in the 320-620 K temperature range. The obtained glasses seem to be promising materials and can be used in solar collector applications.     

Influence of B site substituent Ti on the structure and thermophysical properties of A2B2O7-type pyrochlore Gd2Zr2O7

Since the structural integrity of A₂B₂O₇-type pyrochlores relies mostly on the interconnecting BO₆ octahedra, Ti⁴⁺ was selected to partially substitute Zr⁴⁺ in Gd₂Zr₂O₇ in order to distort the pyrochlore structure in order to improve the material’s thermophysical properties for potential use as high-temperature thermal insulation. As evidenced by X-ray diffraction and Raman spectroscopy studies, incorporation of Ti⁴⁺ simultaneously leads to long-range ordering of the pyrochlore structure as well as local lattice distortion. These two effects have been shown to be competitive in determining the crystal energy of the Gd₂(Zr_1−xTi_x)₂O₇ series and result in a minimum value of the Young’s modulus at x = 0.3 and a maximum value of the coefficient of thermal expansion at x = 0.2. At lower temperatures, the thermal conductivity of Gd₂Zr₂O₇ was significantly reduced by Ti⁴⁺ doping, and its composition dependence was accurately modeled by taking into account the phonon scattering by mass and strain fluctuations at the B site.     

Novel thermal barrier coatings based on La2Ce2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Novel thermal barrier coatings based on La₂Ce₂O₇/8YSZ double-ceramic-layer (DCL) systems, which were deposited by electron beam physical vapor deposition (EB-PVD), were found to have a longer lifetime compared to the single layer La₂Ce₂O₇ (LC) system, and even much longer than that of the single layer 8YSZ system under burner rig test. The DCL coating structure design can effectively alleviate the thermal expansion mismatch between LC coating and bond coat, as well as avoid the chemical reaction between LC and Al₂O₃ in thermally grown oxide (TGO), which occurs above 1000 °C as determined by differential scanning calorimetry (DSC) analysis. The failure mechanism of LC/8YSZ DCL coating is mainly due to the sintering of LC coating surface after long-term thermal cycling.     

Y2O3-BaO-SiO2-B2O3-Al2O3 glass sealant for solid oxide fuel cells

A glass based on Y₂O₃-BaO-SiO₂-B₂O₃-Al₂O₃ (named YBA) has been investigated as sealant for planar solid oxide fuel cells (SOFCs). The YBA glass has been systematically characterized by differential thermal analysis, dilatometer, scanning electron microscopy, impedance analysis, and open circuit voltage to examine their suitability as sealant. The coefficient of thermal expansion of YBA is 11.64 × 10⁻⁶ K⁻¹ between 323 and 873 K. The resistivity is 9.1 × 10⁴ Ω cm at 800 °C. The glass sealant is found to be well adhered with other cell components, such as electrolytes and stainless steels, at an optimum sealing temperature of 800 °C. All measured results showed that the YBA glass appears to be a promising sealant for SOFCs.     

Novel thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and yttria stabilized zirconia (YSZ) were deposited by electron beam-physical vapor deposition (EB-PVD). The thermal cycling test at 1373 K in an air furnace indicates the DCL coating has a much longer lifetime than the single layer LZ7C3 coating, and even longer than that of the single layer YSZ coating. The superior sintering-resistance of LZ7C3 coating, the similar thermal expansion behaviors of YSZ interlayer with LZ7C3 coating and thermally grown oxide (TGO) layer, and the unique growth modes of columns within DCL coating are all very helpful to the prolongation of thermal cycling life of DCL coating. The failure of DCL coating is mainly a result of the reduction-oxidation of cerium oxide, the crack initiation, propagation and extension, the abnormal oxidation of bond coat, the degradation of t′-phase in YSZ coating and the outward diffusion of Cr alloying element into LZ7C3 coating.     

Electrical and thermal characterization of Sm doped ceria electrolytes synthesized by combustion technique

