High-entropy pyrochlore-type structures based on rare-earth zirconates are successfully produced by conventional solid-state reaction method. Six rare-earth oxides(La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, and Y2O3) and ZrO2...High-entropy pyrochlore-type structures based on rare-earth zirconates are successfully produced by conventional solid-state reaction method. Six rare-earth oxides(La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, and Y2O3) and ZrO2 are used as the raw powders. Five out of the six rare-earth oxides with equimolar ratio and ZrO2 are mixed and sintered at different temperatures for investigating the reaction process. The results demonstrate that the high-entropy pyrochlores(5RE1/5)2 Zr2O7 have been formed after heated at 1000 ℃. The(5RE1/5)2Zr2O7 are highly sintering resistant and possess excellent thermal stability. The thermal conductivities of the(5RE1/5)2Zr2O7 high-entropy ceramics are below 1 W·m–1·K–1 in the temperature range of 300–1200 ℃. The(5RE1/5)2Zr2O7 can be potential thermal barrier coating materials.展开更多
The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temper...The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temperature dilatometer, DSC, and laser thermal diffusivity methods were used to analyze thermal expansion coefficient （TEC）, specific heat, and thermal diffusivity. The results showed that CeO2 doped pyrochlores La2（Zr1.8Ce0.2）2O7 and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had higher TEC than La2Zr2O7 and La1.7Dy0.3Zr2O7. La2（Zr1.8Ce0.2）2O7, La1.7Dy0.3Zr2O7, and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had lower thermal conductivity than undoped La2Zr2O7. The Dy2O3, Nd2O3, and CeO2 codoped composition showed the lowest thermal conductivity and the highest TEC. Thermo-physical results also indicated that TEC of rare earth oxide doped La2Zr2O7 ceramic was slightly higher than that of conventional ZrO2-8Wt.% Y2O3 （8YSZ）, and its thermal conductivity was lower than that of 8YSZ.展开更多
Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3＋ cation （La to Lu）, are promising candidate materials for applications as high temperature thermal barrier coatings because of their high melting p...Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3＋ cation （La to Lu）, are promising candidate materials for applications as high temperature thermal barrier coatings because of their high melting points, high thermal expansion coefficients, and low thermal conductivities. In this study, oxides of Sm2Zr2O7, （Smo.75La0.25）2Zr2O7, （Sm0.5 La0.5）2 ZreO7, （Sm0.25La0.75）eZr2O7 and La2Zr2O7 were prepared by solid reactions at 1600℃ for 10 h using Sm2O3, La2O3 and ZrO2 as the reactants. The phase compositions of these ceramic materials were analyzed by X-ray diffractometer （XRD） and fourier transform infrared spectroscopy （FT-IR） methods, respectively. The microstructure was observed by scanning electron microscope （SEM）. The thermal conductivities of these ceramic materials were measured using laser-flash method. XRD and FT-IR results showed that pure ceramic materials with pyrochlore structure were prepared successfully. SEM results indicated that microstructures of these ceramic materials were dense and grain boundaries were very clean. The La2O3 doped Sm2Zr2O7 pyrochlores （Sm0.75 La0.25）2Zr2O7 and （Sm0.5 La0.5）2 Zr2O7 had lower thermal conductivity than the undoped Sm2Zr2O7. The thermal conductivity of （Sm0.25La0.75）2Zr2O7 was found to be lower than that of La2Zr2O7. The results showed that these ceramic materials had the potential to be used as candidate materials for TBCs.展开更多
In this work,Nb^(5+)and Cu^(2+)were selected to partially substitute Zr4+in Gd_(2)Zr_(2)O_(7)for studying the phase structure,microscopic morphology and thermal properties.Gd_(2)(Zr_(1-3 x/2)Nb_(x)CU_(x/2))_(2)O_(7)(x...In this work,Nb^(5+)and Cu^(2+)were selected to partially substitute Zr4+in Gd_(2)Zr_(2)O_(7)for studying the phase structure,microscopic morphology and thermal properties.Gd_(2)(Zr_(1-3 x/2)Nb_(x)CU_(x/2))_(2)O_(7)(x=0,0.05,0.1,0.15,0.2,0.25)ceramic materials were synthesized by high-temperature solid-state reaction method.The results show that the Gd_(2)(Zr_(1-3 x/2)Nb_(x)Cu_(x)/2)_(2)O_(7)ceramics present cubic pyrochlore structure with clear grain boundaries and dense cell structure.And the thermal expansion coefficient of Gd_(2)(Zr_(1-3 x/2)Nb_(x)Cu_(x/2))_(2)O_(7)ceramics gradually decreases because of the incorporation of Nb^(5+)and Cu^(2+)into Zr-site in Gd_(2)Zr_(2)O_(7).Meanwhile,its thermal conductivity decreases firstly and then increases with the doping of Nb^(5+)and Cu^(2+),which reaches the lowest value for the composition of Gd_(2)(Zr_(0.85)Nb_(0.1)Cu_(0.05))_(2)O_(7).展开更多
