The quantum phase transition between Z_(2) plaquette valence bound solid(PVBS) and superfluid(SF) phases on the planar pyrochlore lattice(square ice) is under debate. To gain further insight, here, we focus on the dyn...The quantum phase transition between Z_(2) plaquette valence bound solid(PVBS) and superfluid(SF) phases on the planar pyrochlore lattice(square ice) is under debate. To gain further insight, here, we focus on the dynamical features of the hard-core Bose–Hubbard model on this lattice and study the excitation spectra by combining stochastic analytic continuation and quantum Monte Carlo simulation. In both PVBS and SF phases,a flat band with bow-tie structure is observed and can be explained by certain symmetries. At the transition point,the spectra turn to be continuous and gapless. A(2+1)-dimensional Abelian–Higgs model with mixed 't Hooft anomaly is proposed to describe the transition, where the anomaly matching predicts that the deconfinement can exist on the domain walls. From the snapshot of the spin configuration in real space, we found the existence of the domain wall. We also found that the spectrum along a specific path in momentum space from PVBS phase to the transition point can be well described by an XXZ spin chain, and the critical theory of XXZ spin chain matches the anomaly. The two-spinon continuum along this specific path implies additional domain walls(point defect) can emerge in the domain walls(line defect) and take the role of deconfinement at the transition point.展开更多
The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human he...The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human health.To address this issue,heterogeneous photocatalysis emerges as a promising strategy for breaking down recalcitrant molecules.However,efforts are required to develop efficient and stable photocatalysts capable of operating under visible light.This study explores the photocatalytic potential of Fe-doped RE_(2)Zr_(2)O_(7-δ)(RE=Pr,Sm,Nd,Y)compositions,synthesized through the microwaveassisted solvothermal method,for the degradation of methylene blue.Characterizations,such as X-ray diffraction(XRD)and Raman spectroscopy,reveal the obtention of single-phase ordered pyrochlore for RE=Pr,Sm and Nd or defect fluorite structures for Y.Photocatalytic tests under visible light demonstrate efficient dye degradation for all Fe-doped samples,Y_(2)Zr_(1.9)Fe_(0.1)O_(6.95)(YZF)defect fluorite being the one that exhibits the highest efficiency.Radical scavenging experiments identify hydroxyl radicals as key contributors to the degradation process,along with photoinduced holes.These materials exhibit minimal leaching of iron ions,confirming their stability,and the best material,YZF,demonstrates effective reusability.The results highlight the potential of Fe-doped RE_(2)Zr_(2)O_(7)compositions as an efficient alternative for application as photocatalysts for the degradation of azo dyes under visible light.展开更多
Low thermal conductivity and excellent mechanical strength are essential to pyrochlore A2B2O7 ceramic for environmental/thermal barrier coating applications.To collaboratively tailor the mechanical and thermal propert...Low thermal conductivity and excellent mechanical strength are essential to pyrochlore A2B2O7 ceramic for environmental/thermal barrier coating applications.To collaboratively tailor the mechanical and thermal properties of A2B2O7 ceramic,a novel high entropy pyrochlore ceramic(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) with significant atomic radius and mass fluctuation is proposed by simultaneously introducing various elements with different valence states at A and B cation sites.The as-synthesized(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) exhibits enhanced fracture toughness(1.68 MPa m^(1/2)),amorphous-like low thermal conductivity(1.45 W m^(-1) K^(-1) at 900℃)and matched thermal expansion coefficient(9.0×10^(-6) K^(-1) at 1200℃)with Al_(2)O_(3)/Al_(2)O_(3) CMCs.The extensive misfits in atomic weight,ionic radius among the substitutional cations in combination with the intrinsic oxygen vacancies in the anion sublattice play significant roles in the thermal conductivity reduction of(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) ceramic.The combination of outstanding mechanical and thermal properties indicates that this type of material has a good application prospect for environmental/thermal barrier coatings.展开更多
The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin...The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin-one Haldane chains associated with an orbital ordering of Ru-4d electrons.With an aim to tune and access distinct ground states with strong entanglements of multiple degrees of freedom,i.e.,spin,orbital,charge,and lattice,we utilize a high-pressure approach to regulate the MIT of this system.Our detailed resistivityρ(T) measurements on the polycrystalline Tl_(2)Ru_(2)O_(7) samples under various hydrostatic pressures indeed reveal an unusual evolution of the electronic ground states.At first,the MIT is suppressed monotonically from 120 K at ambient to about 70 K at 1.5 GPa and then vanishes suddenly at about 1.8 GPa without achieving a metallic ground state.Meanwhile,the system evolves into a semiconducting ground state with magnitude ofρ(T) in the entire temperature range enhanced gradually by further increasing pressure.Prior to the abrupt disappearance of MIT,a new electronic order manifested as a kink-like anomaly inρ(T) emerges at T_(0)>T_(MIT) at 1.2 GPa and it continues to increase with pressure,producing a tricritical-point-like behavior in the T–P phase diagram of Tl_(2)Ru_(2)O_(7).The presence of two successive transitions at T_(0 )and T_(MIT )in the pressure range 1.2–1.5 GPa indicates an inhomogeneous electronic state nearby the tricritical point.At P≥3 GPa,another broad anomaly emerges inρ(T) at T_(1)>T_(0),and T_(1)continuously increases with pressure,dividing the semiconductingρ(T) into distinct thermally activated regions.These rich phenomena in the pressurized Tl_(2)Ru_(2)O_(7) should originate from the complex interplay of strongly entangled multiple quantum degrees of freedom in the system near the localized-to-itinerant crossover regime.展开更多
The properties of high entropy pyrochlore have been studied extensively,but there is no consistent conclusion on its radiation tolerance.Besides,the mechanism of the high entropy effect on the radiation tolerance of p...The properties of high entropy pyrochlore have been studied extensively,but there is no consistent conclusion on its radiation tolerance.Besides,the mechanism of the high entropy effect on the radiation tolerance of pyrochlore is still unclear.In this work,combined with experiments and calculations of pyrochlores with similar cationic radius ratios,the A-site and B-site high entropy effects on structural evolution under irradiation are analyzed.In situ irradiation experiments were carried out on A-site high entropy pyrochlores such as(La_(0.2)Nd_(0.2)Sm_(0.2)Gd_(0.2)Er_(0.2))_(2)Zr_(2)O_(7),B-site Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7),and ternary pyrochlore Sm_(2)Zr_(2)O_(7) and Gd_(2)Sn_(2)O_(7) for comparison.The A-site high entropy pyrochlore can maintain a stable structure under high fluence irradiation like corresponding ternary pyrochlore,demonstrated by high angle annular dark field scanning transmission electron microscopy(HAADF-STEM),energy dispersive spectroscopy(EDS)mapping and Raman spectrum.The additional irradiation experiments on A-site high entropy pyrochlores(La_(1/3)Nd_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) and(Nd_(1/3)Sm_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) also confirm the similarity under irradiation between A-site high entropy and ternary pyrochlores.However,the B-site high entropy pyrochlore Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7) becomes amorphous at exceptionally low irradiation fluences,indicating a significantly distinct radiation tolerance compared with the A-site high entropy.The difference between the A-site and B-site high entropy effect is analyzed from cationic lattice distortion,bond strength,and inner electron binding energy by first-principles calculations.The results reveal the role and mechanism of the high entropy effect in pyrochlores and lay a foundation for material design and future applications.展开更多
