Study on La2(Hf1-xTix)2O7 (x ≤ 0.20) pyrochlores for potential thermal/environmental barrier coating applications

Lanthanum hafnate (La₂Hf₂O₇) with a pyrochlore structure has excellent high temperature stability and low thermal conductivity, which is promising for thermal/environmental barrier coatings (T/EBCs) applications. To reduce its thermal expansion coefficient (TEC) so as to better match SiC_f/SiC composites, a smaller tetravalent dopant Ti⁴⁺ has been introduced in the Hf-sites to form La₂(Hf_1-xTi_x)₂O₇ (x ≤ 0.20). The phase composition and microstructure confirms that La₂(Hf_1-xTi_x)₂O₇ solid solutions possess a pure pyrochlore structure. With an increase of x, their TECs are decreasing consistently, whilst their thermal conductivities of La₂(Hf_1-xTi_x)₂O₇ are slightly increasing at high temperature but still much lower than those of meta-stable yttria partially stabilized zirconia, both of which are attributing to an increase of elastic modulus after Ti⁴⁺ doping on Hf-sites. The extremely excellent high temperature stability, relatively low thermal conductivities and low TECs suggest that La₂(Hf_1-xTi_x)₂O₇ is a prospective candidate material for T/EBC applications.     

Synthesis and thermophysical performances of (Nd1-xYbx)2AlTaO7 oxides for heat-insulation coating applications

A series of novel (Nd_1-xYb_x)₂AlTaO₇ oxides for thermal barrier coating application were synthesized exploring multi-step solid state clotting technology, the phase composition and thermophysical performances were analyzed. Results show that with increasing Yb₂O₃ content, the obvious phase transformation from weberite lattice to pyrochlore structure can be found. Owning to influence of oxygen vacancy, thermal conductivity of obtained products is less than that of 8YSZ. The thermal conductivity for (Nd_1-xYb_x)₂AlTaO₇ oxides decreases gradually with increasing Yb₂O₃ content, and (Nd_0.3Yb_0.7)₂AlTaO₇ has the lowest value. For (Nd_1-xYb_x)₂AlTaO₇ (x = 0, 0.1, 0.3) oxides, the lattice-energy has primary influence on thermal expansion coefficient, and electro-negativity governs the thermal expansion coefficient of (Nd_1-xYb_x)₂AlTaO₇ (x = 0.5, 0.7, 0.9 and 1) oxides. Thermal expansion coefficient of obtained oxides is close to that of 8YSZ.     

Potential of pyrochlore structure materials in solid oxide fuel cell applications

Pyrochlore structure material (A₂B₂O₇) has gained interest in diverse applications like catalysis, nuclear waste encapsulation, sensors, and various electronic devices due to the unique crystal structure, electrical property, and thermal stability. This review deals with the ionic/electronic conductivity of numerous pyrochlore structure materials (titanates, zirconates, hafnates, stannates, niobates, ruthenates, and tantalite based pyrochlore) as electrolyte and electrode materials for solid oxide fuel cells (SOFCs). The impact of cation radius ratio (r_A/r_B) on the lattice constant and oxygen ‘x’ parameter of different pyrochlore structure materials obtained by various synthesis methods are reported. Higher ionic conductivity is essential for better ion transport in an electrolyte, and mixed ionic and electronic conductivity in electrode is essential for attaining higher efficiency in a typical SOFC. Gd_xTi₂O_7-δ, Gd_2-xCa_xTi₂O_7-δ, Nd_2-yGd_yZr₂O₇, Y₂Zr₂O₇, Y₂Zr_2-xMn_xO_7-δ, SmDy_1-xMg_xZr₂O_7-x/2, Gd_2-xCa_xTi₂O_7-δ pyrochlore are reported as electrolytes for fuel cell applications. Some pyrochlore material (La_2-xCa_xZr₂O₇, Sm_2-xM_xTi₂O₇ (M = Mg, Co, and Ni) pyrochlore) shows protonic conductivity at lower temperatures and ionic conductivity at higher temperature condition. Also, the mixed ionic-electronic conductivity behavior is reported in electrode materials for SOFC such as R₂MnTiO₇ (R = Er and Y), R₂MnRuO₇ (R = Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y), R₂Ru₂O₇ (R = Bi, Pb and Y), Y_2-xPr_xRu₂O₇, Ni-(Gd_0.9Ca_0.1)₂Ti₂O_7-δ, (Gd_0.9Ca_0.1)₂Ti₂O_7-δ, Gd₂(Ti_0.8Ru_0.2)₂O_7-δ, (Sm_0.9Ca_0.1)₂Ti₂O_7-δ and (Y_0.9Ca_0.1)₂Ti₂O_7-δ pyrochlore. The detailed study of the electronic behavior of these pyrochlore system confirms the necessity of defect structure with high oxygen mobility, lower activation energy, ionic radii ratio criterion should satisfy, and possess notable ion-ion interaction. Ionic conductivity in pyrochlore is increased by enhancing the oxygen migration through 48f-48f site with the formation of oxygen vacancy. Vacancy formation can be achieved by adding a suitable dopant that creates oxygen vacancy by charge compensation mechanism or as anion Frenkel defects. Similarly, the electrical conductivity is improved while adding suitable dopant (Ce, Pr, Ru, etc.) due to disordered structure and anti-Frenkel defect formation which leads to oxygen vacancy formation and thus improves conductivity.     