In this research, Zr-doped Gd_2Ti_2O_7 pyrochlores, with the composition of Gd_2(Ti_(1-x)Zr_x)_2O_7, were firstly synthesized by self-propagating high-temperature synthesis plus quick pressing(SHS/QP) using CuO as the...In this research, Zr-doped Gd_2Ti_2O_7 pyrochlores, with the composition of Gd_2(Ti_(1-x)Zr_x)_2O_7, were firstly synthesized by self-propagating high-temperature synthesis plus quick pressing(SHS/QP) using CuO as the oxidant and Ti as the reductant. To improve the radiation resistance of titanate–pyrochlore, up to 35 at% Zr was incorporated to substitute the Ti site of Gd_2Ti_2O_7 pyrochlore(Gd_2(Ti_(0.75)Zr_(0.35))_2O_7). XRD and SEM microstructural characterizations showed the formation of a composite ceramic with the major pyrochlore phase and the minor Cu phase. The generated temperature of samples decreased from 1702to 1011 ℃ with increasing Zr content. The effects of sintering temperature and pressure time on phase composition and microstructure were systematically studied. Besides, the influence of thermal transmission on the whole combustion process was also explored. The pyrochlore-based waste form possessed high bulk density of 6.25 g/cm^3 and Vickers hardness of 10.81 GPa. The MCC-1 leaching test showed the normalized elemental leaching rates(42d) of Cu, Gd, and Zr are 1.27×10^(-2), 1.33×10^(-3), and 8.44×10^(-7)g·m^(-2)·d^(-1), respectively.展开更多
Lattice engineering and distortion have been considered one kind of effective strategies for discovering advanced materials.The instinct chemical flexibility of high-entropy oxides(HEOs)motivates/accelerates to tailor...Lattice engineering and distortion have been considered one kind of effective strategies for discovering advanced materials.The instinct chemical flexibility of high-entropy oxides(HEOs)motivates/accelerates to tailor the target properties through phase transformations and lattice distortion.Here,a hybrid knowledge-assisted data-driven machine learning(ML)strategy is utilized to discover the A_(2)B_(2)O_(7)-type HEOs with low thermal conductivity(κ)through 17 rare-earth(RE=Sc,Y,La-Lu)solutes optimized A-site.A designing routine integrating the ML and high throughput first principles has been proposed to predict the key physical parameter(KPPs)correlated to the targetedκof advanced HEOs.Among the smart-designed 6188(5RE_(0.2))_(2)Zr_(2)O_(7)HEOs,the best candidates are addressed and validated by the princi-ples of severe lattice distortion and local phase transformation,which effectively reduceκby the strong multi-phonon scattering and weak interatomic interactions.Particularly,(Sc_(0.2)Y_(0.2)La_(0.2)Ce_(0.2)Pr_(0.2))_(2)Zr_(2)O_(7)with predictedκbelow 1.59 Wm^(−1)K^(−1)is selected to be verified,which matches well with the ex-perimentalκ=1.69 Wm^(−1)K^(−1)at 300 K and could be further decreased to 0.14 Wm^(−1)K^(−1)at 1473 K.Moreover,the coupling effects of lattice vibrations and charges on heat transfer are revealed by the cross-validations of various models,indicating that the weak bonds with low electronegativity and few bond-ing charge density and the lattice distortion(r∗)identified by cation radius ratio(r A/r B)should be the KPPs to decreaseκefficiently.This work supports an intelligent designing strategy with limited atomic and electronic KPPs to accelerate the development of advanced multi-component HEOs with proper-ties/performance at multi-scales.展开更多
