Synthesis and Electrical Properties of La0.6M0.4FeO3-δ(M=Ca, Sr, Ba) as Cathodes for SOFCs

A series samples of La0.6M0.4FeO3-δ (M=Ca, Sr, Ba) perovskite-type oxides were prepared by glycine nitrate process (GNP). FTIR, TG-DSC, XRD and TEM techniques were used to characterize the chemical constitution, thermal stability and phase structure. The electrical conductivity of the samples was investigated by four-probe technique. With the increase of substituted-ionic radius, the temperature of phase formation increases, and the solid solubility decreases gradually, respectively. The La0.6Ca0.4FeO3-δ(LCF)powder is pure cubic perovskite-type crystalline after fired at 850 ℃ for 2 h. The XRD patterns of La0.6Sr0.4FeO3-δ(LSF) powder shows a small quantity of SrO peaks sintered at 1050 ℃ for 2 h. The electrical conductivity of LCF and LSF at 500～800 ℃ is over 100 S·cm-1, and the value of LCF is 1170 S·cm-1 at 800 ℃, which indicate that LCF and LSF may be used as a profitable cathode for IT-SOFCs. The characteristic of La0.6Ba0.4FeO3-δ(LBF) is poor, and the electrical conductivity at intermediate temperatures is 1/20 less than that of LSF.     

Surface and Texture Properties of Tb-Doped Ceria-Zirconia Solid Solution Prepared by Sol-Gel Method

The three-way catalysts （TWCs） promoters Ce0.6Zr0.4- x TbxO2-y were prepared by sol-gel method. BET surface areas analysis indicated that an increase of the dopant Tb content from x = 0.05 to x = 0.15 favors an increase of surface area from 66.8 to 80.4 m^2· g^-1 compared with the undoped sample Ce0 .6oZr0.40O2 65.1 m^2·g^- 1 after calcination at 650℃. Transmission electron microscopy （TEM） observation indicated that the doped samples have a higher thermal stability. The XRD and Raman spectra confirmed that the Ce0.6Zr0.4-xTbxO2-y cubic solid solution is formed. XPS analysis revealed that Ce and Tb mainly existed in the form of Ce^4＋ and Tb^3 ＋ , and Zr existed in the form of Zr^4＋ on the surface of the samples. The doped samples were homogenous in composition ; the introduction of Tb into the CeO2-ZrO2 promoters resuited in the formation of a solid solution, and the concentration of surface lattice oxygen was increased.     

Microstructure and properties evolution of plasma sprayed Al_2O_3-Y_2O_3 composite coatings during high temperature and thermal shock treatment

Al_2O_3-Y_2O_3 composite powder with TiO_2 additive was plasma sprayed to prepare Al_2O_3-Y_2O_3 composite coatings.The micro structure and properties evolution of the Al_2O_3-Y_2O_3 coatings during high temperature and thermal shock resistance were investigated.The results show that the micro structure of the Al_2O_3-Y_2O_3-TiO_2 coating is more uniform than that of the Al_2O_3-Y_2O_3 coating.Meanwhile,amorphous phase is formed in the two coatings.The Al_2O_3-Y_2O_3(-TiO_2) coatings were heat treated for 2 h at temperatures of 800,1000 and 1200℃,respectively.It is found that the microstructure and properties of the two coatings have no obvious change at 800℃.Some of the amorphous phase is crystallized at1000℃,and meanwhile Y_2O_3 and Al_2O_3 react to form YAG phase and YAM phase.At 1200℃,all of the amorphous phases are crystallized.After heat treatment,the micro hardness of the two coatings is increased.The thermal shock resistance of the Al_2O_3-Y_2O_3 system coatings can be improved by using TC4 titanium alloy as substrate and with NiCrAlY bonding layer.Moreover,the Al_2O_3-Y_2O_3-TiO_2 coating exhibits better thermal shock resistance due to the addition of TiO_2.     

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.     