Tuning of dielectric properties in Ti-Doped granular HfO2 nanoparticles for high-k applications

An array of titanium (Ti) doped HfO₂ [(Hf_1-xTi_xO₂) (x = 0.0–1.0)] nanoparticles (NPs) synthesis and the study of their structural, spectroscopic, and dielectric properties is reported. The Hf_1-xTi_xO₂ NPs were synthesized by a sol-gel type wet chemical process. The crystal structure of pure HfO₂ and TiO₂ NPs revealed by structural analysis is monoclinic (m) and tetragonal (t), respectively. The crystallinity of the doped samples was found to be dopant concentration-dependent. The microstructure of the obtained NPs was investigated along with their spectroscopic and dielectric characteristics. The tunable dielectric properties of Hf_1-xTi_xO₂ NPs make them ideal for high frequency, high-k applications.     

Near-infrared luminescent properties of Ln:LaGdZr2O7 (Ln = Nd,Yb) transparent ceramics for solid-state laser applications

Via a facile solid reactive method, transparent Ln_0.1La_0.9GdZr₂O₇ (Ln = Nd, Yb) ceramics were successfully fabricated for the first time. The highest in-line transmittances of Nd:LaGdZr₂O₇ and Yb:LaGdZr₂O₇ ceramics reached 68% and 69%, respectively, at 1100 nm. The microstructure and crystal structure of Ln_0.1La_0.9GdZr₂O₇ transparent ceramics were fully investigated, indicating that the solid reactive technique is a good method of industrially fabricating Ln_0.1La_0.9GdZr₂O₇ transparent ceramics. The PL spectra demonstrated that Ln_0.1La_0.9GdZr₂O₇ ceramics can effectively be excited at 808 nm and 976 nm, which correlates with the widely applied output wavelengths of AlGaAs and InGaAs laser diodes. The luminescence decay curves were also studied, showing that the average fluorescence lifetimes of Nd_0.1La_0.9GdZr₂O₇ and Yb_0.1La_0.9GdZr₂O₇ transparent ceramics was 355 μs and 663 μs, respectively. Combined with its high temperature resistance and good mechanical strength, Ln_0.1La_0.9GdZr₂O₇ (Ln = Nd, Yb) transparent ceramics can have potential applications in Nd/Yb solid-state laser construction.     

Low-temperature firing and microwave dielectric properties of MgNb2-xVx/2O6-1.25x ceramics

MgNb_2-xV_x/2O_6-1.25x (0.1≤x≤0.6) ceramics with orthorhombic columbite structures were prepared at low-temperature by a solid-phase process. The phase component, microscopic morphology, low-temperature sintering mechanism and microwave dielectric performance of MgNb_2-xV_x/2O_6-1.25x ceramics were comprehensively investigated. Low-temperature sintering densification of dielectric ceramics was achieved via the nonstoichiometric substitution of vanadium (V) at the Nb-site. In contrast to pure MgNb₂O₆ ceramics, the sintering temperature of MgNb_2-xV_x/2O_6-1.25x (x = 0.2) ceramics was reduced by nearly 300 °C owing to the liquid-phase assisted sintering mechanism. The liquid phase arises from the autogenous low-melting-point phase. Meanwhile, MgNb_2-xV_x/2O_6-1.25x (x = 0.2) samples with nonstoichiometric substitution could achieve a more than 900% improvement in the Q × f value, compared with stoichiometrically MgNb_2-xV_xO₆ (x = 0.1, 0.2) ceramics. Finally, MgNb_2-xV_x/2O_6-1.25x dielectric ceramics possess outstanding microwave dielectric properties: ε_r = 20.5, Q × f = 91000, and τ_f = -65 ppm/°C when sintered at 1030 °C for x = 0.2, which provides an alternative material for LTCC technology and an effective approach for low-temperature sintering of Nb-based microwave dielectric ceramics.     