A novel high-entropy material,(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7)was successfully synthesized by the solid state reaction method and spark plasma sintering,and investigated as a promising thermal ...A novel high-entropy material,(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7)was successfully synthesized by the solid state reaction method and spark plasma sintering,and investigated as a promising thermal barrier coating material.Rare-earth elements were distributed homogeneously in the pyrochlore structure.It was found that the prepared high-entropy ceramic maintains pyrochlore structure at the temperature up to 1600℃,and it possesses a similar thermal expansion coefficient(10.2×10^(−6)K^(−1) at 25-900℃)to that of YSZ,low thermal conductivity(<0.9 W m^(-1)K^(−1) at 100-1000℃)and good CMAS resistance(infiltration depth is 22μm after annealed at 1300℃for 24 h).The corrosion process was investigated,and RE elements distributing homogeneously in(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7)show different diffusion rates in CMAS.RE^(3+) with a larger radius(closer to Ca^(2+))is easier to react with CMAS to form an apatite phase.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
A series of Ni/La2Zr2O7 pyrochlore catalysts prepared by impregnation method and treated by dielectric barrier discharge（DBD） plasma in different atmospheres and varied sequences were prepared and applied for dry re...A series of Ni/La2Zr2O7 pyrochlore catalysts prepared by impregnation method and treated by dielectric barrier discharge（DBD） plasma in different atmospheres and varied sequences were prepared and applied for dry reforming of methane（DRM）. It is found that all of the plasma treated catalysts show evidently improved activity and coke resistance in comparison with the non-plasma treated one. The best performance is achieved on Ni/La2Zr2O7–H2P–C,a catalyst treated in H2 plasma before calcination. TGA-DSC and SEM demonstrate that carbon deposition is significantly suppressed on all of the plasma treated samples. Moreover,XRD and TEM results testify that both Ni O and Ni sizes on the calcined and reduced samples treated by plasma are also decreased,which results in higher Ni metal dispersion on the reduced and used catalysts and enhances the interactions between Ni sites and the support. It is believed that these are the inherent reasons accounting for the promotional effects of plasma treatment on the reaction performance of the Ni/La2Zr2O7 pyrochlore catalysts.展开更多
基金Financial support from the National Natural Science Foundation of China (Nos. 51532009, 51602324, and 51872405) are gratefully acknowledged.
文摘High-entropy pyrochlore-type structures based on rare-earth zirconates are successfully produced by conventional solid-state reaction method. Six rare-earth oxides(La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, and Y2O3) and ZrO2 are used as the raw powders. Five out of the six rare-earth oxides with equimolar ratio and ZrO2 are mixed and sintered at different temperatures for investigating the reaction process. The results demonstrate that the high-entropy pyrochlores(5RE1/5)2 Zr2O7 have been formed after heated at 1000 ℃. The(5RE1/5)2Zr2O7 are highly sintering resistant and possess excellent thermal stability. The thermal conductivities of the(5RE1/5)2Zr2O7 high-entropy ceramics are below 1 W·m–1·K–1 in the temperature range of 300–1200 ℃. The(5RE1/5)2Zr2O7 can be potential thermal barrier coating materials.
基金supported by the Postdoctoral Foundation of China (20060400261)the Special Finance Scheme of Post Doctoral Foundation of China (200801350)
文摘The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temperature dilatometer, DSC, and laser thermal diffusivity methods were used to analyze thermal expansion coefficient （TEC）, specific heat, and thermal diffusivity. The results showed that CeO2 doped pyrochlores La2（Zr1.8Ce0.2）2O7 and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had higher TEC than La2Zr2O7 and La1.7Dy0.3Zr2O7. La2（Zr1.8Ce0.2）2O7, La1.7Dy0.3Zr2O7, and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had lower thermal conductivity than undoped La2Zr2O7. The Dy2O3, Nd2O3, and CeO2 codoped composition showed the lowest thermal conductivity and the highest TEC. Thermo-physical results also indicated that TEC of rare earth oxide doped La2Zr2O7 ceramic was slightly higher than that of conventional ZrO2-8Wt.% Y2O3 （8YSZ）, and its thermal conductivity was lower than that of 8YSZ.
