Rapid synthesis of Gd2Zr2O7 glass-ceramics using spark plasma sintering

Glass-ceramics are possible host matrix for high level waste immobilization. The Gd₂Zr₂O₇ glass-ceramic matrix was successfully synthesized using spark plasma sintering (SPS) method in 5 minutes. The phase transition with sintering temperature was studied using X-ray diffraction, Raman and transmission electron microscopy. It revealed that samples kept a main defected fluorite phase as being sintered below 1800°C. Glass phase increased rapidly beyond 1850°C. The amorphous structure became the main body at 1900°C, with nanoscale crystal scattered in the bulk. With the increase of glass phase, the grain boundary became almost indistinguishable. The relationship between the final phase of Gd₂Zr₂O₇ with its synthetic temperature range and corresponding technology was reviewed. Gd₂Zr₂O₇ glass-ceramics could be acquired by extending the sintering temperature beyond 1850°C using SPS method.     

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.     

Formation of single-phase multicomponent zirconate with colossal atomic radius difference via reactive flash sintering

In this study, multicomponent rare-earth zirconate ceramics (Sm_0.2Eu_0.2Tb_0.2Dy_0.2Lu_0.2)₂Zr₂O₇ and (La_0.2Eu_0.2Gd_0.2Yb_0.2Y_0.2)₂Zr₂O₇ were synthesized via conventional sintering and reactive flash sintering, respectively. Single-phase (Sm_0.2Eu_0.2Tb_0.2Dy_0.2Lu_0.2)₂Zr₂O₇ ceramics, with the defect fluorite structure, were successfully obtained via conventional sintering and reactive flash sintering, while secondary phase segregation and precipitation were observed only in conventionally-sintered (La_0.2Eu_0.2Gd_0.2Yb_0.2Y_0.2)₂Zr₂O₇ ceramics. This study proposes that the critical electric field of reactive flash sintering introduces defects to soften the lattice, which not only improves the mass transportation, but also relieves the lattice stress induced by the atomic radius difference, resulting in the single-phase defect fluorite structure of (La_0.2Eu_0.2Gd_0.2Yb_0.2Y_0.2)₂Zr₂O₇. Thus, reactive flash sintering is an efficient route for synthesizing and developing novel multicomponent oxides that cannot be synthesized via conventional sintering due to pronounced lattice stress.     

Role of structural ordering on the radiation response of Gd2Zr2O7 pyrochlore

Complex oxides with pyrochlore and fluorite phases offer several advantages for the Immobilization of actinides or high-level radioactive wastes. In this report, we present the different behavior of structural ordering/crystallinity of Gd₂Zr₂O₇ (GZO) ceramics upon sintering at two different temperatures (1400°C–1500 °C). XRD and Raman spectroscopy studies revealed the enhancement of structural ordering/crystallinity with the increase of sintering temperature. Further, the ion irradiation experiments using 100 MeV iodine at the fluence of 1.0 × 10¹⁴ ions/cm² were performed to investigate the radiation effects on both GZO ceramics. The irradiation studies insinuate that the GZO ceramic sintered at 1500 °C possesses relatively better radiation resistance than GZO ceramic sintered at 1400 °C. The variation in the radiation resistance response of GZO ceramics seems associated with the different degrees of structural ordering. These results suggest the role of structural ordering in the radiation resistance response of GZO ceramics. The relatively better radiation tolerance of GZO15 ceramic with some extant pyrochlore phase ordering may be suitable for applications in harsh environments.     

Reactive flash sintering of high-entropy oxide (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7: Microstructural evolution and aqueous durability

Herein, the phase evolution, densification and grain growth process of the high entropy ceramics during flash sintering were systematically characterized and quantified to understand the microstructural evolution for the first time. It was demonstrated that the densification rate of (La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)₂Zr₂O₇ by flash sintering in this work was generally around 60 times that of conventional sintering at 1600 °C, while the grain growth rate by flash sintering was only around 1.5–6 times that of conventional sintering, indicating that grain growth was suppressed during flash sintering. The grain growth mechanisms by flash sintering and conventional sintering could be both attributed to surface diffusion and volume diffusion. In addition, the flash sintered high-entropy ceramics as promising immobilization materials for high-level radioactive waste (HLW) exhibited excellent aqueous durability with normalized leaching rates of Nd, Gd and Zr approximately 10^?6～10^?7 g m^?2 d^?1 after 42 days, which were much lower than most reported pyrochlore materials.     