Nanocrystalline samarium doped ceria electrolyte [Ce_0.9Sm_0.1O_1.95] was synthesized by citrate gel combustion technique involving mixtures of cerium nitrate oxidizer (O) and citric acid fuel (F) taken in the ratio of O/F = 1. The as-combusted precursors were calcined at 700 °C/2 h to obtain fully crystalline ceria nano particles. It was further made into cylindrical pellets by compaction and sintered at 1200 °C with different soaking periods of 2, 4 and 6 h. The sintered ceria was characterized for the microstructures, electrical conductivity, thermal conductivity and thermal diffusivity properties. In addition, the combustion derived ceria powder was also analysed for the crystallinity, BET surface area, particle size and powder morphology. Sintered ceria samples attained nearly 98% of the theoretical density at 1200 °C/6 h. The sintered microstructures exhibit dense ceria grains of size less than 500 nm. The electrical conductivity measurements showed the conductivity value of the order of 10⁻² S cm⁻¹ at 600 °C with activation energy of 0.84 eV between the temperatures 100 and 650 °C for ceria samples sintered at 1200 °C for 6 h. The room temperature thermal diffusivity and thermal conductivity values were determined as 0.5 × 10⁻⁶ m² s⁻¹ and 1.2 W m⁻¹ K⁻¹, respectively.     

SmBaCoCuO5+x as cathode material based on GDC electrolyte for intermediate-temperature solid oxide fuel cells

The performance of SmBaCoCuO_5+x (SBCCO) cathode has been investigated for their potential utilization in intermediate-temperature solid oxide fuel cells (IT-SOFCs). The powder X-ray diffraction (XRD), thermal expansion and electrochemical performance on Ce_0.9Gd_0.1O_1.95 (GDC) electrolyte are evaluated. XRD results show that there is no chemical reaction between SBCCO cathode and GDC electrolyte when the temperature is below 950 °C. The thermal expansion coefficient (TEC) value of SBCCO is 15.53 × 10⁻⁶ K⁻¹, which is ∼23% lower than the TEC of the SmBaCo₂O_5+x (SBCO) sample. The electrochemical impedance spectra reveals that SBCCO symmetrical half-cells by sintering at 950 °C has the best electrochemical performance and the area specific resistance (ASR) of SBCCO cathode is as low as 0.086 Ω cm² at 800 °C. An electrolyte-supported fuel cell generates good performance with the maximum power density of 517 mW cm⁻² at 800 °C in H₂. Preliminary results indicate that SBCCO is promising as a cathode for IT-SOFCs.     

Direct synthesis of Fe3O4 nanopowder by thermal decomposition of Fe-urea complex and its properties

An easy synthesis route of magnetite (Fe₃O₄) nanopowder is developed by using thermal decomposition of Fe-urea complex ([Fe(CON₂H₄)₆](NO₃)₃). The formation of Fe₃O₄ is confirmed from X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. The morphological properties and magnetic properties of the Fe₃O₄ are characterized by transmission electron microscopy (TEM) and magnetic measurements, respectively. By an increase in reaction temperature from 200 to 300 °C, the average crystallite size of the Fe₃O₄ nanopowder increases from 37 to 50 nm. Room temperature magnetization hysteresis curves show that the Fe₃O₄ nanopowder possesses ferrimagnetic characteristics. The saturation magnetization of the Fe₃O₄ nanopowder increases from 70.7 to 89.1 emu/g when the reaction temperature increases from 200 to 300 °C.     

Neodymium-cerium oxide as new thermal barrier coating material

Neodymium-cerium oxide (Nd₂Ce₂O₇) was proposed as a new thermal barrier coating material in this work. Monolithic Nd₂Ce₂O₇ powder was prepared by the solid-state reaction at 1400 °C. The phase composition, thermal stability and thermophysical properties of Nd₂Ce₂O₇ were investigated. Nd₂Ce₂O₇ with fluorite structure was thermally stable in the temperature range of interest for TBC applications. The results indicated that the thermal expansion coefficient (TEC) of Nd₂Ce₂O₇ was higher than that of YSZ (6-8 wt.% Y₂O₃ + ZrO₂) and even more interesting was the TEC change as a function of temperature paralleling that of the superalloy bond coat. Moreover, the thermal conductivity of Nd₂Ce₂O₇ is 30% lower than that of YSZ, which was discussed based on the theory of heat conduction. Thermal barrier coating of Nd₂Ce₂O₇ was produced by atmospheric plasma spraying (APS) using the spray-dried powder. The thermal cycling was performed with a gas burner test facility to examine the thermal stability of the as-prepared coating.     