基金supported by Doctoral Fund of Henan Institute of Engineering (D2007012)
文摘Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3＋ cation （La to Lu）, are promising candidate materials for applications as high temperature thermal barrier coatings because of their high melting points, high thermal expansion coefficients, and low thermal conductivities. In this study, oxides of Sm2Zr2O7, （Smo.75La0.25）2Zr2O7, （Sm0.5 La0.5）2 ZreO7, （Sm0.25La0.75）eZr2O7 and La2Zr2O7 were prepared by solid reactions at 1600℃ for 10 h using Sm2O3, La2O3 and ZrO2 as the reactants. The phase compositions of these ceramic materials were analyzed by X-ray diffractometer （XRD） and fourier transform infrared spectroscopy （FT-IR） methods, respectively. The microstructure was observed by scanning electron microscope （SEM）. The thermal conductivities of these ceramic materials were measured using laser-flash method. XRD and FT-IR results showed that pure ceramic materials with pyrochlore structure were prepared successfully. SEM results indicated that microstructures of these ceramic materials were dense and grain boundaries were very clean. The La2O3 doped Sm2Zr2O7 pyrochlores （Sm0.75 La0.25）2Zr2O7 and （Sm0.5 La0.5）2 Zr2O7 had lower thermal conductivity than the undoped Sm2Zr2O7. The thermal conductivity of （Sm0.25La0.75）2Zr2O7 was found to be lower than that of La2Zr2O7. The results showed that these ceramic materials had the potential to be used as candidate materials for TBCs.
基金the National Natural Science Foundation of China(51762036)。
文摘In this work,Nb^(5+)and Cu^(2+)were selected to partially substitute Zr4+in Gd_(2)Zr_(2)O_(7)for studying the phase structure,microscopic morphology and thermal properties.Gd_(2)(Zr_(1-3 x/2)Nb_(x)CU_(x/2))_(2)O_(7)(x=0,0.05,0.1,0.15,0.2,0.25)ceramic materials were synthesized by high-temperature solid-state reaction method.The results show that the Gd_(2)(Zr_(1-3 x/2)Nb_(x)Cu_(x)/2)_(2)O_(7)ceramics present cubic pyrochlore structure with clear grain boundaries and dense cell structure.And the thermal expansion coefficient of Gd_(2)(Zr_(1-3 x/2)Nb_(x)Cu_(x/2))_(2)O_(7)ceramics gradually decreases because of the incorporation of Nb^(5+)and Cu^(2+)into Zr-site in Gd_(2)Zr_(2)O_(7).Meanwhile,its thermal conductivity decreases firstly and then increases with the doping of Nb^(5+)and Cu^(2+),which reaches the lowest value for the composition of Gd_(2)(Zr_(0.85)Nb_(0.1)Cu_(0.05))_(2)O_(7).
基金supported by the National Natural Science Foundation of China(Nos.51672228 and 51202203)the Open Project of State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials(No.11zxfk26)+1 种基金the Young Outstanding Scientist Fund of Southwest University of Science and Technology(No.13zx9108)the Postgraduate Innovation Fund Project by Southwest University of Science and Technology(No.16ycx010)
文摘In this research, Zr-doped Gd_2Ti_2O_7 pyrochlores, with the composition of Gd_2(Ti_(1-x)Zr_x)_2O_7, were firstly synthesized by self-propagating high-temperature synthesis plus quick pressing(SHS/QP) using CuO as the oxidant and Ti as the reductant. To improve the radiation resistance of titanate–pyrochlore, up to 35 at% Zr was incorporated to substitute the Ti site of Gd_2Ti_2O_7 pyrochlore(Gd_2(Ti_(0.75)Zr_(0.35))_2O_7). XRD and SEM microstructural characterizations showed the formation of a composite ceramic with the major pyrochlore phase and the minor Cu phase. The generated temperature of samples decreased from 1702to 1011 ℃ with increasing Zr content. The effects of sintering temperature and pressure time on phase composition and microstructure were systematically studied. Besides, the influence of thermal transmission on the whole combustion process was also explored. The pyrochlore-based waste form possessed high bulk density of 6.25 g/cm^3 and Vickers hardness of 10.81 GPa. The MCC-1 leaching test showed the normalized elemental leaching rates(42d) of Cu, Gd, and Zr are 1.27×10^(-2), 1.33×10^(-3), and 8.44×10^(-7)g·m^(-2)·d^(-1), respectively.