Hydroxycalciopyrochlore,ideally （Ca,Na,U,□）2（Nb,Ti）2O6（OH）,cubic,is a new mineral species （IMA2011-026） within the pyrochlore supergroup that was found occurring at the Maoniuping mine,Mianning County,Xichang...Hydroxycalciopyrochlore,ideally （Ca,Na,U,□）2（Nb,Ti）2O6（OH）,cubic,is a new mineral species （IMA2011-026） within the pyrochlore supergroup that was found occurring at the Maoniuping mine,Mianning County,Xichang prefecture,Sichuan Province,southwest China.The mineral is found in an alkali feldspar granite rare-earth ore deposit （26-27 Ma）.Associated minerals include calcite,barite,celestine,albite,aegirine,aegirine-augite,fluorite,parasite-（Ce）,thorite,thorianite,zircon,galena,sphalerite,magnetite,and pyrite.Crystals occur mostly as octahedra,and less often as dodecahedra and tetrahexahedra or combinations thereof.Some occur with an allotriomorphic habit with a thick triangular tabular form.Crystals generally range from 0.1 to 1 mm in size.The mineral is brownishblack,greenish-black and black on fresh sections with a brown streak.The crystal is translucent,and has a greasy lustre on fresh sections.It is metamict without any observed parting or cleavage and with a conchoidal fracture.The Vickers microhardness is 572 kg/mm2 （5-6 on the Mohs hardness scale）.The density measured by hydrostatic weighing is 5.10（3） g/cm3.The strongest four reflections in the X-ray powder-diffraction pattern [d in（A） （Ⅰ） hkl] are：2.9657 （100） 2 2 2,1.8142 （34） 0 4 4,1.5463 （21） 2 2 6,2.5688 （18） 0 0 4.The unit-cell parameters are a =10.381（4） （A）,V=1118.7（7）（A）3,Z =8.The structure was solved and refined in the space group Fd3m with R =0.09.The empirical formula is （Ca0.74Na0.5sU0.40Ce0.05Fe0.02□0.21）2.00（Nb1.15Ti0.s0Ta0.03Al0.01Mg0.01）2.00O6.02 [（OH）1.01F0.09]1.10,on the basis of 2 atoms of B pfu; the simplified formula is （Ca,Na,U,□）2（Nb,Ti）2O6（OH）.Type material is deposited in the Geological Museum of China,Beijing,People＇s Republic of China,catalogue number M11800.展开更多
A2B2O7 pyrochlore is a kind of important functional materials for different purposes,which has been investigated extensively by crystallographers and material scientists.However,the catalytic chemistry of this type of...A2B2O7 pyrochlore is a kind of important functional materials for different purposes,which has been investigated extensively by crystallographers and material scientists.However,the catalytic chemistry of this type of special compounds has rarely been documented,though a few researchers have tried to synthesize some pyrochlore compounds with different chemical compositions for a variety of green energy production and air pollution control reactions in the history.With the expectation to help catalysis scientists to get better acquaintance with,and gain deeper understanding on this type of compounds as heterogeneous catalysts,the major publications over the past several decades have been screened and reviewed in this paper,based also on our own experience of studying on this type of catalytic materials.The crystalline phase transformations of the compounds with the change of the A and B site cations,the phase change’s influences on the surface and bulk properties,and their subsequent impact on the catalytic performance for different reactions have been summarized.Furthermore,the future work which needs to be performed to perceive in depth this kind of important materials as catalysts has been proposed and suggested.We trust that this short review contains valuable information,which will provide great help for people to get better cognition for A2 B2 O7 pyrochlore compounds,and assist them to develop better catalysts for various reactions.展开更多
Pyrochlore titanate oxides, R2Ti2O7（R=Gd3＋, Tb3＋, Dy3＋）, were synthesized under mild hydrothermal conditions. The crystal growth of pyrochlore titanate oxides and taking place of chemical reaction in the hydrothe...Pyrochlore titanate oxides, R2Ti2O7（R=Gd3＋, Tb3＋, Dy3＋）, were synthesized under mild hydrothermal conditions. The crystal growth of pyrochlore titanate oxides and taking place of chemical reaction in the hydrothermal processing were sensitive to the alkalinity, temperature, reaction time, the nature of the rare earth ion and the composition of initial reaction mixture. The as-prepared samples were characterized by powder X-ray diffraction, scanning electron microscopy, Raman spectrum and variable temperature dc magnetic susceptibility（Superconductivity quantum interference device, SQUIDS）. The magnetic studies gave 7.29×10-23 A·m2/Gd3＋ and -8.28 K, 8.75×10-23 A·m2/ Tb3＋ and -19.7 K, and 8.85×10-23 A·m2/Dy3＋ and 0.84 K effective moments and Weiss constants for Gd2Ti2O7, Tb2Ti2O7 and Dy2Ti2O7, respectively.展开更多
Various excellent properties of rare earth zirconate and stannate pyrochlores are close related with their native point defects.First-principles calculations are performed to systematically investigate the point defec...Various excellent properties of rare earth zirconate and stannate pyrochlores are close related with their native point defects.First-principles calculations are performed to systematically investigate the point defect mechanism and the oxygen diffusion behavior of A_(2)B_(2)O_(7)(A=La,Ce,Pr,Nd,Pm,Sm,Eu,Gd;B=Zr,Sn).The possible defect complexes and their associated reactions under stoichiometric and nonstoichiometric conditions are explored.The O Frenkel pairs are the most stable defect structure in stoichiometric zirconates,whereas the cation antisite defects are the predominant one in stoichiometric stannates.In the case of BO_(2) excess zirconates and stannates,the BA cation antisite defect with the A vacancy and/or the oxygen interstitial is energetically favorable,whereas the ABantisite defect together with the oxygen vacancy and/or the A interstitial is preferable under the A_(2)O_(3) excess condition.Meanwhile,the maximum point defect concentrations of zirconates are much higher than those of stannates.Furthermore,the oxygen migration barriers are similar in these compounds,ranging in 0.68 eV–0.80 eV.The predicted point defects and oxygen diffusion mechanisms play the critical role in their engineering applications and are expected to guide the future property improvement of pyrochlores through the control of point defects and/or composition.展开更多