Preparation and Characterization of La0.8Sr0.2MnO3-δ Cathode for SOFCs Fabricated Using Azeotropic Distillation Method

Strontium doped lanthanum manganite (LSM) powders were synthesized by three different routes: azeotropic distillation, sol-gel and solid state reaction respectively. The LSM samples, made by azeotropic distillation and sol-gel methods were prepared by firing at 1000 ℃ for 6 h, and the LSM sample, made by solid state reaction method was produced by sintering at 1400 ℃ for 18 h. The samples were characterized by XRD, TEC, SEM, EIS and polarization performance analysis. The results show that all the samples made by different methods have pure orthorhombic LSM phase, however exhibit different micro structure and electrochemical characterization, which relates to the different synthesis methods. The solid state reaction method produces the samples with larger particle size compared with azeotropic distillation and sol-gel methods. The powders made by azeotropic distillation method have less agglomerated particles compared with that made by sol-gel method because the precursor in the former is dispersed in n-butanol before sintering. The polarization current density of powder made by azeotropic distillation method was twice of that made by sol-gel method and four times of that made by solid state reaction method. The values of polarization resistance (Rp) are 0.35 Ω·cm2 for the cathode synthesized by azeotropic distillation route, which is much lower than sol-gel (1.5 Ω·cm2) and solid state reaction (2.3 Ω·cm2) at 800 ℃.     

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.     

Effect of Temperature on Carbothermic Reduction of Ilmenite

The reduction of ilmenite (FeTiO3) has been studied extensively. Temperature for the carbothermic reduction of ilmenite ranges from 900 ℃ to 1 400 ℃, and the reduction degree of Panzhihua ilmenite increases with increasing temperature. X ray diffraction analysis and SEM analysis were used to identify the phase before and after reduction, and to identify the morphology of reduced samples respectively. It is found that the reaction initiates at about 860 ℃. The reaction rate varies with temperature simultaneously. Impurities in Panzhihua ilmenite decrease the reduction degree. Magnesium and calcium oxide-rich zone is formed preventing complete reduction of Fe^2 . In general, the reaction products are iron, Ti3O5 and carbon.     

Synthesis and Luminescence Properties of Gd2O3：Eu^3＋ Phosphors

Gd2O3: Eu^3 phosphors were prepared by urea homogeneous precipitation with different surfactant and sol-gel method. XRD patterns show that all the obtained samples are in cubic Gd2O3, and the results of FTIR and fluorescent spectra conformed that OP is a good surfactant for preparing the Gd2O3:Eu^3 phosphors. The SEM photographs show that the particles prepared by urea homogeneous precipitation method are all spherical and well-dispersed, and grain morphology can be controlled by different surfactant. XRD and SEM indicate that the particle sizes prepared by sol-gel method are in the range of 5-30 nm, and the grain sizes increase with increasing of heated temperatures. Luminescence spectra indicat that the main emission peaks of all samples are at 610 nm, the intensities are different from samples prepared with different surfactant and the luminescence intensities increase with increasing of annealed temperatures.     

Synthesis and characterization of tungsten and barium co-doped La_2Mo_2O_9 by sol-gel process for solid oxide fuel cells

Herein, we demonstrate the synthesis of W and Ba co-doped La_2Mo_2O_9(LBMWO) nanocrystalline powder by a sol-gel process. In all the compositions have general formulae La_(1.9)Ba_(0.1)Mo_(2-x)W_xO_(8.95)(x = 0-0.40). The crystal structure, microstructure and conductivity of LBMWO were characterized by X-ray diffraction, scanning electron microscopy and electrical impedance spectroscopy. In addition, the thermal and decomposition properties of the LBMWO gel were analyzed by differential scanning calorimetry-thermogravimetric. The results reveal that all LBMWO powders calcined at 700 ℃ have a cubic structure;the average crystallite size is about 48 nm. The unit cell parameter of LBMWO powders increases with increase in W content. The as-synthesized nanocrystalline LBMWO samples exhibit excellent sinterability and a relatively lower sintering temperature of 900 ℃. A high relative density of -96% is achieved after sintering at 900 ℃ which is in good agreeme nt with the re sults of the SEM. Moreover, W and Ba codoping suppresses the phase transition and effectively stabilizes the β-phase at low temperature. At the same time,La_(1.9)Ba_(0.1)Mo_(1.85)W_(0.15)O_(8.95) exhibits high ionic conductivity, 3.07 x 10~(-2) S/cm at 800 ℃. It is therefore concluded that co-doping can improve the properties of La_2MO_2O_9 electrolytes.     

