Preparation and Electrical Transport Properties of Perovskite Oxide Ln0.5Sr0.5CoO3

The superfine powders of Ln0.5 Sr0.5 CoO3 （Ln = La, Pr, Nd, Sm, Eu） were obtained by solid state reactions. The crystal structure and electrical transport properties of samples doped with different rare earth elements as well as the forming process of the Perovskite structure were studied. The result shows that when the temperature reaches 1200 ℃, the samples will become a steady and unitary Perovskite phase by solid state reactions. The conductive behavor at low temperature is consistent with small polaron mechanism （i. e., localized electronic carriers having a thermally activated mobility）. However, the maximum of conductivity appears at about 700 ℃, and the conductivity of La0.5Sr0.5CoO3 is the biggest in the intermediate-temperature （600 - 850 ℃ ）, so it is fit for cathode material of intermediate-temperature solid oxide fuel cells.     

Synthesis and characterization of calcium and manganese-doped rare earth oxide La_(1-x)Ca_xFe_(0.9)Mn_(0.1)O_(3-δ) for cathode material in IT-SOFC

In order to develop novel cathode materials with high performance for intermediate temperature SOFC(IT-SOFC),Ca and Mn doped rare earth oxides La1-xCaxFe0.9Mn0.1O3-δ(x=0.1,0.3 and 0.5,denoted as LCFM9191,LCFM7391 and LCFM5591) were synthesized by solid state reaction(SSR) method.The formation process,phase structure and microstructure of the synthesized samples were characterized using thermogravimetry/differential scanning calorimetry(TG/DSC),X-ray diffraction(XRD) and scanning electron microscopy(SEM).The thermal expansion coefficients(TEC) of the samples were analyzed at 100-900 oC by thermal dilatometry.The electrical conductivities of the samples were measured with direct current(DC) four-terminal method from 300 to 850 oC.The results indicated that the samples(x=0.1 and 0.3) exhibited a single phase with orthorhombic and cubic perovskite structure,respectively after being sintered at 1200 oC for 3 h.The electrical conductivity of the samples increased with temperature up to a maximum value,and then decreased.The small polaron hopping was regarded as the conducting mechanism for synthesized samples at T≤600 oC.The negative temperature dependence occurring at higher temperature was due to the creation of oxygen vacancies for charge balance.LCFM7391 had higher mixed conductivity(>100 S/cm) at intermediate temperature and could meet the demand of cathode material for IT-SOFC.In addition,the average TECs of LCFM9191 and LCFM7391 were 11.9×10-6 and 13.1×10-6 K-1,respectively,which had good thermal match to the common electrolytes.     

Solid state reaction synthesis and total electrical conductivity of La_(0.7)Sr_(0.3)Cr_yMn_zCo_(1-y-z)O_(3-δ)

The La0.7Sr0.3CryMnzCo(1-y-z)O3-δ samples were prepared by solid state reaction.The phases,microstructure and properties of the samples were investigated by XRD,SEM,DC four-probe method and iodometry method.The single orthorhombic phase La0.7Sr0.3CryMnzCo(1-y-z)O3-δ perovskite oxides were obtained when sintered at l350 °C for 10 h.The oxygen nonstoichiometry of the materials varied inversely with the total electronic conductivity.The sample with composition of La0.7Sr0.3Cr0.5Mn0.35 Co0.15O3-δ had the maximal total electronic conductivity and the lowest oxygen nonstoichiometry which were 22.4 S/cm and 0.040 at 850 °C,respectively.The low total electronic conductivity is related to the low relatively density of the samples directly.The activation energy of conduction changed at 550 °C,and the activation energy of conduction at high temperature(T550 °C) was higher than that at low temperature range(T550 °C).     

