Influence of doping Mg2+ or Ti4+ captions on the microstructures,thermal radiation and thermal cycling behavior of plasma-sprayed Gd2Zr2O7 coatings

Gadolinium zirconate (Gd₂Zr₂O₇) coatings doped by the transition metal Ti and the alkaline earth metal Mg were expected to have improved thermal radiation performance, which could be combined with their excellent thermal barrier properties to comprehensively improve the thermal insulating performance. The results show that the parent Gd₂Zr₂O₇ powder as well as the Gd-site and Zr-site substituted powders crystallize as pyrochlore Gd₂Zr₂O₇ in Fd-3m space group, while all the as-sprayed coatings have the combination of fluorite and a little part of pyrochlore phase. Gd₂Zr₂O₇ ceramic has high mid-infrared emittance and the addition of Ti⁴⁺ into Gd₂Zr₂O₇ can enhance the infrared absorption/emittance in a specific wavenumber range, dominantly in the near-infrared (0.75–2.5 μm) band due to the enhancement of electron transition induced by the impurity energy levels linked to the widening of the conduction band. The normal spectral infrared emissivity of Gd₂Zr₂O₇-based coating was higher than 0.88 at 1073 K. The monolayered doped Gd₂Zr₂O₇ coatings present very low thermal cycling lifetime, similar with the parent coating, mainly related with their low fracture toughness, despite (Gd_1-xMg_x)₂Zr₂O₇ series display lower thermal conductivity than the parent one.     

Phase evolution,microstructure and chemical stability of Ca1-xZr1-xGd2xTi2O7 (0.0 ≤ x ≤ 1.0) system for immobilizing nuclear waste

In order to ascertain the structural relationship of zirconolite and pyrochlore for their potential application in HLW immobilization, the Gd-doped zirconolite-pyrochlore composite ceramics (Ca_1-xZr_1-xGd_2xTi₂O₇) were systematically synthesized with x?=?0.0–1.0 by traditional solid-phase reaction method. The phase evolution and microstructure of the as-prepared samples have been elucidated by XRD and Rietveld refinement, Raman spectroscopy, BSE-EDS and HRTEM analysis. The results showed that zirconolite-2M, zirconolite-4M, perovskite and pyrochlore, four phases were identified in Ca_1-xZr_1-xGd_2xTi₂O₇ system and could be coexisted at x?=?0.4 composition. With the increase of Gd³⁺ substitution, the phase evolution was followed by zirconolite-2M→zirconolite-4M→pyrochlore. It is illustrated that the phase transformation from zirconolite-2M to zirconolite-4M was promoted by the preferential substitution of Gd³⁺ for Ca²⁺. And the solubility of Gd³⁺ in zirconolite-2M, zirconolite-4M and pyrochlore increased in sequence. The chemical stability test was also measured by the PCT leaching method. The normalized elemental release rates of Ca, Zr, Ti and Gd in Ca_1-xZr_1-xGd_2xTi₂O₇ system were fairly low and in the range of 10^?6?10^?8 g?m^?2 d^?1, which indicated a potential ceramics composite ensemble of CaZrTi₂O₇-Gd₂Ti₂O₇ system for nuclear HLW immobilization.     

Particle Size and Crystal Phase Dependent Photoluminescence of La2Zr2O7:Eu3+ Nanoparticles

Herein, La₂Zr₂O₇:5% Eu³⁺ nanoparticles (NPs) with different sizes have been synthesized for the first time through a modified facile molten salt process using a single‐source complex precursor of La(OH)₃·ZrO(OH)₂:Eu(OH)₃·nH₂O. It was found that the concentration of the added ammonia to co‐precipitate the corresponding metallic ions to form the precursor can influence the final particle size of the fluorite La₂Zr₂O₇:5%Eu³⁺ NPs. Furthermore, the crystal phase of the La₂Zr₂O₇:5%Eu³⁺ NPs was transferred from fluorite to pyrochlore after thermal treatment at 1000°C. The relationship between photoluminescence (PL), quantum yield (QY), particles size and crystal phase has been further investigated through fluorescence decay, site symmetry, and Judd–Ofelt (J–O) analysis. Specifically, PLQY and lifetime increase with increasing particle size of the fluorite La₂Zr₂O₇:5%Eu³⁺ NPs. Additionally, crystal phase transfer from fluorite to pyrochlore resulted in large PLQY decrease and moderate lifetime increase in the La₂Zr₂O₇:5%Eu³⁺ NPs.     