Host sensitized photoluminescence in Sr2.9-3x/2LnxAlO4F: 0.1Eu3+ (Ln = Gd,Y) for innovative flexible lighting applications

Tetragonal structured Sr₃AlO₄F is highly strained as reported from its global instability index estimation. Moreover, our results of X-ray photoelectron spectroscopy (XPS) also ascertained that the structure of Sr₃AlO₄F is highly strained with oxygen vacancies. Herein, aliovalent substitutions of divalent Sr ions with trivalent Ln (Ln = Gd/Y) ions were carried out to improve the stability of Sr₃AlO₄F lattice, which subsequently enhanced the photoluminescence in a series of Sr_2.9-3x/2Ln_xAlO₄F: 0.1Eu³⁺ phosphors. All the phosphors showed intense red-orange emission (⁵D₀ → ⁷F_1,2) at excitation with UV and near-UV light. The critical concentrations of Gd³⁺ and Y³⁺ up to which the Eu³⁺ emission intensities increased linearly were observed to be x = 0.09 and x = 0.07, respectively. Nevertheless, further enhancement in the Eu³⁺ luminescence of the optimized phosphors was realized by subsequently annealing in low oxygen atmospheres. The enhancement in oxygen deficiency during the post-annealing in Ar or vacuum led the energy transfer (O^2--Eu³⁺) to a greater extent which afterward increased the Eu³⁺ luminescence. The optimized Sr_2.765Gd_0.09AlO₄F: 0.1Eu³⁺ and Sr_2.795Y_0.07AlO₄F: 0.1Eu³⁺ phosphors showed high red color purity (~99%), as well as CIE coordinates of (0.62, 0.38), indicated that these phosphors could be appropriate red-emitting components for making flexible optical films for many lighting devices. Therefore, flexible polydimethylsiloxane based films were also fabricated using optimized Sr_2.765Gd_0.09AlO₄F: 0.1Eu³⁺ phosphor. The electroluminescence of a flexible PDMS-phosphor composite film showed an intense and pure red color with good thermal stability suggesting its suitability in flexible lighting and display devices.     

Effect of substitution of La3+ on structural and electrical properties of Sr(Fe0.5Nb0.5)O3 ceramic

In this work, we have mainly reported the effect of lanthanum substitution on structural, dielectric, impedance and transport properties of strontium iron niobate (i.e., Sr_1-xLa_x(Fe_0.5Nb_0.5)_1-x/4O₃ (x = 0, 0.05, 0.1, 0.15, 0.2)). The materials were synthesized using standard ceramic technology. The preliminary structural analysis was done by using the room temperature X-ray diffraction data. The samples of higher concentrations (x = 0.15 and x = 0.20) show the development of an additional phase (i.e., LaNbO₄ and Sr₃La₄O₉). Studies of frequency and temperature dependence of dielectric parameters exhibit an anomaly and relaxor behavior in the compounds. The electrical impedance and modulus analysis of frequency and temperature-dependent data show the contributions of grains and grain boundaries in the resistive and capacitive properties of the compounds. The study of transport properties of AC conductivity has provided the conduction and relaxation mechanism. The substitution of La³⁺ has significantly changed the dielectric constant, tangent loss, and transport properties of the material.     

Densification,microstructure, and mechanical properties of V-substituted HfB2-based ceramics

This study firstly developed Hf_1-xV_xB₂ (x = 0, 0.01, 0.02, 0.05) powders, which were derived from borothermal reduction of HfO₂ and V₂O₅ with boron. The results revealed that significantly refined Hf_1-xV_xB₂ powders (0.51 μm) could be obtained by solid solution of VB₂, and x ≥ 0.05 was a premise. However, as the content of V-substitution for Hf increased, Hf_1-xV_xB₂ ceramics sintered by spark plasma sintering at 2000 °C only displayed a slight densification improvement, which was attributed to the grain coarsening effect induced by the solid solution of VB₂. By incorporating 20 vol% SiC, fully dense Hf_1-xV_xB₂-SiC ceramics were successfully fabricated using the same sintering parameters. Compared with HfB₂-SiC ceramics, Hf_0.95V_0.05B₂-20 vol% SiC ceramics exhibited an elevated and comparable value of Vickers hardness (23.64 GPa), but lower fracture toughness (4.09 MPa m^1/2).     

