Ba and Gd Doping Effect in (BaxSr1–x)0.95Gd0.05Co0.8Fe0.2O3–δ (x = 0.1–0.9) Cathode on the Phase Structure and Electrochemical Performance

In this study, Ba_xSr_1–xCo_0.8Fe_0.2O_3–δ (BSCF) doped with trace of Gd were studied for phase structures and properties about thermal expansion, electrical conductivity, and electrocatalytic activity. The solution range of barium in Ba_xSr_1–xCo_0.8Fe_0.2O_3–δ can be extended to 0.1 ≤ x ≤ 0.7 after the introduction of small amount of Gd³⁺ ions (only for 5%) into the Ba/Sr‐site. The calculation results of the crystal structure and the crystal lattice energy show that the ratio of Ba/Sr and doping of Gd³⁺ lead to increase the lattice parameter and the Co/Fe ionic average valence state in B‐site. Moreover, the ratio of Ba/Sr and doping of Gd³⁺ were found to have significant impacts on the high‐temperature physical properties and electrochemical characteristics. All oxides exhibited decreases in the thermal expansion coefficient (TEC) and electrical conductivity with increasing Ba/Sr ratio. Barium insertion was found to change the area‐specific resistance (ASR) of porous (not dense) cathodes. An ASR values of 0.048, 0.072, 0.064, 0.121, and 0.059 Ω cm² under air condition were observed at 650 °C for BSGCF with x = 0.1, 0.2, 0.3, 0.5, and 0.7, respectively.     

Synthesis and Electrochemical Properties of BaFe1−xCuxO3−δ Perovskite Oxide for IT‐SOFC Cathode

A series of iron‐based perovskite oxides BaFe_1−xCu_xO_3−δ (x = 0.10, 0.15, 0.20 and 0.25, abbreviated as BFC‐10, BFC‐15, BFC‐20 and BFC‐25, respectively) as cathode materials have been prepared via a combined EDTA‐citrate complexing sol‐gel method. The effects of Cu contents on the crystal structure, chemical stability, electrical conductivity, thermal expansion coefficient (TEC) and electrochemical properties of BFC‐x materials have been studied. All the BFC‐x samples exhibit the cubic phase with a space group Pm3m (221). The electrical conductivity decreases with increasing Cu content. The maximum electrical conductivity is 60.9 ± 0.9 S cm⁻¹ for BFC‐20 at 600 °C. Substitution of Fe by Cu increases the thermal expansion coefficient. The average TEC increases from 20.6 × 10⁻⁶ K⁻¹ for BFC‐10 to 23.7 × 10⁻⁶ K⁻¹ for BFC‐25 at the temperature range of 30–850 °C. Among the samples, BFC‐20 shows the best electrochemical performance. The area specific resistance (ASR) of BFC‐20 on SDC electrolyte is 0.014 Ω cm² at 800 °C. The single fuel cell with the configguration of BFC‐20/SDC/NiO‐SDC delivers the highest power density of 0.57 W cm⁻² at 800 °C. The favorable electrochemical activities can be attributed to the cubic lattice structure and the high oxygen vacancy concentration caused by Cu doping.     

Complex Effect of Sm3+/W6+ Codoping on α‐β Phase Transformation and Phonon Scattering of Oxygen‐Deficient La2Mo2O9

Lanthanum molybdate, La₂Mo₂O₉, has been attracted considerable attention owing to its high concentration of intrinsic oxygen vacancies, which could be reflected by enhanced phonon scattering and low thermal conductivity. A new series of La₂Mo₂O₉‐based oxides of the general formula La_2?xSm_xMo_2?xW_xO₉, where x ≤ 0.2, were synthesized by citric acid sol–gel process. The variation in thermal conductivity with Sm³⁺and W⁶⁺ fractions was analyzed based on structure information provided by X‐ray diffraction and Raman spectroscopy. The fully dense La_2?xSm_xMo_2?xW_xO₉ ceramics showed a minimum thermal conductivity value [κ = 0.84 W·(m·K)^?1,T = 1073 K] at the composition of La_1.8Sm_0.2Mo_1.8W_0.2O₉, which stems from the multiple enhanced phonon scatterings due to mass and strain fluctuations at the La³⁺ and Mo⁶⁺ sites as well as the high concentration of intrinsic oxygen vacancies embedded in the crystal lattice. The thermal conductivities present an abrupt decrease at the structural transition, which is due to the phase transformation from a low‐temperature ordered form (monoclinic α‐La₂Mo₂O₉) to a high‐temperature disordered form (cubic β‐La₂Mo₂O₉₎.     