Characterizations of vacuum sintered Gd2Zr2O7 transparent ceramics using combustion synthesized nanopowder

Highly transparent Gd₂Zr₂O₇ ceramic was fabricated by vacuum sintering using combustion synthesized nanopowder with mean particle size of about 80 nm. The morphology and structure were analyzed by X-ray diffractometer, scanning electron microscopy, Raman spectroscopy and transmission electronic microscopy. The Gd₂Zr₂O₇ nanopowder and transparent ceramic are both in low ordered pyrochlore structure. The effects of sintering temperature on the density and transmittance of Gd₂Zr₂O₇ ceramic were investigated, and the optimum sintering temperature (1825 °C) was obtained. Gd₂Zr₂O₇ transparent ceramic sintered at 1825 °C for 6 h shows the highest transmittance of 77.3 % and the average grain size of about 80 μm.     

Glycol-citrate synthesis of fine-grained oxides La2−xGdxZr2O7 and preparation of corresponding ceramics using FAST/SPS process

Single-phase superfine refractory oxides of composition La_2?xGd_xZr₂O₇ (x = 0, 0.5, 1, 1.5, 2) have been synthesized using glycol-citrate route. Dependencies of degree of dispersion and phase composition on chemical composition for such oxides were determined. Fluorite-pyrochlore transition observed during thermal treatment of these oxides was examined. It was stated that this transition occurred in the temperature range 1000–1200?°C for all formulations with exception of gadolinium zirconate Gd₂Zr₂O₇ which kept the fluorite structure even after long-term exposure (4?h) at a temperature of 1400?°С. Samples of corresponding ceramics which density amount to 95–98% of the theoretical value were obtained using FAST/SPS process. Coefficients of linear thermal expansion (CLTE) of manufactured materials were measured. It was found that CLTE values for all samples except for gadolinium zirconate were independent of temperature in the range 400–1000?°C. It was shown that Gd₂Zr₂O₇ kept the fluorite structure under conditions of FAST/SPS process at a temperature of 1600?°C.     

Gd2Zr2O7 ceramics synthesized by solid-state reactive sintering: Effects of starting powders with different-scale particle sizes

In this work, the effects of starting oxide powders with different-scale particle sizes on the synthesis of gadolinium zirconate pyrochlore (Gd₂Zr₂O₇, GZO) and its physical properties were studied. Micron Gd₂O₃ (μG), micron ZrO₂ (μZ), nano Gd₂O₃ (nG), and nano ZrO₂ (nZ) powders were used. GZO ceramics were prepared by employing solid-state reactive sintering at 1300 °C, 1400 °C, 1500 °C and 1600 °C with mixed powders of different sizes (μGμZ, μGnZ, nGμZ and nGnZ). X-ray diffraction and Raman analyses of the ceramics revealed that nG has a more significant impact on the crystallization process than nZ. All ceramics synthesized with different sized oxide powders crystallized into pyrochlore phases except for those synthesized with μGnZ mixed powders, which resulted in a fluorite phase. The results indicated that decreasing the particle size of only ZrO₂ to synthesize pyrochlore-phase Gd₂Zr₂O₇ with high crystallinity may not be effective. Samples obtained at 1500 °C were further analyzed. Scanning electron microscopy results revealed that all four ceramics have a non-homogeneous grain size and that the average grain size ranges from 5.40 to 8.30 μm. In addition, the density and Vickers hardness measurements showed that the use of nanopowders significantly improves the mechanical properties.     

Rapid preparation of Gd2Zr2−xCexO7 waste forms by flash sintering and their chemical durability

A simple and low-energy-consuming approach for preparing ceramic nuclear waste forms is greatly preferred for disposal of ever-increasing amounts of radioactive nuclear wastes. Herein, simulated radionuclide Ce could be rapidly incorporated into Gd₂Zr₂O₇ ceramic via flash sintering technique. Under an electric field of 250 V/cm, Gd₂Zr_2−xCe_xO₇ (0.0 ≤x ≤ 1.2) waste forms with a single phase of defect-fluorite were flash sintered at relatively low temperatures of 889–997 °C in 60 s. The onset temperature of flash sintering was decreased with the enhancement of Ce content. Furthermore, the density and grain size of Gd₂Zr_2−xCe_xO₇ waste forms were increased with the increase of the current limit. The nearly full dense Gd₂Zr_2−xCe_xO₇ waste forms were flash sintered at a current limit of 200 mA. The normalized leaching rates of Gd, Ce, and Zr in Gd₂Zr_0.8Ce_1.2O₇ after 28 d were 6.5475 × 10⁻⁵, 1.1624 × 10⁻⁷, and 1.1613 × 10⁻⁷ g·m⁻²·d⁻¹, respectively, which exhibited a good chemical durability.     

Preparation and fine thermal insulation performance of Gd2Zr2O7/ZrO2 composite fibers

Gd₂Zr₂O₇/ZrO₂ (GZC) composite fibers were prepared by electro-spinning method. The XRD, XPS and Raman results showed that there were three crystalline phases, tetragonal phase ZrO₂, cubic phase ZrO₂ and defect fluorite phase Gd₂Zr₂O₇ in GZC composite fibers. GZC fibers remained an intact fiber texture up to 1400 °C according to SEM photographs. The thermal conductivity of GZC fibers was between 0.173 W/(m·K) at 400 °C and 0.309 W/(m·K) at 800 °C, which was lower than that of 7YSZ under the same experimental conditions. The fiber sheet with density about 3.5 g/cm³ has thermal shrinkage less than 3% at 1400 °C. Hence, GZC fibers could be used as refractories for heat protection.     