Crystal structure,thermal expansion and electrical conductivity of Pr（Ga1-xCox）0.9Mg0.1O3-δ （x=0, 0.1, 0.2, 0.3）

Pr（Ga1-xCox）0.9Mg0.1O3-δ （x=0, 0.1, 0.2, 0.3） was synthesized using solid-state reaction technique to study the effects of Co doping on their structure and properties. Room and high temperature XRD, DSC and electrical conductivity measurement with D.C. four-probe technique were adopted in the study. The results indicated its orthorhombic-distorted perovskite structure at room temperature. PrGa0.9Mg0.1O3-δ maintained its orthorhombic-distorted structure between 298 and 1173 K. For Pr（Ga0.7Co0.3）0.9Mg0.1O3-δ, such structure existed below 873 K. From 873 to 1173 K, it possessed tetragonal structure. The transformation from orthorhombic to tetragonal structure at 873 K was of second order. The intrinsic volume thermal expansion of tetragonal structured Pr（Ga0.7Co0.3）0.9Mg0.1O3-δ Was about 50% higher than those of PrGa0.9Mg0.1O3-δ. The electrical conductivity increased with Co content. The activation energies of conduction for Pr（Ga1-xCox）0.9Mg0.1O3-δ are in range from 0.197 to 0.246 eV, much lower than 1.543 eV for PrGaO3.     

Crystal structure, thermal expansion and electrical conductivity of Pr(Ga1-xCox)0.9Mg0.1O3-δ(x=0,0.1,0.2,0.3)

Pr(Ga1-xCox)0.9Mg0.1O3-δ(x=0, 0.1, 0.2, 0.3) was synthesized using solid-state reaction technique to study the effects of Co doping on their structure and properties. Room and high temperature XRD, DSC and electrical conductivity measurement with D.C. four-probe technique were adopted in the study. The results indicated its orthorhombic-distorted perovskite structure at room temperature. PrGa0.9Mg0.1O3-δ maintained its orthorhombic-distorted structure between 298 and 1173 K. For Pr(Ga0.7Co0.3)0.9Mg0.1O3-δ, such structure existed below 873 K. From 873 to 1173 K, it possessed tetragonal structure. The transformation from orthorhombic to tetragonal structure at 873 K was of second order. The intrinsic volume thermal expansion of tetragonal structured Pr(Ga0.7Co0.3) 0.9Mg0.1O3-δ was about 50% higher than those of PrGa0.9Mg0.1O3-δ. The electrical conductivity increased with Co content. The activation energies of conduction for Pr(Ga1-xCox)0.9Mg0.1O3-δ are in range from 0.197 to 0.246 eV, much lower than 1.543 eV for PrGaO3.     

Cathode Materials for Solid Oxide Fuel Cells(SOFC)

A detailed overview has been given concerning the use of rare earth materials in cathode fabrica-tion of solid oxide fuel cells(SOFC).It is focused on the various synthesis methods of the perovskite-typemixed rare earth oxides and the physical and chemical properties of the materials for cathode application ofSOFC.Also discussed is the doping mechanism of the related materials.Documented investigations showthat lanthanide of transition metals,especially manganese,chromium doped with strontium are most advan-tageous for the application.The crystallography,defect structure,conductivity and thermal matching withthe electrolyte and high temperature stability of cathode in oxidative gases are particularly emphasized.     

Preparation of Sr_2Fe_(1-x)Sc_xMoO_(6-δ) nanopowders and its electrical conductivity

Double-perovskite Sr2Fe1-xScxMoO6-δ (x=0, 0.05, 0.1, 0.2, 0.3, 0.4) powders applied to the cathode of solid oxide electrolysis cells were synthesized by the sol-gel citrate combustion method. Initial powders were calcined at different temperatures under different atmosphere (air, H2(4 vol.%)/Ar), and the effects of the preparation process on the structure and the morphology of the powders were investigated by thermal analysis (TG/DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and surface area analysis. The electric conductiv-ity of the materials was measured by electrochemical work station using wafers prepared by dry pressing. It was found that the formation of perovskite structure was related to the content of Sc and combustion improver (NH4NO3), pH value, calcining temperature and atmosphere. A single perovskite phase of Sr2Fe1-xScxMoO6-δ could be formed after 3 h calcining in reducing atmosphere of H2 (4 vol.%)/Ar at 1100 oC. The electrical property indicated that, this material had a potential to be used in medium/high temperature solid oxide fuel cells or electrolysis cells.     