Pyroelectric energy harvesting using low–TC (1–x)(Ba0.7Ca0.3)TiO3–xBa(Zr0.2Ti0.8)O3 bulk ceramics

Lead‐free ferroelectric ceramics (1–x)(Ba_0.7Ca_0.3)TiO₃–xBa(Zr_0.2Ti_0.8)O₃ (BCTZ100x) with x = 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, and 0.80 were evaluated for their pyroelectric energy harvesting performance, using the Olsen cycle. As the composition ratio x increased, the crystal phase changed to tetragonal, orthorhombic, rhombohedral, and cubic; the phase boundaries crossed each other in the vicinity of BCTZ70. The crossover phase transition behavior between first‐order and diffuse phase transition changed to only the diffusion phase transition with increasing x. A pinching effect occurred because an increase in dielectric constant was also observed. Energy densities N_D of 229 mJ/cm³ and 256 mJ/cm³ for BCTZ50 and BCTZ80 were obtained, respectively, in temperature of 30°C‐100°C and an electric field of 0‐30 kV/cm. These N_D values are over two times higher than that of soft–Pb(Ti,Zr)O₃ (PZT), which exhibits piezoelectric performance equivalent to BCTZ50 at room temperature. Compared with soft–PZT, BCTZ50 and BCTZ80 exhibited larger N_D values owing to their lower Curie temperatures (T_C ~ 50°C‐110°C). We conclude that low–T_C ferroelectrics are useful for pyroelectric energy conversion based on the Olsen cycle even if they are unsuitable for piezoelectric applications at high temperatures.     

Efficient red‐emitting phosphor of Eu3+‐activated (Na0.5Gd1.5)(TiSb)O7 derived via cation‐substitutions in Gd‐Pyrochlore

Rare‐earth (RE) titanate pyrochlore with perovskite‐layered structure is a well‐known engineering material in applied in many field. In this work, a red‐emitting phosphor of Gd_2?xNa_xTi_2?2xSb_2xO₇:Eu³⁺ (x = 0‐0.5) was developed via cation substitutions of (Sb⁵⁺→Ti⁴⁺) and (Na⁺→Gd³⁺) in Gd₂Ti₂O₇. The motivation is based on the fact that the introduction of cation‐disorders has been regarded to be an effective approach for improving the luminescent efficiency and thermal stability of RE‐activated materials. All the samples were synthesized via facile solid‐state reaction method. The morphology properties were measured via SEM and EDS measurements. The structural Rietveld refinement was performed to investigate the microstructure in pyrochlore lattices. The luminescence properties of Gd_2?xNa_xTi_2?2xSb_2xO₇:0.15Eu³⁺ (x = 0‐0.5) has a strict dependence on the cation substitution levels. The band energy of Gd₂Ti₂O₇ is 2.9 eV with a direct transition nature. The incorporation of Sb⁵⁺ and Na⁺ in the lattices moves the optical absorption to a longer wavelength. The cation disorder results in significant improvements of luminescence intensity, excitation efficiency in the blue region, longer emission lifetime and thermal stability.     