Coprecipitation synthesis and sintering property of (YbxSm1-x)2Zr2O7 ceramic powders

Abstract

Abstract

(Yb_xSm_1-x)₂Zr₂O₇ (0<x<1·0) ceramic powders were synthesised with chemical coprecipitation and calcination method. Thermal decomposition behaviour of precipitates was studied by differential scanning calorimetry-thermogravimetry. The powders were characterised by X-ray diffractometry, scanning electron microscopy and transmission electron microscopy with energy dispersive spectroscopy. The synthesised powders have a particle size of about 100?nm, and exhibit to a certain extent agglomeration. The sintering behaviour of (Yb_xSm_1-x)₂Zr₂O₇ powders was studied by pressureless sintering method at 1550-1700°C for 10?h in air. The relative densities of (Yb_xSm_1-x)₂Zr₂O₇ ceramics increase with increasing sintering temperature, and reach above 95% when sintered at 1700°C for 10?h in air. Sm₂Zr₂O₇ and (Yb_0·1Sm_0·9)₂Zr₂O₇ ceramics have a pyrochlore structure; however, (Yb_xSm_1-x)₂Zr₂O₇ (0·3<x<1·0) ceramics exhibit a defective fluorite type structure.     

Effect of CaO doping on densification and microstructure control of highly transparent La0.4Gd1.6Zr2O7 ceramics

Calcium oxide (CaO) as sintering additive was first used to fabricate La_0.4Gd_1.6Zr₂O₇ transparent ceramics by a simple solid-state reaction and one-step vacuum sintering method. The effects of CaO dopant amount on the densification, as well as sintering behaviors and microstructure evolution of the as-fabricated La_0.4Gd_1.6Zr₂O₇ ceramics, were systematically investigated. Under the different sintering temperatures, the relationships during the sintering process between grain growth and zpore elimination were analyzed as well. It was found that 0.1 wt% CaO doping can effectively control the rate of grain growth and promote densification dominated by surface diffusion. Furthermore, Ca²⁺ entered the lattice of La_0.4Gd_1.6Zr₂O₇ ceramics to accelerate ion diffusion and suppress grain boundary migration. With the introduction of 0.1 wt% CaO doping, the highly transparent La_0.4Gd_1.6Zr₂O₇ ceramics (T = 80.4% at 1100 nm) were successfully fabricated at the traditional sintering temperature (1850°C).     

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.     

Ultrafast densification of high-entropy oxide (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 by reactive flash sintering

Pyrochlore-type high-entropy oxides (HEOs) are usually sintered at high temperatures for a long time to achieve full density. Herein, we synthesized pyrochlore-structured (La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)₂Zr₂O₇ HEOs with densities up to 99 % at a furnace temperature of 1200 °C in seconds via reactive flash sintering (RFS). The resultant HEOs achieved compositional uniformity at the atomic level and exhibited superior modulus, hardness and fracture toughness compared to the counterparts prepared by conventional solid-state sintering (at 1600 °C for 6 h). The underlying mechanisms for the ultrafast densification of the RFSed-HEOs were addressed in view of the roles of electric field, rapid heating, external pressure and internal reactions.     

Preparation of multicomponent A2Zr2O7 transparent ceramics by vacuum sintering

Recently, high-entropy oxide ceramics have become a hot topic in the field of high entropy materials. In this paper, multicomponent pyrochlore A₂Zr₂O₇ transparent ceramics were prepared via vacuum sintering using combustion synthesized nanopowders. The phase analysis results indicate that the powders exhibit defective fluorite structure and the ceramics are in pyrochlore structure. The structural order degree of ceramics varies with the increase of incorporated components. It is found that the grain size of A₂Zr₂O₇ ceramics is related with the component of A-site. The main fracture mode of final ceramics exhibit typical transgranular fracture. The multicomponent A₂Zr₂O₇ ceramics exhibit excellent optical transmittance, and the highest in-line transmittance reaches to 80% for #A2ZO ceramic at 1880 nm.     