基金supported by National defense ba-sic scientific research(Grant Nos.2022-JCKY-JJ-1086 and 211-CXCY-N103-03-04-00).
文摘Lattice engineering and distortion have been considered one kind of effective strategies for discovering advanced materials.The instinct chemical flexibility of high-entropy oxides(HEOs)motivates/accelerates to tailor the target properties through phase transformations and lattice distortion.Here,a hybrid knowledge-assisted data-driven machine learning(ML)strategy is utilized to discover the A_(2)B_(2)O_(7)-type HEOs with low thermal conductivity(κ)through 17 rare-earth(RE=Sc,Y,La-Lu)solutes optimized A-site.A designing routine integrating the ML and high throughput first principles has been proposed to predict the key physical parameter(KPPs)correlated to the targetedκof advanced HEOs.Among the smart-designed 6188(5RE_(0.2))_(2)Zr_(2)O_(7)HEOs,the best candidates are addressed and validated by the princi-ples of severe lattice distortion and local phase transformation,which effectively reduceκby the strong multi-phonon scattering and weak interatomic interactions.Particularly,(Sc_(0.2)Y_(0.2)La_(0.2)Ce_(0.2)Pr_(0.2))_(2)Zr_(2)O_(7)with predictedκbelow 1.59 Wm^(−1)K^(−1)is selected to be verified,which matches well with the ex-perimentalκ=1.69 Wm^(−1)K^(−1)at 300 K and could be further decreased to 0.14 Wm^(−1)K^(−1)at 1473 K.Moreover,the coupling effects of lattice vibrations and charges on heat transfer are revealed by the cross-validations of various models,indicating that the weak bonds with low electronegativity and few bond-ing charge density and the lattice distortion(r∗)identified by cation radius ratio(r A/r B)should be the KPPs to decreaseκefficiently.This work supports an intelligent designing strategy with limited atomic and electronic KPPs to accelerate the development of advanced multi-component HEOs with proper-ties/performance at multi-scales.
基金supported by the National Key Research and Development Program of China(No.2016YFB070204)the National Natural Science Foundation of China(Nos.52072381 and U1904217)。
文摘A novel high-entropy material,(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7)was successfully synthesized by the solid state reaction method and spark plasma sintering,and investigated as a promising thermal barrier coating material.Rare-earth elements were distributed homogeneously in the pyrochlore structure.It was found that the prepared high-entropy ceramic maintains pyrochlore structure at the temperature up to 1600℃,and it possesses a similar thermal expansion coefficient(10.2×10^(−6)K^(−1) at 25-900℃)to that of YSZ,low thermal conductivity(<0.9 W m^(-1)K^(−1) at 100-1000℃)and good CMAS resistance(infiltration depth is 22μm after annealed at 1300℃for 24 h).The corrosion process was investigated,and RE elements distributing homogeneously in(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7)show different diffusion rates in CMAS.RE^(3+) with a larger radius(closer to Ca^(2+))is easier to react with CMAS to form an apatite phase.
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supported by the Chinese Natural Science Foundation (21263015 and 21203088)the Education Department of Jiangxi Province (KJLD14005 and GJJ14205)the Natural Science Foundation of Jiangxi Province (20142BAB213013)
文摘A series of Ni/La2Zr2O7 pyrochlore catalysts prepared by impregnation method and treated by dielectric barrier discharge（DBD） plasma in different atmospheres and varied sequences were prepared and applied for dry reforming of methane（DRM）. It is found that all of the plasma treated catalysts show evidently improved activity and coke resistance in comparison with the non-plasma treated one. The best performance is achieved on Ni/La2Zr2O7–H2P–C,a catalyst treated in H2 plasma before calcination. TGA-DSC and SEM demonstrate that carbon deposition is significantly suppressed on all of the plasma treated samples. Moreover,XRD and TEM results testify that both Ni O and Ni sizes on the calcined and reduced samples treated by plasma are also decreased,which results in higher Ni metal dispersion on the reduced and used catalysts and enhances the interactions between Ni sites and the support. It is believed that these are the inherent reasons accounting for the promotional effects of plasma treatment on the reaction performance of the Ni/La2Zr2O7 pyrochlore catalysts.