High entropy pyrochlores(HEP)are potential candidates as dispersoids in the oxide dispersed strengthened steels or alloys,which can be used in nuclear reactors and supercritical boilers.For the first time,HEP oxides Y...High entropy pyrochlores(HEP)are potential candidates as dispersoids in the oxide dispersed strengthened steels or alloys,which can be used in nuclear reactors and supercritical boilers.For the first time,HEP oxides Y_(2)(TiZrHfMoV)_(2)O_(7) were synthesized with Y_(2)Ti_(2)O_(7) as a base structure with the B site(Ti)substituted with five cations through reverse co-precipitation technique in the nanocrystalline form at lowest synthesis temperature.The synthesis parameters for Y_(2)(TiZrHfMoV)_(2)O_(7)(5C)and other derived compositions(five compositions of four cationic systems with each cation eliminated at B site from 5 C)are optimised to obtain lower crystallite and particle sizes.5C has a smaller crystallite size(27 nm)than other single-phase compositions.The cation’s influence,oxidation state,and oxygen vacancy in the phase formation were analysed through XPS.The single-phase HEPs are consolidated through spark plasma sintering.Y_(2)(TiZrHfMo)_(2)O_(7)(4 C-V)shows the highest hardness among the compositions reported so far due to its finer grain size,and Y_(2)(TiHfMoV)_(2)O_(7)(4 C-Zr)has a higher Young’s modulus compared to other single-phase composition due to its higher degree of order in the structure.展开更多
A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic propertie...A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic properties of ideal Lu2Sn207 pyrochlore. The results are in excellent agreement with available experimental measurements. Density of states （DOS） of this compound was presented and analysed. We also notice the presence of the hybridization between oxygen and Lu metal. The band structure calculations show that the compound has direct band gap of 2.67 eV at the F point in the Brillouin zone and this indicates that the material has a semi-conducting feature.展开更多
To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO lo...To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO loadings were fabricated and characterized by different techniques and density functional theory calculations.In these catalysts,a spontaneous dispersion of CuO on the La_(2)Sn_(2)O_(7)pyrochlore support formed,having a monolayer dispersion capacity of 1.90 mmol CuO/100 m^(2) La_(2)Sn_(2)O_(7)surface.When loaded below this capacity,CuO exists in a sub-monolayer or monolayer state.X-ray photoelectron spectroscopy(XPS),Raman spectroscopy,and Bader charge and density of states analyses indicate that there are strong interactions between the sub-monolayer/monolayer CuO and the La_(2)Sn_(2)O_(7)support,mainly through the donation of electrons from Cu to Sn at the B-sites of the structure.In contrast,Cu has negligible interactions with La at the A-sites.This suggests that,in composite oxide supports containing multiple metals,the supported metal oxide interacts preferentially with one kind of metal cation in the support.The Raman,in situ diffuse reflectance infrared Fourier transform spectroscopy,and XPS results confirmed the formation of both O2^(-)and O2^(2-)as the active sites on the surfaces of the CuO/La_(2)Sn_(2)O_(7)catalysts,and the concentration of these active species determines the soot combustion activity.The number of active oxygen anions increased with increase in CuO loading until the monolayer dispersion capacity was reached.Above the monolayer dispersion capacity,microsized CuO crystallites formed,and these had a negative effect on the generation of active surface oxygen sites.In summary,a highly active catalyst can be prepared by covering the surface of the La_(2)Sn_(2)O_(7)support with a CuO monolayer.展开更多
We perform a detailed investigation of the new ＇breathing＇ pyrochlore compound LiInCr4O8 through Rh substi- tution with measurements of magnetic susceptibility, specific heat, and x-ray powder diffraction. The antif...We perform a detailed investigation of the new ＇breathing＇ pyrochlore compound LiInCr4O8 through Rh substi- tution with measurements of magnetic susceptibility, specific heat, and x-ray powder diffraction. The antiferro- magnetic phase of LiInCr4O8 is found to be slowly suppressed with increasing Rh, up to the critical concentration of x = 0.1 where the antiferromagnetic phase is still observed with the peak in specific heat Tp = 12.5 K, slightly lower than Tp =14.3 K for the x = 0 compound. From tile measurements of magnetization we also uncover evidence that substitution increases the amount of frustration. Comparisons are made with the LiGayIn1-yCr4O8 system as well as other frustrated pyrochlore-related materials and comparable amounts of frustration are found. The results of this work show that the engineered breathing pyrochlores present an important method to further understand the complex magnetism in frustrated systems.展开更多
The phase of pyrochlore Gd_2Zr_2O_7 used for immobilization of Pu （Ⅳ） was investigated, tetravalent cerium was used as the simulacrum for plutonium with tetravalence, and the compounds in the system Gd_2Zr_2-_xCe_x...The phase of pyrochlore Gd_2Zr_2O_7 used for immobilization of Pu （Ⅳ） was investigated, tetravalent cerium was used as the simulacrum for plutonium with tetravalence, and the compounds in the system Gd_2Zr_2-_xCe_xO_7 （0.0≤x≤2.0） were synthesized via a high temperature solid reaction method with Gd_2O_3 and ZrO_2 powders being used as the starting materials. Based on the collected XRD data of the gained samples, the phase and microstructural change of compounds were calculated by means of rietveld structural refinement method. The experimental results indicated that the phases of compounds were changed from pyrochlore to fluorite-type phase with the increasing x. The linear relation between a and x was discovered in the range of fluorite-type phase, which accorded with a = 0.52748 ＋ 0.00825 x （0.2≤x≤2.0）, while V= 0.14668 ＋ 0.00711 x （0.2≤x≤2.0） was also achieved.展开更多
We reported a rapid synthesis of Sm^(3+)/Zr^(4+)co-doped Gd2Ti2O7 pyrochlore simulated nuclear wastes solidification by self-propagation plus quick pressing technique.With increment excess contents of Sm2O3 and ZrO2 f...We reported a rapid synthesis of Sm^(3+)/Zr^(4+)co-doped Gd2Ti2O7 pyrochlore simulated nuclear wastes solidification by self-propagation plus quick pressing technique.With increment excess contents of Sm2O3 and ZrO2 from 0 to 10wt%,the phase composition of the products is a mixed phase of pyrochlore structure and defective fluorite structure by X-ray diffraction(XRD)analysis and Raman spectrum.In addition,the SEM results demonstrate the fracture surface and microstructure of Gd2Ti2O7-based pyrochlore.The densified pyrochlore waste form exhibits high bulk density of 5.56 g·cm^(-3) and vickers hardness of 11.20±0.2 GPa.The leaching tests show that the elemental leaching rates of Gd,Sm,and Cu after 42 days are 1.92×10^(-4),1.51×10^(-4),and 3.90×10^(-3) g·m^(-2)·d^(-1),respectively.展开更多
Based on defect chemistry theory and molecular dynamics,the defect formation energy and its relationship with the mechanism of pyrochlore-fluorite phase change were investigated,so as to reveal the underlying mechanis...Based on defect chemistry theory and molecular dynamics,the defect formation energy and its relationship with the mechanism of pyrochlore-fluorite phase change were investigated,so as to reveal the underlying mechanism of high-temperature stability of pyrochlore zirconates.Results showed that with the rise of the atom mass of A,the defect formation energies decreased that meant the crystal structure tended to become more disordered.Noticeably,the first nearest cation antisite dominated the pyrochlore disorder transformation process.In addition,it was found that the diffusion of oxygen atoms was far higher than that of cations,and was increased with the temperature,thus also promoting the pyrochlore-fluorite transformation process.展开更多