Asymmetric 1,3‐Dipolar Cycloaddition Reaction between α,β‐Unsaturated Aldehydes and Nitrones Catalyzed by Well‐Defined Iridium or Rhodium Catalysts

Reaction of the complexes (S_M,R_C)‐[(η⁵‐C₅Me₅)M{(R)‐Prophos}(H₂O)](SbF₆)₂ (M=Rh, Ir) with α,β‐unsaturated aldehydes diastereoselectively gave complexes (S_M,R_C)‐[(η⁵‐C₅Me₅)M{(R)‐Prophos}(enal)](SbF₆)₂ which have been fully characterized, including an X‐ray molecular structure determination of the complex (S_Rh,R_C)‐[(η⁵‐C₅Me₅)Rh{(R)‐Prophos}(trans‐2‐methyl‐2‐pentenal)](SbF₆)₂. These enal complexes efficiently catalyze the enantioselective 1,3‐dipolar cycloaddition of the nitrones N‐benzylideneaniline N‐oxide and 3,4‐dihydroisoquinoline N‐oxide to the corresponding enals. Reactions occur with excellent regioselectivity, perfect endo selectivity and with enantiomeric excesses up to 94 %. The absolute configuration of the adduct 5‐methyl‐2,3‐diphenylisoxazolidine‐4‐carboxaldehyde was determined through its (R)‐(−)‐α‐methylbenzylamine derivative.     

Hydrothermal formation and up‐conversion luminescence of Er3+‐doped GdNbO4

The effect of concentration of Er³⁺ on the up‐conversion and photoluminescence properties of Gd_1.00?xEr_xNbO₄, x=0‐0.50 which has monoclinic fergusonite‐type structure as a main phase has been investigated, using a processing technique based on hydrothermal method. Under weakly basic hydrothermal condition at 240°C for 5 hours, a single phase of fergusonite‐type Gd_1.00?xEr_xNbO₄ solid solution was directly formed as nanocrystals by the substitutional incorporation of Er³⁺ into GdNbO₄ because of the gradual and linear decrease in the lattice parameters of the monoclinic phase corresponding to the Vegard's Law. The gadolinium niobate doped with 2 mol% Er³⁺, Gd_0.98Er_0.02NbO₄ after heating at 1300°C for 1 hour, which has nanocrystalline structure whose crystallite size is around 29 nm, exhibits the highest photoluminescence intensity in the green spectral region, 515‐560 nm under excitation at wavelength of 254 nm. On the other hand, the up‐converted luminescence intensity of the niobate nanocrystals becomes the maximum at the concentration of 20 mol% Er³⁺, Gd_0.80Er_0.20NbO₄ under excitation at 980 nm. These results demonstrate that the material, Er³⁺‐doped GdNbO₄ nanocrystals prepared through hydrothermal route and postheating has potential for up‐converting phosphor.     

Synthesis,Crystal Structure,and Thermal Behaviors of 3‐Nitro‐1,5‐bis(4,4′‐dimethylazide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP)

The energetic material, 3‐nitro‐1,5‐bis(4,4′‐dimethyl azide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP), was firstly synthesized by means of Click Chemistry using 1,5‐diazido‐3‐nitrazapentane as main material. The structure of NDTAP was confirmed by IR, ¹H NMR, and ¹³C NMR spectroscopy; mass spectrometry, and elemental analysis. The crystal structure of NDTAP was determined by X‐ray diffraction. It belongs to monoclinic system, space group C2/c with crystal parameters a=1.7285(8) nm, b=0.6061(3) nm, c=1.6712(8) nm, β=104.846(8)°, V=1.6924(13) nm³, Z=8, μ=0.109 mm⁻¹, F(000)=752, and D_c=1.422 g cm⁻³. The thermal behavior and non‐isothermal decomposition kinetics of NDTAP were studied with DSC and TG‐DTG methods. The self‐accelerating decomposition temperature and critical temperature of thermal explosion are 195.5 and 208.2 °C, respectively. NDTAP presents good thermal stability and is insensitive.     

Optically Active 4‐Substituted (S)‐2‐Phenyl‐2‐oxazolines

(R)‐4‐Hydroxymethyl‐2‐phenyl‐2‐oxazoline (R)‐ 1 ) was prepared from (L)‐serine. The respective tosylate ((S)‐ 2 ) was converted into sulfides (S)‐ 4 and (S)‐ 5 , and sulfone (S)‐ 6 , useful starting materials for the elaboration of additional chiral centers. A previously reported [ α]_D ²⁵ value for (R)‐ 4 is corrected.     