Free occupying mechanism of simulated tetravalent waste ions in Gd2Zr2O7 and performance evaluation of the waste forms

To extend the practicability of ceramics in immobilizing nuclear waste with fluctuant composition, structural design should be abandoned. The simulated tetravalent actinide waste An⁴⁺ (Ce⁴⁺) was directly doped into prepared Gd₂Zr₂O₇, and the waste forms were synthesized by high-temperature solid-state reaction. It has been shown that the maximum loading of CeO₂ in Gd₂Zr₂O₇ lies between 20 and 30 wt.%, and Ce elements are uniformly distributed in the matrix. Existing in Ce³⁺ and Ce⁴⁺, cerium ions automatically occupied both the Gd and Zr sites in Gd₂Zr₂O₇ according to valence equilibrium. This occupation causes the change of r(A³⁺)/r(B⁴⁺) and eventually leads to the structure transition from pyrochlore to fluorite. In addition, the normalized leaching rate of the sample with 60 wt.% of dopant was about 2.5 × 10⁻⁷ g m⁻² d⁻¹ on the 35th day. In this study, a free occupation of simulated waste ions in ceramics was proposed.     

Marked reduction in the thermal conductivity of (La0.2Gd0.2Y0.2Yb0.2Er0.2)2Zr2O7 high-entropy ceramics by substituting Zr4+ with Ti4+

The (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ (x = 0–0.5) high-entropy ceramics were successfully prepared by a solid state reaction method and their structures and thermo-physical properties were investigated. It was found that the high-entropy ceramics demonstrate pure pyrochlore phase with the composition of x = 0.1–0.5, while (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂Zr₂O₇ shows the defective fluorite structure. The sintered high-entropy ceramics are dense and the grain boundaries are clean. The grain size of high-entropy ceramics increases with the Ti⁴⁺ content. The average thermal expansion coefficients of the (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics range from 10.65 × 10^?6 K^?1 to 10.84 × 10^?6 K^?1. Importantly, the substitution of Zr⁴⁺ with Ti⁴⁺ resulted in a remarkable decrease in thermal conductivity of (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics. It reduced from 1.66 W m^?1 K^?1 to 1.20 W m^?1 K^?1, which should be ascribed to the synergistic effects of mass disorder, size disorder, mixed configuration entropy value and rattlers.     

Rapid synthesis of Gd2Zr2O7 ceramics by flash sintering and its aqueous durability

The high radiation resistance and long time stability of Gd₂Zr₂O₇ ceramics make it a promising candidate for high level waste (HLW) immobilization materials. In this study, single phase nanocrystalline Gd₂Zr₂O₇ was successfully synthesized and consolidated at temperatures around 1050 °C for only 1 min by flash sintering for the first time. The phase evolution and microstructural development during flash sintering were systematically studied and compared with the conventionally sintered samples. The flash sintered Gd₂Zr₂O₇ exhibit defect fluorite structure, and a following heat treatment at 1400 °C could transform the Gd₂Zr₂O₇ ceramics from defect fluorite phase into pyrochlore phase. The MCC-1 leaching test shows that the flash sintered Gd₂Zr₂O₇ samples exhibit good aqueous durability.     