Facile one-pot synthesis of porous Ln2Ti2O7 (Ln = Nd,Gd, Er) with photocatalytic degradation performance for methyl orange

Porous nanocrystalline Ln₂Ti₂O₇ (Ln = Nd, Gd, Er) was prepared by a facile self-propagating combustion method using metal nitrates (Ln(NO₃)₃ (Ln = Nd, Gd, Er), TiO(NO₃)₂) and glycine. The photocatalytic activity of Ln₂Ti₂O₇ (Ln = Nd, Gd, Er) was evaluated by the photocatalytic degradation of methyl orange (MO). The results showed that the photocatalytic activity of Ln₂Ti₂O₇ (Ln = Gd, Er) with cubic pyrochlore structure was higher than that of Nd₂Ti₂O₇ with monoclinic perovskite structure and Gd₂Ti₂O₇ showed the best photocatalytic activity. The different photocatalytic activities observed for Ln₂Ti₂O₇ (Ln = Nd, Gd, Er) could be related to its different crystal structures and Ln 4f shells.     

Sr-induced color-tunable and thermal stability enhancing in the phosphor (Ba1-xSrx)9Lu2Si6O24:Eu2+ for solid-state lighting

Rare earth ions’ site occupation is significant for studying luminescence properties by changing the host composition. The (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ (x = 0-0.4) tunable-color phosphors were synthesized via a high temperature solid-state reaction. With the Sr²⁺ ions concentration increase, the luminescent color could be tuned from blue to green. This phenomenon is discussed in detail through the ions occupation in the host lattice. More importantly, the temperature-dependent luminescence of (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphors was investigated and exhibited excellent thermal stability. Furthermore, white LED device has been fabricated using (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphor mixed with commercial red phosphor Sr₂Si₅N₈:Eu³⁺ combined with a 370 nm UV-chip. This device showed correlated color temperature (CCT) of 5125 K and high color render index (CRI) of 91. This phosphor will be a promising candidate as a tunable-color phosphor for UV-based white LEDs.     

Eu-substitution-induced commensurate phase with enhanced ferroelectric property in Ba4(EuxLa1−x)2Fe2Nb8O30 multiferroics

Effects of Eu-substitution on the crystal structure, dielectric, ferroelectric, and magnetic properties have been systematically studied for Ba₄(Eu_xLa_1−x)₂Fe₂Nb₈O₃₀ (x = 0, 0.3, 0.5, 0.7, 0.9, 0.95, 1) tungsten bronze ceramics. The tetragonal bronze structure is confirmed in all compositions. With the increase of x, Ba₄(Eu_xLa_1−x)₂Fe₂Nb₈O₃₀ ceramics transform from paraelectric to ferroelectric. The compositions of x = 0.9, 0.95, and 1 show first-order ferroelectric phase transitions above room temperature (391 K for x = 0.9, 404 K for x = 0.95, and 425 K for x = 1). The ferroelectric behavior is associated with a commensurate octahedral tilting, which is caused by large A2-A1 ionic-radius difference. Magnetic hysteresis loops for all compositions at room temperature have been obtained, which could be ascribed to both the secondary phase and tungsten bronze structure per se. It is confirmed that the radius difference between A2 and A1 cations plays a critical role on the structure, dielectric, and ferroelectric characteristics.     

Room-temperature multiferroic properties of Al-doped hexaferrites sintered at high oxygen atmospheric concentrations

The room-temperature magnetoelectric effects of Al-doped polycrystalline hexaferrites Sr₃Co₂(Fe_1-xAl_x)₂₄O₄₁(x = 0.00, 0.02, and 0.04) sintered under high oxygen atmospheric concentrations were comprehensively investigated. The magnetic phases and magnetic structures were modulated by high sintering oxygen atmospheric concentrations as demonstrated by M-T tests and magnetic hysteresis loops. Compared with previous specimens sintered under low oxygen atmospheric concentrations, the transverse conical spin structures of the Sr₃Co₂(Fe_1-xAl_x)₂₄O₄₁(x = 0.00, 0.02, and 0.04) were obviously strengthened by high sintering oxygen atmospheric concentrations, exhibiting magnetoelectric effects in high magnetic field ranges (>1 T).     