Thermally grown oxides(TGOs)at the ceramic top-coat/metallic bond-coat interface are a pressing chal-lenge in advanced thermal barrier coating(TBC)systems as they can affect the performance and ser-vice lifetime of TB...Thermally grown oxides(TGOs)at the ceramic top-coat/metallic bond-coat interface are a pressing chal-lenge in advanced thermal barrier coating(TBC)systems as they can affect the performance and ser-vice lifetime of TBCs.Thus,developing novel TBC materials with ultralow oxygen ion diffusivity is very urgent.In this study,we reported the diffusive properties of oxygen ions in a novel pyrochlore-type La_(2)(Zr_(0.7)Ce_(0.3))_(2)O_(7)(LZ7C3)material.The measured ionic conductivity and atomistic simulation revealed that the oxygen ion diffusivity in LZ7C3 grains is two orders of magnitude lower than that in conventional 8 wt.%yttria-stabilized zirconia(8YSZ)grains.This is due to the relatively high energy barrier for oxygen hopping in LZ7C3.In addition,it was found that enhancing the order distribution of cations is a strategy to reduce the intrinsic oxygen diffusion of pyrochlore-type oxides.On the other hand,we observed that La^(3+) cations segregate at the grain boundaries(GBs)of LZ7C3,which results in the electrostatic poten-tial at GBs being comparable to that in the bulk.Furthermore,we found that the oxygen ion diffusion is facilitated at the GBs of LZ7C3 due to the stretched O-Zr/Ce bond and the low coordination at GBs.How-ever,the segregations of Y^(3+)cations and the increase in the number of oxygen vacancies resulted in the formation of an electrostatic layer at the GBs of 8YSZ,which shielded the oxygen ion diffusion.Despite this,the oxygen ion diffusivity in LZ7C3 was still considerably less than that in conventional 8YSZ.This study offers a stepping stone toward utilizing pyrochlore-type LZ7C3 materials as advanced TBCs at high temperatures.展开更多
This paper studies the helium ions irradiation effects on Nd and Ce co-doped Gd_2 Zr_2 O_7 ceramics. where Nd replaces the Gd site and Ce replaces the Zr site respectively. A series of（Gd_（1-x）Nd_x）_2（Zr_（1-y）C...This paper studies the helium ions irradiation effects on Nd and Ce co-doped Gd_2 Zr_2 O_7 ceramics. where Nd replaces the Gd site and Ce replaces the Zr site respectively. A series of（Gd_（1-x）Nd_x）_2（Zr_（1-y）Ce_y）_2 O_7（0 ≤ x, y ≤ 1） ceramics were irradiated with a 500 keV He ions at room temperature at fluences ranging from 1 × 10^（15） to 1 × 10^（17） ions/cm^2. The irradiated samples were characterized using GIXRD, Raman and SEM measurements. From the GIXRD and Raman observations, the results indicate that all the samples display a deficient fluorite structure after irradiation. The irradiation toleration increases with the irradiation depth increasing under experimental conditions, and Nd_2 Ce_2 O_7 has the best irradiation stability in the（Gd_（1-x）Nd_x）_2（Zr_（1-y）Ce_y）_2 O_7（0≤ x. y≤1）. Based on SEM results, the irradiated samples are still relatively dense and uniform, and no second phase exists.展开更多
We study the structure, magnetization, electrical transport properties and heat capacity of the pyrochlore iridates A2Ir2O7（A=Y, Eu, Bi）. It is found that magnetic frustration and long-range magnetic order coexist i...We study the structure, magnetization, electrical transport properties and heat capacity of the pyrochlore iridates A2Ir2O7（A=Y, Eu, Bi）. It is found that magnetic frustration and long-range magnetic order coexist in Y2Ir2O7 and Eu2Ir2O7, while Bi2Ir2O7 shows magnetic frustration or short-range magnetic order without long-range magnetic order. The former two compounds show insulating behavior. However, the latter one shows metallic behavior. The variations of the radius of A-site ion affect the conduction bandwidth, correlation and Ir-Ir exchange energy, which in turn determine transport properties and magnetic properties. We also find that the antiferromagnetic ordering of pyrochlore iridates is weakly frustrated. The all-in/all-out type of anisotropy based on spin-orbit coupling plays a key role in releasing the frustration.展开更多
Polycrystalline samples of La2Zr2O7 pyrochlore are irradiated by different energetic heavy ions to investigate the dependence of the vibrational mode variations on the irradiation parameters. The applied electronic en...Polycrystalline samples of La2Zr2O7 pyrochlore are irradiated by different energetic heavy ions to investigate the dependence of the vibrational mode variations on the irradiation parameters. The applied electronic energy loss(d E/dx)e increases from about 5.2 keV/nm to 39.6 keV/nm. The ion fluence ranges from 1× 10^11 ions/cm^2 to 6× 10^15 ions/cm^2.Vibrational modes of irradiated pyrochlore are analyzed by using Raman spectrum. Infrared active modes F1 uat 192, 308,and 651 cm^-1 appear in Raman spectra, and the F2 gband at 265 cm-1 rises up due to the irradiation by 200-MeV Kr ions with(d E/dx)e of 16.0 keV/nm. Differently, for the pyrochlore irradiated by 1750-MeV Bi ions with(d E/dx)e of 39.6 keV/nm, in spite of the appearance of infrared active mode F1 u651 cm^-1, the amorphous structure occurs according to the vibrational mode variations of pyrochlore irradiated at higher ion fluences. Amorphous tracks are observed in the samples, which confirm the occurrence of pyrochlore–amorphous transition in pyrochlore irradiated with(d E/dx)e of 39.6 keV/nm.展开更多
基金supported by the start-up funding of CQNU (Grant No. 24XLB010)supported by the Science and Technology Research Program of Chongqing Municipal Education Commission (Grant No. KJQN202100514)+3 种基金funding from Chongqing Natural Science Foundation under Grant No. CSTB2022NSCQ-JQX0018the Fundamental Research Funds for the Central Universities Grant No. 2021CDJZYJH-003Xiaomi Foundation/Xiaomi Young Talents Programfunding from the National Science Foundation of China under Grant Nos. 12404169, 12147172, 12274046, 11874094, 12147102, and 12347101。
文摘The quantum phase transition between Z_(2) plaquette valence bound solid(PVBS) and superfluid(SF) phases on the planar pyrochlore lattice(square ice) is under debate. To gain further insight, here, we focus on the dynamical features of the hard-core Bose–Hubbard model on this lattice and study the excitation spectra by combining stochastic analytic continuation and quantum Monte Carlo simulation. In both PVBS and SF phases,a flat band with bow-tie structure is observed and can be explained by certain symmetries. At the transition point,the spectra turn to be continuous and gapless. A(2+1)-dimensional Abelian–Higgs model with mixed 't Hooft anomaly is proposed to describe the transition, where the anomaly matching predicts that the deconfinement can exist on the domain walls. From the snapshot of the spin configuration in real space, we found the existence of the domain wall. We also found that the spectrum along a specific path in momentum space from PVBS phase to the transition point can be well described by an XXZ spin chain, and the critical theory of XXZ spin chain matches the anomaly. The two-spinon continuum along this specific path implies additional domain walls(point defect) can emerge in the domain walls(line defect) and take the role of deconfinement at the transition point.