High permittivity and low dielectric loss of the Ca1−xSrxCu3Ti4O12 ceramics

The Ca_1−xSr_xCu₃Ti₄O₁₂ (CSCTO) giant dielectric ceramics were prepared by conventional solid-state method. X-ray diffraction patterns revealed that a small amount of Sr²⁺ (x < 0.2) had no obvious effect on the phase structure of the CSCTO ceramics, while with increasing the Sr²⁺ content, a second phase of SrTiO₃ appeared. Electrical properties of CSCTO ceramics greatly depended on the Sr²⁺ content. The Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics exhibited a higher permittivity (71,153) and lower dielectric loss (0.022) when measured at 1 kHz at room temperature. The ceramics also performed good temperature stability in the temperature range from −50 °C to 100 °C at 1 kHz. By impedance spectroscopy analysis, all compounds were found to be electrically heterogeneous, showing semiconducting grains and insulating grain boundaries. The grain resistance was 1.28 Ω and the grain boundary resistance was 1.31 × 10⁵ Ω. All the results indicated that the Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics were very promising materials with higher permittivity for practical applications.     

Combustion synthesis of CaSc2O4:Ce nano-phosphors in a closed system

The CaSc₂O₄:Ce³⁺ nano-phosphors were successfully prepared by a single-step combustion method at an ignition temperature as low as 200 °C in a closed autoclave using glycine as a fuel and PEG4000 as a dispersant. The samples were characterized by X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscope (TEM). The results revealed that CaSc₂O₄:Ce³⁺ nano-phosphors can be conveniently prepared at an ignition temperature as low as 200 °C, which was much lower than that in the ordinary combustion methods. The optimized ignition temperature was 220 °C. The CaSc₂O₄:Ce³⁺ nano-phosphors give a uniform particle size in the range of 15-20 nm. The low ignition temperature and the addition of PEG4000 dispersant play important roles in the formation of small sized nanoparticles. The as-prepared nano-phosphors were incompact aggregates, but highly dispersed nano-phosphors can be obtained after further ultrasonic treatment. The CaSc₂O₄:Ce³⁺ nano-phosphors give satisfactory luminescence characteristic benefiting from the closed circumstance, in which cerium atoms can be isolated from the oxidizing atmosphere and non-fluorescent Ce⁴⁺ ions can be ruled out. The present highly dispersed CaSc₂O₄:Ce³⁺ nano-phosphors with efficient fluorescence are promising in the field of biological labeling, and the present low temperature combustion method is facile and convenient and can be applied as a universal process for preparing non-aggregate oxide nano-phosphors, especially those being sensitive to air at high temperature.     

Hot corrosion behaviour of Yb2Zr2O7 ceramic coated with V2O5 at temperatures of 600-800 °C in air

To better understand the hot corrosion behaviour of Yb₂Zr₂O₇ ceramic in molten V₂O₅, hot corrosion experiments were performed in a temperature range of 600-800 °C in air. Different reaction products of ZrV₂O₇, YbVO₄ and m-ZrO₂ were identified depending upon the hot corrosion conditions, for example, ZrV₂O₇ and YbVO₄ at 600 °C for 2 h and 8 h; ZrV₂O₇, m-ZrO₂ and YbVO₄ at 700 °C for 2 h; m-ZrO₂ and YbVO₄ either at 800 °C for 2 h or at 700-800 °C for 8 h. The hot corrosion reaction mechanisms were further discussed based on the thermal instability of ZrV₂O₇ at elevated temperatures.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

Mg-substituted ZnNb2O6-TiO2 composite ceramics for RF/microwaves ceramic capacitors

Microstructure and microwave dielectric properties of Mg-substituted ZnNb₂O₆-TiO₂ microwave ceramics were investigated. Mg acted as a grain refining reagent and columbite phase stabilization reagent. With an increasing Mg content, the amount of ixiolite (Zn, Mg) TiNb₂O₈ decreased, and the amount of (Zn_0.9Mg_0.1)_0.17Nb_0.33Ti_0.5O₂ and columbite increased. ZnO-Nb₂O₅-1.75TiO₂-5 mol.%MgO exhibited excellent dielectric properties (at 950 °C): ?_r = 35.6, Q × f = 16,000 GHz (at 5.6 GHz) and τ_f = −10 ppm/°C. The material was applied successfully to make RF/microwaves ceramic capacitor, whose self-resonance frequency was 19 GHz at low capacitance of 0.13 pF.     

Structure and dielectric characterization of xNd(Mg1/2Ti1/2)O3-(1 − x)Ca0.6La0.8/3TiO3 in the microwave frequency range

The crystal structures, phase compositions and the microwave dielectric properties of the xLa(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.8Sr_0.2TiO₃ composites prepared by the conventional solid state route have been investigated. The formation of solid solution is confirmed by the XRD patterns. Doping with B₂O₃ (0.5 wt.%) can effectively promote the densification and the dielectric properties of xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. It is found that xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics can be sintered at 1375 °C, due to the liquid phase effect of B₂O₃ addition observed by Scanning Electronic Microscopy. At 1375 °C, 0.4Nd(Mg_1/2Ti_1/2)O₃-0.6Ca_0.6La_0.8/3TiO₃ ceramics with 1 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 49, a Q × f value of 13,000 (at 8 GHz) and a temperature coefficients of resonant frequency (τ_f) of 1 ppm/°C. As the content of Nd(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 20,000 GHz for x = 0.9 is achieved at the sintering temperature 1400 °C.     