Structural dependence of microwave dielectric properties in ilmenite-type Mg(Ti1-xNbx)O3 solid solutions by Rietveld refinement and Raman spectra

Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were prepared by the conventional solid-state reaction method. The phase composition, sintering characteristics, microstructure and dielectric properties of Ti⁴⁺ replacement by Nb⁵⁺ in the formed solid solution Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were systematically studied. The structural variations and influence of Nb⁵⁺ doping in Mg(Ti_1-xNb_x)O₃ were also systematically investigated by X-ray diffraction and Raman spectroscopy, respectively. X-ray diffraction and its Rietveld refinement results confirmed that Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics crystallised into an ilmenite-type with R-3 (148) space group. The replacement of the low valence Ti⁴⁺ by the high valence Nb⁵⁺ can improve the dielectric properties of Mg(Ti_1-xNb_x)O₃ (x = 0–0.09). This paper also studied the different sintering temperatures for Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics. The obtained results proved that 1350 °C is the best sintering temperature. The permittivity and Q × f initially increased and then decreased mainly due to the effects of porosity caused by the sintering temperature and the doping amount of Nb₂O₅, respectively. Furthermore, the increased Q × f is correlated to the increase in Ti–O bond strength as confirmed by Raman spectroscopy, and the electrons generated by the oxygen vacancies will be compensated by Nb⁵⁺ to a certain extent to suppress Ti⁴⁺ to Ti³⁺, which was confirmed by XPS. The increase in τ_f from ?47 ppm/°C to ?40.1 ppm/°C is due to the increment in cell polarisability. Another reason for the increased τ_f is the reduction in the distortion degree of the [TiO₆] octahedral, which was also confirmed by Raman spectroscopy. Mg(Ti_0.95Nb_0.05)O₃ ceramics sintered at 1350 °C for 2 h possessed excellent microwave dielectric properties of ε_r = 18.12, Q × f = 163618 GHz and τ_f = ?40.1 ppm/°C.     

Multiple magnetic phase transitions in NixMn1-xCo2O4

We prepared pure-phase Ni_xMn_1-xCo₂O₄ (x = 0, 0.25, 0.5, 0.75 and 1) nanoparticles using a low-temperature solid-state reaction method. Magnetization measurement results showed that with Ni doping, the Curie temperature and coercivity of Ni_xMn_1-xCo₂O₄ increased. Multiple magnetic phases that transition from paramagnetic to ferrimagnetic to ferrimagnetic and antiferromagnetic were observed to coexist in the Ni_0.5Mn_0.5Co₂O₄ sample. At low temperatures, the ferromagnetic and antiferromagnetic phases coexist in Ni_xMn_1-xCo₂O₄ (x = 0 and 0.25), and as the concentration of Ni increases, Ni_xMn_1-xCo₂O₄ (x = 0.75 and 1) show a spin glass state. The structure of Ni_xMn_1-xCo₂O₄ (x < 0.5) is mainly affected by cation defects, and by cation substitution when x is greater than 0.5. The results of first-principles calculations show that covalent bonds exist in Ni_xMn_1-xCo₂O₄ and that the strength of the Ni-O bond is greater than that of the Mn-O bond.     

Effect of Ta5+ doping on the thermal physical properties of defective fluorite Y3NbO7 ceramics

The effects of substituting the B cation in A₃BO₇ ceramics on their thermal physical properties were investigated by applying a large mass difference. Y₃(Nb_1-xTa_x)O₇ (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) ceramics were synthesized, and their structural characteristics were determined. All the fabricated Y₃(Nb_1-xTa_x)O₇ ceramics showed defective fluorite structures and glass-like low thermal conductivity (1.18−2.04 W/m∙K at 25°C) because of the highly distorted crystal structure and significant mass difference. Substitution with Ta⁵⁺ enhanced the sintering resistance, leading to superior thermal-insulating performance via grain boundary scattering. Furthermore, the ceramics exhibited excellent coefficients of thermal expansion, implying the promising applicability of Y₃(Nb_1-xTa_x)O₇ as new thermal barrier materials. The effect of mass difference on the thermomechanical properties of the ceramics was examined, suggesting a simple strategy for engineering the chemical composition of new thermal barrier materials.     