Fabrication and characterization of novel excellent thermal-protection Gd2Zr2O7/ZrO2 composite ceramic fibers with different proportions of Gd2Zr2O7

Three kinds of Gd₂Zr₂O₇/ZrO₂ (GZC) composite fibers with different proportions of Gd₂Zr₂O₇ were prepared by electrospinning method through changing the amount of Gd³⁺ in precursor solutions. The thermal decomposition, crystallization process, high temperature stability and heat-conducting properties of GZC fibers were fully characterized. The results showed that there were three crystalline phases, tetragonal phase ZrO₂, cubic phase ZrO₂ and defect fluorite phase Gd₂Zr₂O₇ in all the GZC fibers. The content of Gd₂Zr₂O₇ increased gradually with the increase of Gd³⁺ in precursor solutions which led to the gradual slowing down of grain growth rate, the decrease of thermal conductivity and the increase of high temperature stability of the obtained composite fibers. The thermal conductivities of all the GZC fiber sheets were lower than that of 7YSZ fiber sheet. The sheets of all the GZC fibers could keep the high temperature stability up to 1300 °C.     

High capacity immobilization of U3O8 in Gd2Zr2O7 ceramics via appropriate occupation designs

An optimal occupation of U⁴⁺ and U⁶⁺ in Gd₂Zr₂O₇ is necessary for a really high immobilization capacity of U₃O₈ in Gd₂Zr₂O₇ based waste forms. Based on four kinds of occupation methods, a series of U₃O₈-doped Gd₂Zr₂O₇ compositions have been synthesized. The effects of U₃O₈ content on the phase and microstructure evolution of Gd₂Zr₂O₇ pyrochlore waste forms were investigated. Detailed XRD analysis show that the four sets of samples exhibit a single defect fluorite structure within the range of 0<x≤0.4, 0<x≤0.66, 0<x≤0.6 and 0<x≤1, respectively. The highest solubility of U₃O₈ is about 82.29 wt% when the occupation design (U⁴⁺ and U⁶⁺ substitute for Gd and Zr, respectively) was employed. It was found that the cell parameters of compounds in Set A (Gd_2–3x(U⁴⁺_xU⁶⁺_2x)Zr₂O_7+7x/2) decrease with increasing _x, while those of the other compositions increase. Moreover, the uranium are almost homogeneously distributed in all samples.     

Effects of heavy-ion irradiation on Gd2Zr2O7 bearing simulated TRPO waste

Considering the urgent demand of nuclear waste disposal, a comprehensive study on the irradiation performance of nuclear waste forms is extremely necessary, especially on those containing multiple-nuclides with multiple-valence. The irradiation effects of Gd₂Zr₂O₇ pyrochlore bearing simulated trialkyl phosphine oxides (TRPO) waste (consisting of ZrO₂, MoO₃, RuO₂ and PdO) were studied in this work. Gd_10.685Mo_4.734Zr_28.924Ru_1.000Pd_1.745O_91.825 and Gd_8.883Mo_9.901Zr_33.760Ru_2.089Pd_3.644O_118.368 were irradiated by 1.5?MeV Xe²⁰⁺ to fluences from 1?×?10¹² to 1?×?10¹⁵ ions/cm² at room temperature. The results showed an irradiation induced disordering with slight micro-swelling. In addition, the ion irradiation tolerance of the solid solutions decreased as the TRPO waste content increased. The decrease and shift of Raman peaks indicated the structural disordering and inner stress after irradiation. The micromorphology and element distribution of the irradiated surface remained almost unchanged. The structural evolution from pyrochlore to fluorite and even amorphous structure were disclosed in this study.     

An abnormal incorporation behavior of Th in Gd2Zr2O7: A first-principles study

A theoretical study of Th accommodation in Gd₂Zr₂O₇ has been performed by density functional theory. Our calculations show that although thorium has only one charge state of Th⁴⁺, it can be incorporated into both Gd³⁺ and Zr⁴⁺ sites in Gd₂Zr₂O₇, depending on the chemical environments. Th occupation at Gd³⁺ site results in charge redistribution and the excess electrons introduced by Th are transferred to the neighboring Zr ions. As compared with the pure state, Th-containing Gd₂Zr₂O₇ pyrochlores are probably more inclined to undergo order-disorder transformation and are less susceptible to radiation-induced amorphization.     