基金Project supported by the Spanish Government and the Ministerio de Ciencia e Innovacion(PID2020-116149 GB-I00)Generalitat Valenciana(GRISOLIA/2019/054)the Brazilian National Council for Scientific and Technological Development(306567/2021-0)。
文摘The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human health.To address this issue,heterogeneous photocatalysis emerges as a promising strategy for breaking down recalcitrant molecules.However,efforts are required to develop efficient and stable photocatalysts capable of operating under visible light.This study explores the photocatalytic potential of Fe-doped RE_(2)Zr_(2)O_(7-δ)(RE=Pr,Sm,Nd,Y)compositions,synthesized through the microwaveassisted solvothermal method,for the degradation of methylene blue.Characterizations,such as X-ray diffraction(XRD)and Raman spectroscopy,reveal the obtention of single-phase ordered pyrochlore for RE=Pr,Sm and Nd or defect fluorite structures for Y.Photocatalytic tests under visible light demonstrate efficient dye degradation for all Fe-doped samples,Y_(2)Zr_(1.9)Fe_(0.1)O_(6.95)(YZF)defect fluorite being the one that exhibits the highest efficiency.Radical scavenging experiments identify hydroxyl radicals as key contributors to the degradation process,along with photoinduced holes.These materials exhibit minimal leaching of iron ions,confirming their stability,and the best material,YZF,demonstrates effective reusability.The results highlight the potential of Fe-doped RE_(2)Zr_(2)O_(7)compositions as an efficient alternative for application as photocatalysts for the degradation of azo dyes under visible light.
基金support from the National Natural Science Foundation of China under grant No.52302065the Yunnan Fundamental Research Projects under grant Nos.202201BE070001-008 and 202201AU070142the National Key Research and Development Program of China under grant No.2023YFB3711200.
文摘Low thermal conductivity and excellent mechanical strength are essential to pyrochlore A2B2O7 ceramic for environmental/thermal barrier coating applications.To collaboratively tailor the mechanical and thermal properties of A2B2O7 ceramic,a novel high entropy pyrochlore ceramic(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) with significant atomic radius and mass fluctuation is proposed by simultaneously introducing various elements with different valence states at A and B cation sites.The as-synthesized(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) exhibits enhanced fracture toughness(1.68 MPa m^(1/2)),amorphous-like low thermal conductivity(1.45 W m^(-1) K^(-1) at 900℃)and matched thermal expansion coefficient(9.0×10^(-6) K^(-1) at 1200℃)with Al_(2)O_(3)/Al_(2)O_(3) CMCs.The extensive misfits in atomic weight,ionic radius among the substitutional cations in combination with the intrinsic oxygen vacancies in the anion sublattice play significant roles in the thermal conductivity reduction of(La_(0.3)Gd_(0.3)Ca_(0.4))_(2)(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))_(2)O_(7) ceramic.The combination of outstanding mechanical and thermal properties indicates that this type of material has a good application prospect for environmental/thermal barrier coatings.
基金supported by the National Key Research and Development Program of China (Grant Nos. 2023YFA1406100 and 2021YFA1400200)the National Natural Science Foundation of China (Grant Nos. 12025408 and 12174424)+2 种基金the Youth Innovation Promotion Association of Chinese Academy of Scineces (Grant No. 2023007)support from the National Natural Science Foundation of China (Grant No. 11904272)the Open Fund of Hubei Provincial Key Laboratory of Metallurgical Industry Process Systems Science (Grant No. Z202202)。
文摘The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin-one Haldane chains associated with an orbital ordering of Ru-4d electrons.With an aim to tune and access distinct ground states with strong entanglements of multiple degrees of freedom,i.e.,spin,orbital,charge,and lattice,we utilize a high-pressure approach to regulate the MIT of this system.Our detailed resistivityρ(T) measurements on the polycrystalline Tl_(2)Ru_(2)O_(7) samples under various hydrostatic pressures indeed reveal an unusual evolution of the electronic ground states.At first,the MIT is suppressed monotonically from 120 K at ambient to about 70 K at 1.5 GPa and then vanishes suddenly at about 1.8 GPa without achieving a metallic ground state.Meanwhile,the system evolves into a semiconducting ground state with magnitude ofρ(T) in the entire temperature range enhanced gradually by further increasing pressure.Prior to the abrupt disappearance of MIT,a new electronic order manifested as a kink-like anomaly inρ(T) emerges at T_(0)>T_(MIT) at 1.2 GPa and it continues to increase with pressure,producing a tricritical-point-like behavior in the T–P phase diagram of Tl_(2)Ru_(2)O_(7).The presence of two successive transitions at T_(0 )and T_(MIT )in the pressure range 1.2–1.5 GPa indicates an inhomogeneous electronic state nearby the tricritical point.At P≥3 GPa,another broad anomaly emerges inρ(T) at T_(1)>T_(0),and T_(1)continuously increases with pressure,dividing the semiconductingρ(T) into distinct thermally activated regions.These rich phenomena in the pressurized Tl_(2)Ru_(2)O_(7) should originate from the complex interplay of strongly entangled multiple quantum degrees of freedom in the system near the localized-to-itinerant crossover regime.
基金supported by the National Natural Science Foundation of China(Grant Nos.12275009,12192280,and 11935004)the National Magnetic Confinement Fusion Energy Research Project(No.2021YFE031100).