Solid-state reactive sintering of La2-xGdxZr2O7 transparent ceramics and their optical properties

Transparent polycrystalline La_2-xGd_xZr₂O₇ (x = 0.4–2.0) ceramics were fabricated by solid-state reactive sintering using commercially available La₂O₃, Gd₂O₃ and ZrO₂ nanopowders as the raw materials. The phase composition, microstructure evolution, densification and optical transmittance of the resulting ceramics were investigated. XRD and Raman results reveal that both the powders and ceramics are in single-phase pyrochlore structure. With the promotion of Gd content, the disorder degree of pyrochlore structure increases gradually while the cell parameters decrease. The x = 1.0, 1.2 and 1.6 samples exhibit high optical transmittance in the 450 nm-6.0 μm range, and the La_0.4Gd_1.6Zr₂O₇ sample shows the highest transmittance of 83.84%. The transparent La_2-xGd_xZr₂O₇ ceramics with high optical quality are available as scintillator matrice and high temperature window material.     

High density nano-grained Gd2Zr2O7 ceramic prepared by combined cold and microwave sintering

In this study, nano-grained Gd₂Zr₂O₇ (NGZO) ceramic with a high relative density was prepared by a novel cold sintering process (CSP) assisted by microwave sintering (CSP-MS). The CSP with water as the liquid phase at 280 °C yielded nano-grained ceramic with a relative density of 71.5%. NGZO with a high relative density of 97.1% and average grain size of 73 nm was obtained by subsequent microwave sintering of the cold-sintered sample at 1300 °C. Therefore, CSP-MS is feasible in preparing dense NGZO ceramics with small grain sizes at relatively low sintering temperatures.     

Densifications and mechanical properties of single-phase Gd2Zr2O7 ceramic waste forms with improved TRPO waste load

A nitrate–citrate combustion method combined with microwave sintering was firstly employed for the rapid fabrication of the Gd₂Zr₂O₇ matrix immobilizing various amounts of simulated nuclear wastes. Phase evolutions, microstructure changes, element distributions, densification processes and mechanical properties of the as-prepared (1 – x)Gd₂Zr₂O₇·xTRPO (0.0 ≤ x ≤ 0.6) at various temperatures were investigated. Compared to the reported studies, we have increased the immobilization amount of simulated TRPO waste within a crystal structure from 45 to 60 wt%. T_d and T_g (the threshold temperatures to trigger accelerated densification and grain growth, respectively) were employed to divide the densification process into three stages. the mechanical properties and the densification stages of the (1 – x)Gd₂Zr₂O₇·xTRPO (0.0 ≤ x ≤ 0.6) ceramics sintered under microwave sintering at various temperatures were finally determined. Fine-grained (1 – x)Gd₂Zr₂O₇·xTRPO (0.0 ≤ x ≤ 0.6) ceramic waste forms with average grain size less than 200 nm and relative density higher than 90% can be obtained by microwave sintering at sintering temperature less than 1400 °C.     

Fabrication of Gd2O3‐MgO nanocomposite optical ceramics with varied crystallographic modifications of Gd2O3 constituent

The fabrication of Gd₂O₃‐MgO nanocomposite optical ceramics via hot‐pressing using sol‐gel derived cubic‐Gd₂O₃ and MgO nanopowders was investigated. The precursor powder calcined at 600°C had an average particle size of 12 nm. The effects of hot‐pressing temperature on constituent phases, microstructure, mid‐infrared transmittance, and microhardness were studied. The crystallographic modifications of Gd₂O₃ phase varied with the increase in sintering temperature from 1250 to 1350°C. The monoclinic‐Gd₂O₃ phase was retained for the composite sintered at 1350°C and the sample had an average grain size of 90 nm, excellent transmission (80.4%‐84.8%) over 3‐6 μm wavelength range, and enhanced hardness value of 14.1 GPa.     

The structure and electrical properties of lithium doped pyrochlore Gd2Zr2O7

The lithium-doped phases Gd_1.7Li_0.3Zr₂O_6.7 and Gd₂Zr_1.7Li_0.3O_6.55 with a pyrochlore structure were prepared by the modified Pechini method using citric acid and glycerol. Monitoring of the lithium content by using a nuclear microanalysis showed that a significant loss of lithium occurred after heat treatment above 1200 °C. Dense ceramics with a stoichiometric lithium content can be prepared by a low temperature microwave sintering (1100 °C). The introduction of lithium in the Gd-sublattice was accompanied by a decrease in the unit cell parameter (a = 10.5208 (1) Å vs 10.5346 (2) Å for Gd₂Zr₂O₇) and during doping at the Zr-sites with lithium, the cell parameter increased (10.5720 (1) Å). The doping in both cases led to an increase in the free cell volume. The impedance spectroscopy results showed that the bulk conductivity can be enhanced by the Li⁺-doping at the Gd³⁺-site by almost an order of magnitude. The sample Gd₂Zr_1.7Li_0.3O_6.55 had a conductivity lower than that of Gd_1.7Li_0.3Zr₂O_6.7 due to the possible trapping of oxygen vacancies by a high-charged acceptor defect LiZr???. The conductivity?pO₂ measurements showed that the Li-containing phase was a pure oxide-ion conductor at T < 800 °C.