Electrical and Thermal Conduction Behaviors in La‐Substituted GdBaCuFeO5+δ Ceramics

Gd_1?xLa_xBaCuFeO_5+δ polycrystalline ceramics have been prepared by a sol–gel method combined with the traditional ceramic processing. Analysis of the microstructure and phase composition reveals that the pure GdBaCuFeO_5+δ phase can be obtained even after the substitution of 50% La at Gd‐site. The band gap can be tuned from 1.47 to 1.36 eV by La substitution, resulting in a significant increase in the electrical conductivity. In addition, the total thermal conductivity can also be suppressed by the substitution of La at Gd‐sites. A ZT value of 0.02 at 1023 K is achieved in the 50% La‐substituted samples, which is over 20 times higher than that of the pure GdBaCuFeO_5+δ sample.     

Structural,optical, and thermodynamic properties of an LiCa2Mg2As3xV3−3xO12 solid-solution garnet

A series of LiCa₂Mg₂As_3xV_3−3xO₁₂ garnet powders (x = 0, 0.25, 0.50, 0.667, 0.75, and 1) were synthesized using solid-state reaction from mixed precursor powders. A complete solid-solution series was found between the endmembers. Energy-dispersive spectroscopy confirmed the homogeneity of the synthesized garnets. The compositions reversibly melted between 1000 and 1160°C and had low sintering temperatures between 650 and 900°C. Thermal diffusivity, heat capacity, thermal conductivity, density, lattice parameter, thermal expansion, index of refraction, and dispersion were measured from room temperature to 800°C.     

Effect of Li2O on the defect polarization in CuO‐added (K0.9Na0.1)NbO3 piezoelectric ceramics

CuO‐added (Li_xK_0.9?xNa_0.1)NbO₃ [C(L_xK_0.9?xN_0.1)N] ceramics with 0.0≤x≤0.05 were well‐sintered at 960°C for 6 hours. The lattice parameters of the specimens decreased with the addition of Li₂O. Defect polarization (P_D) formed between Cu²⁺ions and oxygen vacancies. Double polarization vs electric field (P‐E) hysteresis and sprout‐shaped strain vs electric field (S‐E) curves were observed in these specimens with a large strain of 0.16% at 7.0 kV/mm, possibly owing to the presence of P_D. When the P‐E curve was measured at temperatures higher than 75°C, the C(K_0.9N_0.1)N ceramic exhibited a normal P‐E hysteresis curve, whereas the C(L_0.04K_0.86N_0.1)N ceramic maintained the double P‐E hysteresis curve up to 125°C, indicating that Li₂O increased the thermal stability of P_D. The latter specimen also showed the sprout shaped S‐E curve with a strain of 0.15% at 7.0 kV/mm after 10⁴ cycles of a high electric field of 7.0 kV/mm.     

Effects of Gd Substitution on Sintering and Optical Properties of Highly Transparent (Y0.95−xGdxEu0.05)2O3 Ceramics

Highly transparent (Y_0.95?xGd_xEu_0.05)₂O₃ (x = 0.15–0.55) ceramics have been fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h with the in‐line transmittances of 73.6%–79.5% at the Eu³⁺ emission wavelength of 613 nm (~91.9%–99.3% of the theoretical transmittance of Y_1.34Gd_0.6Eu_0.06O₃ single crystal), whereas the x = 0.65 ceramic undergoes a phase transformation at 1650°C and has a transparency of 53.4% at the lower sintering temperature of 1625°C. The effects of Gd³⁺ substitution for Y³⁺ on the particle characteristics, sintering kinetics, and optical performances of the materials were systematically studied. The results show that (1) calcining the layered rare‐earth hydroxide precursors of the ternary Y–Gd–Eu system yielded rounded oxide particles with greatly reduced hard agglomeration and the particle/crystallite size slightly decreases along with increasing Gd³⁺ incorporation; (2) in the temperature range 1100°C–1480°C, the sintering kinetics of (Y_0.95?xGd_xEu_0.05)₂O₃ is mainly controlled by grain‐boundary diffusion with similar activation energies of ~230 kJ/mol; (3) Gd³⁺ addition promotes grain growth and densification in the temperature range 1100°C–1400°C; (4) the bandgap energies of the (Y_0.95?xGd_xEu_0.05)₂O₃ ceramics generally decrease with increasing x; however, they are much lower than those of the oxide powders; (5) both the oxide powders and the transparent ceramics exhibit the typical red emission of Eu³⁺ at ~613 nm (the ⁵D₀→⁷F₂ transition) under charge transfer (CT) excitation. Gd³⁺ incorporation enhances the photoluminescence and shortens the fluorescence lifetime of Eu³⁺.     