文摘The properties of high entropy pyrochlore have been studied extensively,but there is no consistent conclusion on its radiation tolerance.Besides,the mechanism of the high entropy effect on the radiation tolerance of pyrochlore is still unclear.In this work,combined with experiments and calculations of pyrochlores with similar cationic radius ratios,the A-site and B-site high entropy effects on structural evolution under irradiation are analyzed.In situ irradiation experiments were carried out on A-site high entropy pyrochlores such as(La_(0.2)Nd_(0.2)Sm_(0.2)Gd_(0.2)Er_(0.2))_(2)Zr_(2)O_(7),B-site Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7),and ternary pyrochlore Sm_(2)Zr_(2)O_(7) and Gd_(2)Sn_(2)O_(7) for comparison.The A-site high entropy pyrochlore can maintain a stable structure under high fluence irradiation like corresponding ternary pyrochlore,demonstrated by high angle annular dark field scanning transmission electron microscopy(HAADF-STEM),energy dispersive spectroscopy(EDS)mapping and Raman spectrum.The additional irradiation experiments on A-site high entropy pyrochlores(La_(1/3)Nd_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) and(Nd_(1/3)Sm_(1/3)Gd_(1/3))_(2)Zr_(2)O_(7) also confirm the similarity under irradiation between A-site high entropy and ternary pyrochlores.However,the B-site high entropy pyrochlore Gd_(2)(Ti_(1/3)Sn_(1/3)Zr_(1/3))_(2)O_(7) becomes amorphous at exceptionally low irradiation fluences,indicating a significantly distinct radiation tolerance compared with the A-site high entropy.The difference between the A-site and B-site high entropy effect is analyzed from cationic lattice distortion,bond strength,and inner electron binding energy by first-principles calculations.The results reveal the role and mechanism of the high entropy effect in pyrochlores and lay a foundation for material design and future applications.
基金supported by the National Natural Science Foundation of China (grant #41172052)
文摘Hydroxycalciopyrochlore,ideally （Ca,Na,U,□）2（Nb,Ti）2O6（OH）,cubic,is a new mineral species （IMA2011-026） within the pyrochlore supergroup that was found occurring at the Maoniuping mine,Mianning County,Xichang prefecture,Sichuan Province,southwest China.The mineral is found in an alkali feldspar granite rare-earth ore deposit （26-27 Ma）.Associated minerals include calcite,barite,celestine,albite,aegirine,aegirine-augite,fluorite,parasite-（Ce）,thorite,thorianite,zircon,galena,sphalerite,magnetite,and pyrite.Crystals occur mostly as octahedra,and less often as dodecahedra and tetrahexahedra or combinations thereof.Some occur with an allotriomorphic habit with a thick triangular tabular form.Crystals generally range from 0.1 to 1 mm in size.The mineral is brownishblack,greenish-black and black on fresh sections with a brown streak.The crystal is translucent,and has a greasy lustre on fresh sections.It is metamict without any observed parting or cleavage and with a conchoidal fracture.The Vickers microhardness is 572 kg/mm2 （5-6 on the Mohs hardness scale）.The density measured by hydrostatic weighing is 5.10（3） g/cm3.The strongest four reflections in the X-ray powder-diffraction pattern [d in（A） （Ⅰ） hkl] are：2.9657 （100） 2 2 2,1.8142 （34） 0 4 4,1.5463 （21） 2 2 6,2.5688 （18） 0 0 4.The unit-cell parameters are a =10.381（4） （A）,V=1118.7（7）（A）3,Z =8.The structure was solved and refined in the space group Fd3m with R =0.09.The empirical formula is （Ca0.74Na0.5sU0.40Ce0.05Fe0.02□0.21）2.00（Nb1.15Ti0.s0Ta0.03Al0.01Mg0.01）2.00O6.02 [（OH）1.01F0.09]1.10,on the basis of 2 atoms of B pfu; the simplified formula is （Ca,Na,U,□）2（Nb,Ti）2O6（OH）.Type material is deposited in the Geological Museum of China,Beijing,People＇s Republic of China,catalogue number M11800.
基金Project supported by the National Natural Science Foundation of China(21962009,21567016,21666020)Natural Science Foundation of Jiangxi Province(20181ACB20005,20171BAB213013,20181BAB203017)Key Laboratory Foundation of Jiangxi Province for Environment and Energy Catalysis(20181BCD40004)。
文摘A2B2O7 pyrochlore is a kind of important functional materials for different purposes,which has been investigated extensively by crystallographers and material scientists.However,the catalytic chemistry of this type of special compounds has rarely been documented,though a few researchers have tried to synthesize some pyrochlore compounds with different chemical compositions for a variety of green energy production and air pollution control reactions in the history.With the expectation to help catalysis scientists to get better acquaintance with,and gain deeper understanding on this type of compounds as heterogeneous catalysts,the major publications over the past several decades have been screened and reviewed in this paper,based also on our own experience of studying on this type of catalytic materials.The crystalline phase transformations of the compounds with the change of the A and B site cations,the phase change’s influences on the surface and bulk properties,and their subsequent impact on the catalytic performance for different reactions have been summarized.Furthermore,the future work which needs to be performed to perceive in depth this kind of important materials as catalysts has been proposed and suggested.We trust that this short review contains valuable information,which will provide great help for people to get better cognition for A2 B2 O7 pyrochlore compounds,and assist them to develop better catalysts for various reactions.
基金Supported by the National Natural Science Foundation of China(Nos.90922034 20771042)
文摘Pyrochlore titanate oxides, R2Ti2O7（R=Gd3＋, Tb3＋, Dy3＋）, were synthesized under mild hydrothermal conditions. The crystal growth of pyrochlore titanate oxides and taking place of chemical reaction in the hydrothermal processing were sensitive to the alkalinity, temperature, reaction time, the nature of the rare earth ion and the composition of initial reaction mixture. The as-prepared samples were characterized by powder X-ray diffraction, scanning electron microscopy, Raman spectrum and variable temperature dc magnetic susceptibility（Superconductivity quantum interference device, SQUIDS）. The magnetic studies gave 7.29×10-23 A·m2/Gd3＋ and -8.28 K, 8.75×10-23 A·m2/ Tb3＋ and -19.7 K, and 8.85×10-23 A·m2/Dy3＋ and 0.84 K effective moments and Weiss constants for Gd2Ti2O7, Tb2Ti2O7 and Dy2Ti2O7, respectively.
基金supported by the National Natural Science Foundation of China(No.51602188)the Program for Professor of Special Appointment(Eastern Scholar)by Shanghai Municipal Education Commission(No.TP2015040)。
文摘Various excellent properties of rare earth zirconate and stannate pyrochlores are close related with their native point defects.First-principles calculations are performed to systematically investigate the point defect mechanism and the oxygen diffusion behavior of A_(2)B_(2)O_(7)(A=La,Ce,Pr,Nd,Pm,Sm,Eu,Gd;B=Zr,Sn).The possible defect complexes and their associated reactions under stoichiometric and nonstoichiometric conditions are explored.The O Frenkel pairs are the most stable defect structure in stoichiometric zirconates,whereas the cation antisite defects are the predominant one in stoichiometric stannates.In the case of BO_(2) excess zirconates and stannates,the BA cation antisite defect with the A vacancy and/or the oxygen interstitial is energetically favorable,whereas the ABantisite defect together with the oxygen vacancy and/or the A interstitial is preferable under the A_(2)O_(3) excess condition.Meanwhile,the maximum point defect concentrations of zirconates are much higher than those of stannates.Furthermore,the oxygen migration barriers are similar in these compounds,ranging in 0.68 eV–0.80 eV.The predicted point defects and oxygen diffusion mechanisms play the critical role in their engineering applications and are expected to guide the future property improvement of pyrochlores through the control of point defects and/or composition.