Effects of Gd3+ substitution on the structure,photoluminescence, scintillation,and thermometric features of Pr3+:Lu2Zr2O7 phosphors

In this study, it is shown how the photoluminescence, scintillation, and optical thermometric properties are managed via the introduction of Gd³⁺ ions into Pr³⁺:Lu₂Zr₂O₇. Raman spectra validate that partial replacement of Lu³⁺ with Gd³⁺ can promote the phase transition of Lu₂Zr₂O₇ host from the defective fluorite structure to the ordered pyrochlore one. Upon 289 nm excitation, all the samples emit the 483 (³P₀ → ³H₄), 581 (¹D₂ → ³H₄), 611 (³P₀ → ³H₆), 636 (³P₀ → ³F₂), and 714 nm (³P₀ → ³F₄) emissions from Pr³⁺ ions, which are enhanced with the addition of Gd³⁺ ions due to the modification of crystal structure. Dissimilarly, the X-ray excited luminescence spectra consist of a strong emission located at 314 nm from Gd³⁺ ions (⁶P_7/2 → ⁸S_7/2), together with the typical emissions from Pr³⁺ ions, which exhibit different dependences on the Gd³⁺ concentration. When the luminescence intensity ratio between the ³P₀ → ³H₆ (611 nm) and ¹D₂ → ³H₄ (581 nm) transitions is selected for temperature sensing, Pr³⁺:(Lu_0.75Gd_0.25)₂Zr₂O₇ shows the optimal relative sensing sensitivity of 0.78% K⁻¹ at 303 K, which is higher than that of the Gd³⁺-free sample. Therefore, the developed Pr³⁺:(Lu, Gd)₂Zr₂O₇ phosphors have the applicative potential for optical thermometry, X-ray detection, and photodynamic therapy.     

Phase Evolution and Microstructural Studies in CaZrTi2O7–Nd2Ti2O7 System

A series of compositions with general stoichiometry Ca_1?xZr_1?xNd_2xTi₂O₇ has been prepared by high‐temperature solid‐state reaction of component oxides and characterized by powder X‐ray diffraction and electron probe for microanalyses (EPMA). The phase fields in CaZrTi₂O₇–Nd₂Ti₂O₇ system and distribution of ions in different phases have been determined. Four different phase fields, namely monoclinic zirconolite, cubic perovskite, cubic pyrochlore, and monoclinic Nd₂Ti₂O₇ structure types are observed in this system. The 4M‐polytype of zirconolite structure is stabilized by substitution of Nd³⁺ ion. The addition of Nd³⁺ ions form a cubic perovskite structure‐type phase and thus observed in all the compositions with 0.05 ≤ x ≤ 0.80. Cubic pyrochlore structure‐type phase is observed as a coexisting phase in the nominal composition with 0.20 ≤ x ≤ 0.90. Only a subtle amounts of Ca²⁺ and Zr⁴⁺ are incorporated into the perovskite‐type Nd₂Ti₂O₇ structure. EPMA analyses on different coexisting phases revealed that the pyrochlore and perovskite phases have Nd³⁺‐rich compositions.     

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.     

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.     

Volcanic Ash‐Induced Decomposition of EB‐PVD Gd2Zr2O7 Thermal Barrier Coatings to Gd‐Oxyapatite,Zircon, and Gd,Fe‐Zirconolite