Influence of B-site substituent Ce on thermophysical,oxygen diffusion,and mechanical properties of La2Zr2O7

Pyrochlore-type La₂Zr₂O₇ (LZ) is a promising candidate for high-temperature thermal barrier coatings (TBCs). However, its thermal expansion coefficient and low fracture toughness are not optimal for such application and thus, need to be improved. In this study, we systematically report the effect of CeO₂ addition on phase formation, oxygen-ion diffusion, and thermophysical and mechanical properties of full compositions La₂(Zr₁?_xCe_x)₂O₇ (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1). La₂(Zr₁?_xCe_x)₂O₇ exhibits a pyrochlore structure at x ≤ 0.3, while a fluorite structure is observed outside this range. With the increase in CeO₂ content, thermal expansion coefficient and oxygen-ion diffusivity in La₂(Zr₁?_xCe_x)₂O₇ are increased. Oxygen-ion diffusivity of La₂(Zr₁?_xCe_x)₂O₇ is two orders of magnitude less than that of classical 8YSZ. Among La₂(Zr₁?_xCe_x)₂O₇ compounds, La₂(Zr_0.7Ce_0.3)₂O₇ and La₂(Zr_0.5Ce_0.5)₂O₇ exhibit relatively low oxygen diffusivities. The composition La₂(Zr_0.5Ce_0.5)₂O₇ presents the lowest thermal conductivity due to the strongest phonon scattering and also the highest fracture toughness due to the solid-solution toughening. The highest sintering resistance is achieved by the composition La₂(Zr_0.7Ce_0.3)₂O₇ because of its ordered pyrochlore structure and high atomic mass of Ce. Based on these results, the compositions La₂(Zr_0.5Ce_0.5)₂O₇ and La₂(Zr_0.7Ce_0.3)₂O₇ are alternatives for classical 8YSZ for TBC materials operating at ultrahigh temperatures.     

B-site acceptor doped AgNbO3 lead-free antiferroelectric ceramics: The role of dopant on microstructure and breakdown strength

B-site aliovalent modification of AgNbO₃ with a nominal composition of Ag(Nb_1-xM_x)O_3-x/2 (x = 0.01, M = Ti, Zr and Hf) was prepared. The effects of dopants on microstructure, dielectric, ferroelectric and conduction properties were investigated. The results indicate that the introduction of acceptor dopant does not lead to grain coarsening. Zr⁴⁺ and Hf⁴⁺ doping are beneficial to stabilize the antiferroelectric phase of AgNbO₃. Among all the samples, Ti⁴⁺ doped AgNbO₃ has the minimum resistivity while Hf⁴⁺ doped AgNbO₃ has the maximum resistivity, therefore, Hf⁴⁺ doped AgNbO₃ has high BDS. The XPS results indicate that the conduction behaviour is associated with the concentration of oxygen vacancies. This work hints that acceptor dopant is also effective on the microstructure control and chemical modification of AgNbO₃-based ceramics.     

Thermodynamic assessment of BaO–Ln2O3 (Ln = La,Pr, Eu,Gd, Er) systems

Heat capacities and enthalpies of formation of BaGd₂O₄ were determined by high-temperature differential scanning calorimetry and high-temperature oxide melt solution calorimetry, respectively. Thermodynamic stability of BaLn₂O₄ compounds increases with decreasing Ln³⁺ ionic radius. Previously reported data on BaNd₂O₄ and BaSm₂O₄ corroborate this trend. Missing data for compounds in BaO–Ln₂O₃ (Ln = La, Pr, Eu, Er) systems were estimated from established relations, thermodynamic assessment was performed, and binary phase diagrams were calculated.     

Low Thermal Conductivity of Rare‐Earth Zirconate‐Stannate Solid Solutions (Yb2Zr2O7)1−x(Ln2Sn2O7)x (Ln = Nd,Sm)

Dense monoliths of rare‐earth zirconate‐stannate solid solutions (Yb₂Zr₂O₇)_1?x(Ln₂Sn₂O₇)_x (Ln = Nd, Sm) were prepared by solid‐state reaction. Characterized by XRD, Raman, SEM, and TEM, a double‐phase structure of Yb₂Zr₂O₇‐rich fluorite and Nd₂Sn₂O₇‐rich pyrochlore was observed in the specimens of x = 0.4 and 0.5 of (Yb₂Zr₂O₇)_1?x(Nd₂Sn₂O₇)_x series while complete solid solutions were formed within the whole composition range of (Yb₂Zr₂O₇)_1?x(Sm₂Sn₂O₇)_x series. Except for the defect phonon scattering, lattice softening caused by order–disorder phase transformation between pyrochlore and fluorite structures also plays an important role in minimizing the thermal conductivity. Low thermal conductivity with positive temperature dependence is achieved in both the series. Considering the structure stability and low thermal conductivity, rare‐earth zirconate‐stannate solid solutions may be promising materials for thermal insulating applications, such as thermal barrier coatings.