文摘High entropy pyrochlores(HEP)are potential candidates as dispersoids in the oxide dispersed strengthened steels or alloys,which can be used in nuclear reactors and supercritical boilers.For the first time,HEP oxides Y_(2)(TiZrHfMoV)_(2)O_(7) were synthesized with Y_(2)Ti_(2)O_(7) as a base structure with the B site(Ti)substituted with five cations through reverse co-precipitation technique in the nanocrystalline form at lowest synthesis temperature.The synthesis parameters for Y_(2)(TiZrHfMoV)_(2)O_(7)(5C)and other derived compositions(five compositions of four cationic systems with each cation eliminated at B site from 5 C)are optimised to obtain lower crystallite and particle sizes.5C has a smaller crystallite size(27 nm)than other single-phase compositions.The cation’s influence,oxidation state,and oxygen vacancy in the phase formation were analysed through XPS.The single-phase HEPs are consolidated through spark plasma sintering.Y_(2)(TiZrHfMo)_(2)O_(7)(4 C-V)shows the highest hardness among the compositions reported so far due to its finer grain size,and Y_(2)(TiHfMoV)_(2)O_(7)(4 C-Zr)has a higher Young’s modulus compared to other single-phase composition due to its higher degree of order in the structure.
基金supported by the Scientific Research Foundation of the Education Bureau of Sichuan Province of China (Grant No.2010ZC119)
文摘A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic properties of ideal Lu2Sn207 pyrochlore. The results are in excellent agreement with available experimental measurements. Density of states （DOS） of this compound was presented and analysed. We also notice the presence of the hybridization between oxygen and Lu metal. The band structure calculations show that the compound has direct band gap of 2.67 eV at the F point in the Brillouin zone and this indicates that the material has a semi-conducting feature.
文摘To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO loadings were fabricated and characterized by different techniques and density functional theory calculations.In these catalysts,a spontaneous dispersion of CuO on the La_(2)Sn_(2)O_(7)pyrochlore support formed,having a monolayer dispersion capacity of 1.90 mmol CuO/100 m^(2) La_(2)Sn_(2)O_(7)surface.When loaded below this capacity,CuO exists in a sub-monolayer or monolayer state.X-ray photoelectron spectroscopy(XPS),Raman spectroscopy,and Bader charge and density of states analyses indicate that there are strong interactions between the sub-monolayer/monolayer CuO and the La_(2)Sn_(2)O_(7)support,mainly through the donation of electrons from Cu to Sn at the B-sites of the structure.In contrast,Cu has negligible interactions with La at the A-sites.This suggests that,in composite oxide supports containing multiple metals,the supported metal oxide interacts preferentially with one kind of metal cation in the support.The Raman,in situ diffuse reflectance infrared Fourier transform spectroscopy,and XPS results confirmed the formation of both O2^(-)and O2^(2-)as the active sites on the surfaces of the CuO/La_(2)Sn_(2)O_(7)catalysts,and the concentration of these active species determines the soot combustion activity.The number of active oxygen anions increased with increase in CuO loading until the monolayer dispersion capacity was reached.Above the monolayer dispersion capacity,microsized CuO crystallites formed,and these had a negative effect on the generation of active surface oxygen sites.In summary,a highly active catalyst can be prepared by covering the surface of the La_(2)Sn_(2)O_(7)support with a CuO monolayer.
基金Supported by the Ministry of Science and Technology under Grant No 2016YFA0300503
文摘We perform a detailed investigation of the new ＇breathing＇ pyrochlore compound LiInCr4O8 through Rh substi- tution with measurements of magnetic susceptibility, specific heat, and x-ray powder diffraction. The antiferro- magnetic phase of LiInCr4O8 is found to be slowly suppressed with increasing Rh, up to the critical concentration of x = 0.1 where the antiferromagnetic phase is still observed with the peak in specific heat Tp = 12.5 K, slightly lower than Tp =14.3 K for the x = 0 compound. From tile measurements of magnetization we also uncover evidence that substitution increases the amount of frustration. Comparisons are made with the LiGayIn1-yCr4O8 system as well as other frustrated pyrochlore-related materials and comparable amounts of frustration are found. The results of this work show that the engineered breathing pyrochlores present an important method to further understand the complex magnetism in frustrated systems.
基金Funded Partly by the Key Project of National High Technology Research and Development Program-"863"Program(No.2009AA050703)the National Natural Science Foundation of China(Nos.41302028,41272050,and 21007052)the Open Foundation of Joint Laboratory for Extreme Conditions Matter Properties,Southwest University of Science and Technology and Research Center of Laser Fusion,CAEP(No.12zxjk04)
文摘The phase of pyrochlore Gd_2Zr_2O_7 used for immobilization of Pu （Ⅳ） was investigated, tetravalent cerium was used as the simulacrum for plutonium with tetravalence, and the compounds in the system Gd_2Zr_2-_xCe_xO_7 （0.0≤x≤2.0） were synthesized via a high temperature solid reaction method with Gd_2O_3 and ZrO_2 powders being used as the starting materials. Based on the collected XRD data of the gained samples, the phase and microstructural change of compounds were calculated by means of rietveld structural refinement method. The experimental results indicated that the phases of compounds were changed from pyrochlore to fluorite-type phase with the increasing x. The linear relation between a and x was discovered in the range of fluorite-type phase, which accorded with a = 0.52748 ＋ 0.00825 x （0.2≤x≤2.0）, while V= 0.14668 ＋ 0.00711 x （0.2≤x≤2.0） was also achieved.
基金Funded by the National Natural Science Foundation of China(No.51672228)the Project of State Key Laboratory of Environmentfriendly Energy Materials(Southwest University of Science and Technology,Nos.18fksy0214 and 20fksy11)+1 种基金the Postgraduate Innovation Fund Project by Southwest University of Science and Technology(No.19ycx0016)the Science Development Foundation of China Academy of Engineering Physics。
文摘We reported a rapid synthesis of Sm^(3+)/Zr^(4+)co-doped Gd2Ti2O7 pyrochlore simulated nuclear wastes solidification by self-propagation plus quick pressing technique.With increment excess contents of Sm2O3 and ZrO2 from 0 to 10wt%,the phase composition of the products is a mixed phase of pyrochlore structure and defective fluorite structure by X-ray diffraction(XRD)analysis and Raman spectrum.In addition,the SEM results demonstrate the fracture surface and microstructure of Gd2Ti2O7-based pyrochlore.The densified pyrochlore waste form exhibits high bulk density of 5.56 g·cm^(-3) and vickers hardness of 11.20±0.2 GPa.The leaching tests show that the elemental leaching rates of Gd,Sm,and Cu after 42 days are 1.92×10^(-4),1.51×10^(-4),and 3.90×10^(-3) g·m^(-2)·d^(-1),respectively.