The resistance of EB‐PVD Gd₂Zr₂O₇ thermal barrier coatings against high‐temperature infiltration and subsequent degradation by molten volcanic ash is investigated by microstructural analysis. At 1200°C, EB‐PVD Gd₂Zr₂O₇ coatings with silica‐rich, artificial volcanic ash (AVA) overlay show a highly dynamic and complex recession scenario. Gd₂O₃ is leached out from Gd₂Zr₂O₇ by AVA and rapidly crystallizes as an oxyapatite‐type solid‐solution (Ca,Gd)₂(Gd,Zr)₈(Si,Al)₆O₂₆. The second product of Gd₂Zr₂O₇ decomposition is Gd₂O₃ fully stabilized ZrO₂ (Gd‐FSZ). Both reaction products are forming an interpenetrating network filling open coating porosity. However, first‐generation Gd‐oxyapatite and Gd‐FSZ are exhibiting chemical evolution in the long term. The chemical composition of Gd‐oxyapatite does evolve from Ca,Zr enriched to Gd‐rich. AVA continuously leaches out Gd₂O₃ from Gd‐FSZ followed by destabilization to the monoclinic ZrO₂ polymorph. Finally, zircon (ZrSiO₄) is formed. In addition to the prevalent formation of Gd‐oxyapatite, a Gd‐, Zr‐, Fe‐, and Ti‐rich oxide is observed. From chemical analysis and electron diffraction it is concluded that this phase belongs to the zirconolite‐type family (zirconolite CaZrTi₂O₇), exhibiting an almost full substitution Ca²⁺ + Ti⁴⁺ <> Gd³⁺ + Fe³⁺. As all Gd₂Zr₂O₇ decomposition products with the exception of ZrSiO₄ exhibit considerable solid solubility ranges, it is difficult to conclusively assess the resistance of EB‐PVD Gd₂Zr₂O₇ coatings versus volcanic ash attack.     

Response of structure and mechanical properties of high entropy pyrochlore to heavy ion irradiation

Material with superior damage tolerance, chemical durability, and structure stability is of increasing interest in high-level radioactive waste management and structural components for advanced nuclear systems. In this paper, high-entropy (La_0.2Ce_0.2Nd_0.2Sm_0.2Gd_0.2)₂Zr₂O₇ with pyrochlore-type structure was synthesized through conventional solid-state method. The as-synthesized high-entropy oxide maintained crystalline after being irradiated by using Au³⁺ with 9.0 MeV energy at the fluence of 4.5 × 10¹⁵ ions·cm^-2, indicating its high tolerance to heavy-ion irradiation. The irradiation-induced order-disorder transition from pyrochlore structure to defective fluorite structure occurred in high-entropy (La_0.2Ce_0.2Nd_0.2Sm_0.2Gd_0.2)₂Zr₂O₇. After irradiation, no irradiation-induced segregation was observed at grain boundary. Moreover, the mechanical properties of high-entropy pyrochlore were improved. The heavy-ion irradiation resistance mechanisms of high-entropy pyrochlore were discussed in detail. Our work identified high-entropy (La_0.2Ce_0.2Nd_0.2Sm_0.2Gd_0.2)₂Zr₂O₇ can be a promising candidate for immobilization of high-level radioactive waste as well as advanced nuclear reactor system from the perspective of irradiation resistance.     

Study on the crystal structure of (Gd2−xCex)Ti2O7 (0 ≤ x ≤ 0.8) pyrochlore

Synthesis, characterisation and crystal structure analysis studies of oxides in (Gd_2?x Ce_x)Ti₂O₇ series have been reported, Ce³⁺ used as a surrogate for Pu³⁺ because they have similar physical and chemical properties. In the present report, a series of pyrochlore-type crystal with composition (Gd_2?x Ce_x)Ti₂O₇ (0?≤?x?≤?0.8) were successfully synthesised by the solution combustion followed by high temperature calcining. The phase purity and crystal structure of samples were investigated by X-ray diffraction analysis as well as Rietveld refinement. It was observed that the solubility of Ce³⁺ in the lattice of Gd₂Ti₂O₇ pyrochlore is 39.62?mol.-%. The calculated lattice parameters and the simulated XRD patterns of (Gd_2?x Ce_x)Ti₂O₇ (x?=?0, 0.5, 1) were obtained based on the density functional theory. The results of theoretical calculation are quite consistent with the results of the experiment. Additionally, the grain size and the visual information about the microscopic structure of the (Gd_2?x Ce_x)Ti₂O₇ crystals were obtained by transmission electron microscopy.     