Effects of Gd2O3 and MgSiN2 sintering additives on the thermal conductivity and mechanical properties of Si3N4 ceramics

Si₃N₄ ceramics were prepared by gas pressure sintering at 1900°C for 12 h under a nitrogen pressure of 1 MPa using Gd₂O₃ and MgSiN₂ as sintering additives. The effects of the Gd₂O₃/MgSiN₂ ratio on the densification, microstructure, mechanical properties, and thermal conductivity of Si₃N₄ ceramics were systematically investigated. It was found that a low Gd₂O₃/MgSiN₂ ratio facilitated the thermal diffusivity of Si₃N₄ ceramics while a high Gd₂O₃/MgSiN₂ ratio benefited the densification and mechanical properties. When the Gd₂O₃/MgSiN₂ ratio was 1:1, Si₃N₄ ceramics obtained an obvious exaggerated bimodal microstructure and the optimal properties. The thermal conductivity, flexural strength, and fracture toughness were 124 W·m⁻¹·k⁻¹, 648 MPa, and 9.12 MPa·m^1/2, respectively. Comparing with the results in the literature, it was shown that Gd₂O₃-MgSiN₂ was an effective additives system for obtaining Si₃N₄ ceramics with high thermal conductivity and superior mechanical properties.     

Large Electrostrictive Strain in (Bi0.5Na0.5)TiO3–BaTiO3–(Sr0.7Bi0.2)TiO3 Solid Solutions

Relaxor ferroelectrics (0.94 ? x)(Bi_0.5Na_0.5)TiO₃–0.06BaTiO_3?x(Sr_0.7Bi_0.2□_0.1)TiO₃ (BNT–BT–xSBT) (0 ≤ x ≤ 0.5), were prepared by a solid‐state reaction process, and their structures were characterized by the transmission electron microscopy and Raman spectroscopy. The BNT–BT–0.3SBT has a very high electrostrictive strain S = 0.152% with hysteresis‐free behavior, much more than the reported S in other ferroelectrics. S–P² profiles perfectly follow the quadratic relation, which indicates a purely electrostrictive effect with a high electrostrictive coefficient (Q₁₁) of 0.0297 m⁴/C². Even, its Q₁₁ keeps at a high level in the temperature range from ambient temperature to 180°C. The field‐induced large electrostrictive strain of BNT–BT–0.3SBT was attributed to the existence of ferroelectric nanodomains.     

Effect of Gd Content on Luminescence Properties of Eu3+‐Doped La2−xGdxZr2O7 Transparent Ceramics

3 at.% Eu³⁺‐doped La_2?xGd_xZr₂O₇ (x = 0–2.0) transparent ceramics were fabricated by vacuum sintering. The effect of Gd content on crystal structure, in‐line transmittance, and luminescence property of the ceramics were investigated. The ceramics are all cubic pyrochlore structure with high transparency. The cut‐off edge of the transmittance curve of the ceramics varied with Gd content and was also affected by the annealing process. The luminescence intensity became stronger for the ceramics annealed in air. As Gd content increased, the energy band structure as well as the luminescence behavior of the ceramics was changed; in addition, the symmetry of the crystal lattice reduced, resulting in the shift of the strongest luminescence peak from 585 nm to around 630 nm.     