Enthalpy of formation of selected mixed oxides in a CaO-SrO-Bi2O3-Nb2O5 system

The heats of drop-solution in 3Na₂O + 4MoO₃ melt at 973 K and 1073 K for calcium and strontium carbonates, Bi₂O₃, Nb₂O₅ and several stoichiometric mixed oxides in CaO-Nb₂O₅, SrO-Nb₂O₅ and Bi₂O₃-Nb₂O₅ systems were measured using a Setaram Multi HTC-96 calorimeter. The values of enthalpy of formation from constituent binary oxides at 298 K, Δ_oxH, were derived for the mixed oxides under investigation: Δ_oxH(CaNb₂O₆) = −132.0 ± 23.8 kJ mol⁻¹, Δ_oxH(Ca₂Nb₂O₇) = −208.0 ± 31.9 kJ mol⁻¹, Δ_oxH(SrNb₂O₆) = −167.9 ± 19.1 kJ mol⁻¹, Δ_oxH(Sr₂Nb₂O₇) = −289.2 ± 37.5 kJ mol⁻¹ and Δ_oxH(BiNbO₄) = −41.9 ± 11.1 kJ mol⁻¹. Additionally, the values Δ_oxH for other mixed oxides with different stoichiometries were estimated on the basis of these experimental results.     

Effect of a magnetron sputtered (Al2O3-Y2O3)/(Pt-Au) laminated coating on hot corrosion resistance of 8Nb-TiAl alloy

Novel (Al₂O₃-Y₂O₃)/(Pt-Au) laminated coatings were prepared on 8Nb-TiAl alloy by magnetron sputtering methods. (Na₂SO₄-NaCl)-induced hot corrosion and cyclic oxidation tests were adopted to investigate the high-temperature corrosion behaviours and the mechanical properties of the as-prepared laminated coatings. The results revealed that the multi-sealed (Al₂O₃-Y₂O₃) and (Pt-Au) layers can effectively suppress the inward diffusion of oxygen and corrosive fused salt to an extremely low level at 1000 °C and 900 °C respectively. Consequently, the high-temperature corrosion resistance of the 8Nb-TiAl alloy can be significantly improved. In addition, cyclic tests revealed the (Al₂O₃-Y₂O₃)/(Pt-Au) laminated coating can exhibit enhanced spallation and fracture resistance, which are attributable to the brittle/ductile laminated composite structure by means of energy release mechanisms and the increased thermal expansion coefficient of the coating by the addition of Pt-Au alloy.     

Microstructural evolution of 7 wt.% Y2O3-ZrO2 thermal barrier coatings due to stress relaxation at elevated temperatures and the concomitant changes in thermal conductivity

The purpose of this study was to evaluate the combined effect of stress and temperature on the microstructure of air plasma-sprayed 7 wt.% Y₂O₃-ZrO₂ thermal barrier coatings, and relate microstructural changes to the thermal conductivity, k_th. To simulate TBC service conditions, stand-alone tubes of YSZ were stress relaxed, starting from a compressive stress of 60 MPa, at temperatures of 1000 °C or 1200 °C. The duration of the stress relaxation test was either 5 min or 3 h. Detailed scanning electron microscopy (SEM) and Porod's specific surface area (SSA) analysis of small angle neutron scattering (SANS) results were used to determine which void systems, either interlamellar pores or intralamellar cracks, contributed to the observed relaxation of stress in the coatings. SEM investigations revealed closure of intralamellar cracks located perpendicular to the stress direction. For thinner YSZ coatings, SANS measurements indicated a statistically significant reduction in the total SSA and SSA associated with intralamellar cracks after stress relaxation at the times, temperatures, and stress investigated compared to those samples that were exposed to identical times and temperatures, but no stress. The SSA associated with the interlamellar pores was not significantly smaller in YSZ coatings stress relaxed from 60 MPa at 1200 °C for 3 h compared to as-sprayed coatings. The thermal conductivity of the coatings was strongly influenced by stress, with increases in k_th observed after only 5 min at 60 MPa and 1200 °C. Reductions in the total SSA were directly linked to increases in k_th.