Phase evolution from Ln2Ti2O7 (Ln=Y and Gd) pyrochlores to brannerites in glass with uranium incorporation

Ln₂Ti₂O₇ (Ln=Y and Gd) pyrochlore glass‐ceramics have been fabricated successfully via internal crystallization. Subsequently, the phase evolution from Ln₂Ti₂O₇ pyrochlores to Ln_0.5U_0.5Ti₂O₆ brannerites in glass with uranium (U) substitutions on the Ln‐site of Ln₂Ti₂O₇ has been investigated using X‐ray diffraction, scanning electron microscope‐electron dispersive spectroscopy, transmission electron microscopy, Raman and diffuse reflectance spectroscopy. Combined characterization by XRD, SEM‐EDS and TEM SAED confirms the structures and phase evolution while Raman spectroscopy reveals characteristic vibration modes for both pyrochlore and brannerite. In addition, DRS of the U⁵⁺ ion has been used to probe the phase evolution, with the corresponding f‐f transition band of ²F_7/2 energy level significantly shifting to longer wavenumbers due to the local coordination environment changing from eightfold coordination in pyrochlore to sixfold coordination in brannerite.     

Preparation of Gd2Zr2O7 nanopowders by polyacrylamide gel method and their sintering behaviors

Well-crystallized and good-dispersed Gd₂Zr₂O₇ nanopowders with defect-fluorite structure are successfully prepared by the polyacrylamide gel method. The mole ratio of acrylamide/Gd and calcination temperature have the significant effects on the phase composition, particle size, and agglomeration degree of the Gd₂Zr₂O₇ nanopowders. The sintering behaviors of the as-prepared Gd₂Zr₂O₇ nanopowders are investigated at temperatures of 1200?1500 °C. The Gd₂Zr₂O₇ nanopowders can be sintered into dense ceramics with a high relative density of 98 % at 1500 °C for 2 h. Moreover, the defect-fluorite phase of Gd₂Zr₂O₇ transforms to pyrochlore phase of Gd₂Zr₂O₇ with the increase of sintering temperature. In addition, the two-step sintering is performed to prepare the Gd₂Zr₂O₇ nanoceramics using the as-prepared Gd₂Zr₂O₇ nanopowders as starting materials. This work presents a simple and industrially feasible approach for preparing the Gd₂Zr₂O₇ nanopowders with excellent sinterability.     

Improvement of Electrical Conductivity of Trivalent Rare‐earth Cation‐doped Neodymium Zirconate by Co‐doping Gadolinium and Ytterbium

Pyrochlore oxides of A₂Zr₂O₇, where A represents trivalent rare‐earth elements, have a high electrical conductivity, which makes them suitable for applications as high‐temperature solid electrolytes. The influence of Gd and Yb cations co‐doping at the Nd site on structure and electrical conductivity of a pyrochlore oxide Nd₂Zr₂O₇ is investigated using X‐ray diffraction and impedance spectra measurements. Different zirconate ceramics of Nd₂Zr₂O₇, Nd_1.8Gd_0.2Zr₂O₇, Nd_1.8Gd_0.1Yb_0.1Zr₂O₇, Nd_1.4Gd_0.6Zr₂O₇ and Nd_1.4Gd_0.3Yb_0.3Zr₂O₇ are prepared by pressureless‐sintering method at 1,973 K for 10 h in air. Nd₂Zr₂O₇ doped with Gd and Yb cations at the Nd site exhibit a single phase of pyrochlore‐type structure. The measured values of the total conductivity obey the Arrhenius relation. Nd₂Zr₂O₇ and its doped zirconate ceramics are oxide‐ion conductors in the oxygen partial pressure range of 1.0 × 10^–4 to 1.0 atm at all test temperature levels. The total conductivity increases with reducing average ionic radii of A‐site rare‐earth cations. The dual Yb+Gd intermix doping causes a distinctly enhanced total conductivity as compared to unmodified Nd₂Zr₂O₇ and singly Gd‐doped zirconate ceramics. The highest total conductivity value obtained in this work is 1.02 × 10^–2 S cm × ¹ at 1,173 K for Nd_1.4Gd_0.3Yb_0.3Zr₂O₇ ceramic.