Thermophysical performances of Sm2O3-doped Gd3TaO7 oxides for thermal barrier coatings

To investigate the effect of Sm₃O₃ addition on the thermophysical performances of Gd₃TaO₇, (Gd_1−xSm_x)₃TaO₇ oxides were synthesised using sol-gel and sintering with high-temperature technologies, and their thermophysical properties were researched. The investigations exhibit that the obtained powders comprise well-distributed particles, and the bulk specimens have densified microstructures. The obtained ceramics have single pyrochlore-lattice. Owing to varied scattering strength coefficient of phonon caused by the differences in ionic radius and mass between the substituting and substituted elements, the value of thermal conductivity of (Gd_1−xSm_x)₃TaO₇ decreases firstly and further increases with the increase fraction of Sm₂O₃. The coefficient of thermal expansion of (Gd_1−xSm_x)₃TaO₇ is ameliorated owing to the higher ionic radius of Sm³⁺ than Gd³⁺. Except for Sm₃TaO₇, the synthesised ceramics display outstanding lattice steadiness up to 1400 °C.     

Structures and electrical conductivities of Gd3+ and Fe3+ co-doped cerium oxide electrolytes sintered at low temperature for ILT-SOFCs

Gd³⁺ and Fe³⁺ co-doped cerium oxide electrolytes, Ce_0.9Gd_0.1‐xFe_xO_2-δ (x?=?0.00, 0.01, 0.03, 0.05, 0.07, 0.10), were prepared by co-precipitation for ultrafine precursor powders and sintering for densified ceramic pellets. The crystal and microscopic structures were characterized by XRD, FESEM and Raman spectroscopy and their electrical properties were studied by AC impedance spectroscopy and the measurement of single cell's outputs. In comparison with Ce_0.9Gd_0.1O_1.95, the ceramic pellets of Ce_0.9Gd_0.1‐xFe_xO_2-δ with a relative density of 95% can be obtained after sintered at 1000?°C for 5?h, showing a remarkably enhanced sintering performance with a sintering temperature reduction of 500?°C, which might be ascribed to the highly activated migration of constituent species in the cerium oxide lattice doped with Gd³⁺ and Fe³⁺ions. Moreover, the electrical conductivity of Ce_0.9Gd_0.1‐xFe_xO_2-δ can be significantly enhanced depending on the mole fraction x, with Ce_0.9Gd_0.07Fe_0.03O_1.95 exhibiting the highest electrical conductivity of 38 mS/cm at 800?°C, about 36% higher than that of Ce_0.9Gd_0.1O_1.95 electrolyte sintered at 1500?°C for 5?h. So, The Gd³⁺ and Fe³⁺ co-doped cerium oxide would be an excellent candidate electrolyte for ILT SOFCs due to its prominent sintering performance and enhanced electrical conductivity.     

Preparation of polyethylene oxide/LixV2‐δO4‐δ nanocomposites

Polyethylene oxide (PEO)/LixV_2‐δO_4‐δ nanocomposites were prepared in aqueous solution. Characterization of the nanocomposites using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), powder X‐ray diffraction (XRD), and Fourier transform infrared spectrum (FTIR) shows that polymer chains intercalate inorganic host lamella and exhibit lattice expansion along the stacking direction of 4.2 Å. A possible model for the structure of the nanocomposite is also provided. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2162–2166, 2001     

Electrical transport and thermoelectric properties of Ca0.8Y0.2−xDyxMnO3−δ (0 ≤ x ≤ 0.2)

Ca_0.8Y_0.2?xDy_xMnO_3?δ (0≤x≤0.2) samples were fabricated by the solid‐state reaction method, and their thermoelectric properties were studied from 500°C to 800°C. Upon the substitution of Dy³⁺ for Y³⁺ in the Ca_0.8Y_0.2?xDy_xMnO_3?δ, the electrical and thermal conductivities gradually decreased with increasing Dy³⁺ concentration, whereas the absolute value of the Seebeck coefficient significantly increased. The Ca_0.8Dy_0.2MnO_3?δ showed the largest value of dimensionless figure of merit (0.180) at 800°C as a result of the combination of the largest absolute value of the Seebeck coefficient and the lowest thermal conductivity. We believe that the Ca_0.8Dy_0.2MnO_3?δ is a promising thermoelectric material at high temperatures.