Microwave assisted synthesis,sinterability and properties of Ca-Zn co-doped LaCrO_3 as interconnect material for IT-SOFCs

The interconnect materials La0.7Ca0.3Cr1-xZnxO3-δ(x=0,0.01,0.03,0.05,0.07) were prepared by a microwave assisted sol-gel auto-ignition process.The crystalline structures of the samples were characterized by X-ray diffraction(XRD) and the lattice parameters were evaluated with Rietveld method.For Ca-Zn co-doped LaCrO3 with x=0.03,the sintering activity was improved,and the relative density came up to 96.5% for the sample sintered at 1300 oC for 10 h.The electrical conductivity of the samples was increased from 21.1 S/cm to the maximum of 70.9 S/cm at 650 oC in air,with the x content increasing from 0.01 to 0.03.However,with x further increasing,the electrical conductivity was decreased.The average thermal expansion coefficient(TEC) of the samples at RT-1000 oC in air was ca.10.0×10-6 K-1.All data indicated that the La0.7Ca0.3Cr1-xZnxO3-δ series ceramics would be potential candidate to be used as an interconnect materials for IT-SOFCs.     

Preparation of Nanocrystalline Rare Earth Mixed Oxides DyFexCo1-xO3-δ and Its Conductivity

Nanocrystalline rare earth mixed oxides DyFexCo1-xO3-δ were prepared by sol-gel method and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TG-DTA) and scanning electron microscope(SEM). The results show that DyFexCo1-xO3-δ has the structure of perovskite type at 800℃ for 2 h calcination.The conductivity of the materials at different temperature was measured by four-probe instrumentation and two-pole method. The results show that the conductivity of mixed oxides DyFexCo1-xO3-δ is higher than those of un-mixed oxides DyFeO3 and DyCoO3 and the conductivity is the best at x = 0.8 in the matter of DyFexCo1-xO3-δ. The conduetivity of these materials always increases with the temperature rising and there is an apparent change between 600 and 800℃. However, the spinodals are different with different ration of Fe^3 and Co^3 . This kind of oxide is a conductive pottery material.     

Phase Behavior and Crystal Structure of Perovskite-Type Rare Earth Complex Oxides

Several compounds of rare earth complex oxides containing manganese and titanium were synthesized in Ar, and their crystal structures were analyzed by powder X-ray diffraction data and Rietveld method. Structures of A0.67Ln0.33 Mn0.33Ti0.6703（A = Ca or Sr and Ln = rare earth） were found to have orthorhombic symmetry with the space group Pnrna, and their interatomic distances and bond angles were obtained. This space group was also derived from electron microscopic study. Electrical conductivity of Cao.67Ln0.33Mn0.33Ti0.6703 for several rare earth elements showed a semiconducting property with the activation energy of 0.4 eV. Some of these compounds of the strontium system show the antiferromagnetic properties below 10 K.     

Synthesis of rare earth metal-organic frameworks （Ln-MOFs） and their properties of adsorption desulfurization

The rare earth metal-organic frameworks(Ln-MOFs) materials,Ln(BTC)(H2O)·(DMF),were synthesized using the rare earth metal(Ln=Sm,Eu,Tb,Y) and 1,3,5-trimesic acid(BTC) as a metal ion center and ligand,respectively.X-ray diffraction(XRD) and infrared spectroscopy(FT-IR) were employed to characterize the Ln-MOFs structural features.The property of adsorption desulfurization of Ln-MOFs materials was evaluated with thiophene/n-octane as model oil.The results showed that Ln-MOFs with rare earth metals Sm,Eu,Tb and Y had perfect crystalline and good adsorption desulfurization ability.Y(BTC)(H2O)·(DMF) material had a comparatively better activity for the adsorption desulfurization with desulfurization rate up to 80.7% and the sulfur adsorption capacity was found 30.7 mgS/g(Y-MOFs).The Ln-MOFs materials had excellent reusability.     

Preparation and characterization of La0.9Sr0.1Ga0.8Mg0.2O3–δ thin film deposited by radio frequency magnetic sputtering

La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolyte materials were synthesized by the solid state reaction method.The conductivity of LSGM materials was detected by four probe method,and it was 0.08 S/cm at 850 ℃.Dense and uniform films of LSGM materials were deposited by the magnetic sputtering on substrates of Si and La0.7Sr0.3Cr0.5Mn0.5O3-δ (LSCM).The experimental results showed that the deposition rates dropped and the average grain sizes of the films enlarged with increase in the substrate temperatures.In the sputtering process,the LSGM film was deposited with preferred growth direction.After annealing,the preferred growth direction disappeared and the film surface became smoother and denser.Through observing the deposition process,deposition mechanism was proposed,which was consistent with a model of island growth.     