基金Sponsored by the National Natural Science Foundation of China (50801005)
文摘Based on defect chemistry theory and molecular dynamics,the defect formation energy and its relationship with the mechanism of pyrochlore-fluorite phase change were investigated,so as to reveal the underlying mechanism of high-temperature stability of pyrochlore zirconates.Results showed that with the rise of the atom mass of A,the defect formation energies decreased that meant the crystal structure tended to become more disordered.Noticeably,the first nearest cation antisite dominated the pyrochlore disorder transformation process.In addition,it was found that the diffusion of oxygen atoms was far higher than that of cations,and was increased with the temperature,thus also promoting the pyrochlore-fluorite transformation process.
基金supported by the National Natural Science Foundation of China(Nos.11774280 and 11947136)Fundamental Research Funds for the Central Universities(No.xzy022019004)Natural Science Foundation of the Shaanxi Province(No.2020JQ339)。
文摘Thermally grown oxides(TGOs)at the ceramic top-coat/metallic bond-coat interface are a pressing chal-lenge in advanced thermal barrier coating(TBC)systems as they can affect the performance and ser-vice lifetime of TBCs.Thus,developing novel TBC materials with ultralow oxygen ion diffusivity is very urgent.In this study,we reported the diffusive properties of oxygen ions in a novel pyrochlore-type La_(2)(Zr_(0.7)Ce_(0.3))_(2)O_(7)(LZ7C3)material.The measured ionic conductivity and atomistic simulation revealed that the oxygen ion diffusivity in LZ7C3 grains is two orders of magnitude lower than that in conventional 8 wt.%yttria-stabilized zirconia(8YSZ)grains.This is due to the relatively high energy barrier for oxygen hopping in LZ7C3.In addition,it was found that enhancing the order distribution of cations is a strategy to reduce the intrinsic oxygen diffusion of pyrochlore-type oxides.On the other hand,we observed that La^(3+) cations segregate at the grain boundaries(GBs)of LZ7C3,which results in the electrostatic poten-tial at GBs being comparable to that in the bulk.Furthermore,we found that the oxygen ion diffusion is facilitated at the GBs of LZ7C3 due to the stretched O-Zr/Ce bond and the low coordination at GBs.How-ever,the segregations of Y^(3+)cations and the increase in the number of oxygen vacancies resulted in the formation of an electrostatic layer at the GBs of 8YSZ,which shielded the oxygen ion diffusion.Despite this,the oxygen ion diffusivity in LZ7C3 was still considerably less than that in conventional 8YSZ.This study offers a stepping stone toward utilizing pyrochlore-type LZ7C3 materials as advanced TBCs at high temperatures.
基金Project supported by the National Natural Science Foundation of China(21507105,51574201)Ministry of Housing and Urban-Rural Development(2014-K3-037)+1 种基金Sichuan Science and Technology Innovation Talent Project(2016119)Scientific and Technical Youth Innovation Group(Southwest Petroleum University)(2015CXTD05)
文摘This paper studies the helium ions irradiation effects on Nd and Ce co-doped Gd_2 Zr_2 O_7 ceramics. where Nd replaces the Gd site and Ce replaces the Zr site respectively. A series of（Gd_（1-x）Nd_x）_2（Zr_（1-y）Ce_y）_2 O_7（0 ≤ x, y ≤ 1） ceramics were irradiated with a 500 keV He ions at room temperature at fluences ranging from 1 × 10^（15） to 1 × 10^（17） ions/cm^2. The irradiated samples were characterized using GIXRD, Raman and SEM measurements. From the GIXRD and Raman observations, the results indicate that all the samples display a deficient fluorite structure after irradiation. The irradiation toleration increases with the irradiation depth increasing under experimental conditions, and Nd_2 Ce_2 O_7 has the best irradiation stability in the（Gd_（1-x）Nd_x）_2（Zr_（1-y）Ce_y）_2 O_7（0≤ x. y≤1）. Based on SEM results, the irradiated samples are still relatively dense and uniform, and no second phase exists.
基金Supported by the National Natural Science Foundation of China(11604071)the Natural Science Foundation of the Education Department of Anhui Province(KJ2016SD49)the Natural Science Foundation of Hefei University(16ZR06ZDB,15RC13,14KY15ZR,2016dtr02)
文摘We study the structure, magnetization, electrical transport properties and heat capacity of the pyrochlore iridates A2Ir2O7（A=Y, Eu, Bi）. It is found that magnetic frustration and long-range magnetic order coexist in Y2Ir2O7 and Eu2Ir2O7, while Bi2Ir2O7 shows magnetic frustration or short-range magnetic order without long-range magnetic order. The former two compounds show insulating behavior. However, the latter one shows metallic behavior. The variations of the radius of A-site ion affect the conduction bandwidth, correlation and Ir-Ir exchange energy, which in turn determine transport properties and magnetic properties. We also find that the antiferromagnetic ordering of pyrochlore iridates is weakly frustrated. The all-in/all-out type of anisotropy based on spin-orbit coupling plays a key role in releasing the frustration.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11705246,11675233,and 11690041)the Natural Science Foundation of Gansu Province,China(Grant No.17JR5RA316)
文摘Polycrystalline samples of La2Zr2O7 pyrochlore are irradiated by different energetic heavy ions to investigate the dependence of the vibrational mode variations on the irradiation parameters. The applied electronic energy loss(d E/dx)e increases from about 5.2 keV/nm to 39.6 keV/nm. The ion fluence ranges from 1× 10^11 ions/cm^2 to 6× 10^15 ions/cm^2.Vibrational modes of irradiated pyrochlore are analyzed by using Raman spectrum. Infrared active modes F1 uat 192, 308,and 651 cm^-1 appear in Raman spectra, and the F2 gband at 265 cm-1 rises up due to the irradiation by 200-MeV Kr ions with(d E/dx)e of 16.0 keV/nm. Differently, for the pyrochlore irradiated by 1750-MeV Bi ions with(d E/dx)e of 39.6 keV/nm, in spite of the appearance of infrared active mode F1 u651 cm^-1, the amorphous structure occurs according to the vibrational mode variations of pyrochlore irradiated at higher ion fluences. Amorphous tracks are observed in the samples, which confirm the occurrence of pyrochlore–amorphous transition in pyrochlore irradiated with(d E/dx)e of 39.6 keV/nm.