Characterization of A-site excessive perovskite La0.7-xSmx＋0.02Ca0.3CrO3-δ

La0.7-xSmx+0.02Ca0.3CrO3-δ(0≤x≤0.4) powders with A-site excessive perovskite structure were synthesized by auto-ignition process and characterized. X-ray diffraction (XRD) patterns of samples after sintering at 1400℃ for 4 h were indexed as tetragonal structure. The relative densities were all above 96% although decreased slightly with the increasing content of samarium, indicating that the excessive A-site element was helpful to enhance their sinterability. Conductivities of the specimens in air increased with increasing content of samar-ium. The conductivity of La0.6Sm0.12Ca0.3CrO3-δ was 33.6 S/cm in air at 700 ℃ which was about 1.7 times as high as that of La0.7Ca0.3CrO3-δ (20.1 S/cm). Average thermal expansion coefficients (TECS) of the specimens increased from 11.06×10-6 to 12.72×10-6 K-1 when x in-creased from 0 to 0.4, and they were close to that of Y doped ZrO2 (YSZ). La0.7-xSmx+0.02Ca0.3CrO<3-δ>(0.1≤x≤0.3) were good choices for in-termediate temperature solid oxide fuel cells (IT-SOFCs) interconnect materials.     

Fabrication and Characterization of Glass-Ceramics Doped with Rare Earth Oxide and Heavy Metal Oxide

Cordierite-based glass-ceramics with non-stoichiometric composition doped with rare earth oxide (REO2) and heavy metal oxide (M2O3) respectively were fabricated from glass powders. After sintering and crystallization heat treatment, various physical properties, including compact density and apparent porosity, were examined to evaluate the sintering behavior of cordierite-based glass-ceramics. Results show that the additives both heavy metal oxide and rare earth oxide promote the sintering and lower the phase temperature from μ- to α-cordierite as well as affect the dielectric properties of sintered glass-ceramics. The complete-densification temperature for samples is as low as 900 ℃. The materials have a low dielectric constant (≈5), a low thermal expansion coefficient ((2.80～3.52)×10-6 ℃-1) and a low dissipation factor (≤0.2%) and can be co-fired with high conductivity metals such as Au, Cu, Ag/Pd paste at low temperature (below 950 ℃), which makes it to be a promising material for low-temperature co-fired ceramic substrates.     

Formation of intermetallic compound at interface between rare earth elements and ferritic-martensitic steel by fuel cladding chemical interaction

The intermetallic compounds formation at interface between rare earth elements and clad material were investigated to demonstrate the effects of rare earth elements on fuel-cladding chemical interaction(FCCI)behavior.Mischmetal(70Ce-30La)and Nd were prepared as rare earth elements.Diffusion couple testing was performed on the rare earth elements and cladding(9Cr2W steel)near the operation temperature of(sodium-cooled fast reactor)SFR fuel.The performance of a diffusion barrier consisting of Zr and V metallic foil against the rare earth elements was also evaluated.Our results showed that Ce and Nd in the rare earth elements and Fe in the clad material interdiffused and reacted to form intermetallic species according to the parabolic rate law,describing the migration of the rare earth element.The diffusion of Fe limited the reaction progress such that the entire process was governed by the cubic rate law.Rare earth materials could be used as a surrogate for high burnup metallic fuels,and the performance of the barrier material was demonstrated to be effective.     

Cathode catalysis performance of SmBaCuMO5+δ (M=Fe,Co,Ni) in ammonia synthesis

The SmBaCuMO5+δ (M=Fe, Co, Ni) (SBCM) powders were synthesized by the citrate sol-gel method and the powders were sintered to ceramic pellets. The powders and sintered ceramic pellets were characterized with XRD, TEM and SEM measurements. The cathode catalytic performances of SBCM ceramic pellets for ammonia synthesis were studied from wet hydrogen and dry nitrogen at atmospheric pressure and low temperature, using SBCM ceramic pellets as cathode, Nafion proton exchange membrane as electrolyte, Ni-Ce0.8Sm0....     

Wet chemical synthesis of La9.83–xSrxSi6O26+δ（0≤x≤0.50） powders,characterization of intermediate and final products

In this paper we reported the preparation and extensive characterization of La9.83–x Sr x Si6O26+δ(0≤x≤0.50) precursors, intermediate and final products. The sintering reactions, the phase formation, the structure as well as the powders’ morphology were studied by means of thermogravimetric analysis, X-ray diffraction(XRD), Fourier-transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM). Moreover, the effect of stoichiometry on precursor’s structure and morphology as well as on intermediate and final products was reported. As was concluded pure La9.83Si6O26+δ, La9.38Sr0.45Si6O26+δ and La9.33Sr0.50Si6O26+δ could be prepared after sintering at 1400 °C for 20 h while La9.68Sr0.15Si6O26+δ and La9.53Sr0.30Si6O26+δ compounds contained minor traces(<3.5%) of La2Si2O7 secondary phase. Concerning the synthesis, there have been no previous reports on the preparation of pure La9.83Si6O26+δ, La9.38Sr0.45Si6O26+δ and La9.33Sr0.50Si6O26+δ compounds. The final powders consisted of spherical particles and an increase of Sr content seemed to inhibit sintering phenomena. The existence of interstitial oxygen at intermediate crystallographic positions of apatite structure had great effect on Si O4 sub-structure distortion. The increase of Sr content led to a major reduction of interstitial oxygen quantity and the refutation of silicon tetrahedron distortion.     

Research on toughening mechanisms of alumina matrix ceramic composite materials improved by rare earth additive

Mixed rare earth elements were incorporated into alumina ceramic materials. Hot-pressing was used to fabricate alumina matrix composites in nitrogen atmosphere protection. Microstructures and mechanical properties of the composites were tested. It was indicated that the bending strength and fracture toughness of alumina matrix ceramic composites sintered at 1550 ℃ and 28 MPa for 30 min were improved evidently. Besides mixed rare earth elements acting as a toughening phase, AlTiC master alloys were also added in as sintering assistants, which could prompt the formation of transient liquid phase, and thus nitrides of rare earth elements were produced. All of the above were beneficial for improving the mechanical properties of alumina matrix ceramic composites.     

Defect structure and electrical properties of LaSr_3Fe_3O_(10-δ)

As a mixed conductor,LaSr3Fe3O10-δ with triple layer perovskite intergrowth structure can be used as an oxygen separation membrane material and cathode material in solid oxide fuell cells.LaSr3Fe3O10-δ was synthesized via citrate acid route.Iodine titration method was used to determine the average valence of transition metal Fe and oxygen nonstoichiometry δ.Conductivities of LaSr3Fe3O10-δ were measured in the oxygen partial pressure range from 10-2×105 to 1×105 Pa,by Ac four probe method.Seebeck coefficient...     

Characterization and Stability of La0.5Sr0.5CoO2.91 Perovskite-Type Oxide

Compositely doped oxide La0.5Sr0.5CoO2.91 （LSC） was synthesized using solid state reaction and citric acid-nitrate low temperature self-propagating combustion methods. The crystal structure and the particle size micrograph of LSC powders synthesized by different methods were investigated with XRD and SEM. The experimental results show that the single perovskite phase of LSC can be synthesized by solid state reaction method, but LaSrCoO4 phase appears in LSC powder synthesized by citric acid-nitrate low temperature self-propagating combustion method. The LSC particle by citric acid-nitrate low temperature self- propagating combustion method has smaller size. To analyze the character of cathode material based on Ceo.gGdo.101.95（GDC） electrolyte, two types of cathode wafers were fabricated with the two kinds of LSC and GDC powders at the mass rate of 6：4, respectively. The electrical conductivity of the sintered samples was measured by four probe DC method from 300 to 800 ℃. The cathode with LSC particle by citric acid- nitrate low temperature self-propagating combustion method has higher electrical conductivity. In order to investigate the stability, the two samples were put into the muffle furnace to heat up in air at 800℃for 800 h. To analysis the reason for reduced electrical conductivity, the crystal structure and the particle micrograph of the cathode wafers before and after an exposure were investigated with XRD and SEM. The result shows that new crystal structure appears in both the two kinds of cathode wafers and crystal micrographs change a lot.