Magnetic Transition of La0.8Sr0.2Mn1-xCoxO3（x =0, 0.3, 0.5, 1.0）

A series of rare earth compound oxides with the formula of La0.8Sr0.2Mn1-xCoxO3（ were prepared by the method of citric acid. Structures, figures and magnetic properties of the x=0.0, 0.3, 0.5, 1.0） samples were analyzed by means of XRD, SEM and SQUID. Experiment results prove that all the samples are hexagonal, but their figures and magnetic properties are different. La0.8Sr0.2MnO3 is ferromagnetic. La0.8Sr0.2Mn0.7CO0.3O3 and La0.8Sr0.2Mn0.5Co0.5O3 are ferrimagnetic. La0.8Sr0.2CoO3 is antiferromagnetic. SEM results indicate that the structure of the first three are three-dimensional reticulations which are made up of some small ellipsoids which link up at the head and the end. The fourth sample looks like some dispersed small balls.     

High Temperature Rapid Tempering Process of SS400 Steel With Thermomechanical Simulation Tester

 The effect of refined precipitations and dispersed phases on the toughness of SS400 steel was investigated by rapid tempering with thermomechanical simulation tester, and the electromagnetic induction rapid tempering process was simulated. The conventional tempering and rapid tempering process were proceeded respectively, and both samples were quenched in 10% of agitated iced brine. The tempering temperatures were designed as 560, 620 and 680 ℃, respectively. Rapid tempering specimens were heated at a heating rate of 20 ℃/s, and all samples of these three tempering temperatures were maintained 30, 40 and 50 s with the Gleeble1500-D tester, respectively. The impact test at -40 ℃ were carried out on a Charpy impact machine (CBD-300) with a maximum measurement range of 300 J and the microstructures were analyzed in detail using optical microscope (OM) and scanning electron microscope (SEM). The experiment results show that the upper bainite, martensite and small amount of austenite were obtained in the rapidly quenched samples. In comparison to the conventional process, the matrix microstructure was changed from the larger size and bulk ferrite to the refined banding structure, and the cementites were obviously refined and precipitated inside the grains and along the grain boundaries. The cryogenic impact test implies that the maximum values of impact toughness with holding time of 30 or 50 s are achieved at tempering temperature of 620 ℃. Furthermore, a favorite value of impact toughness with holding time of 40 s is available.     

Effects of Nanometer Carbon Black on Performance of Low-Carbon MgO-C Composites

The low-carbon magnesia-carbon(MgO-C)composites containing 3%(mass fraction,the same below)carbon were prepared by adding various types of carbon black(CB).The mechanical properties,oxidation resistance at 1100 ℃ in oxidizing atmosphere,and thermal shock resistance after 5 times dipping in 1600 ℃ molten steel of the low-carbon composite samples were investigated,compared with a commercial high-carbon MgO-C composite containing carbon of 16%.The results show that the mechanical properties,oxidation resistance and thermal shock resistance of the low-carbon samples are improved with the decrease of CB particle size.Thermal shock resistance of the low-carbon sample containing nanometer CB N220 is obviously better than that of other low-carbon samples,and reaches the level of the high-carbon samples.     

Electrical Properties and Applications of （ZrO2）0.92 （Y2O3）0.08 Electrolyte Thin Wall Tubes Prepared by Improved Slip Casting Method

8%(mole fraction) yttria-stabilized zirconia electrolyte thin wall tubes were prepared by improved slip casting method. The length and wall thickness of the tubes are 266 mm and 0.4 - 0.9 mm, respectively and the relative density is 96.7 %. The microstructure and electrical properties of samples sintered at different temperatures were studied using SEM and ac impedance spectroscopy. The effect of sintered density, grain and grain boundary on the electrical properties of the samples was analyzed. The research results show that the density of the samples increases gradually with increasing sintering temperatures. The microstructurc of samples strongly influences its electrical properties, and the electrical prop.erties of samples enhance with the increase of sintered density. The ionic conductivity of grain and grain boundary is increased as the sintering temperature increases. Better sinterability of the samples was obtained at the sintering temperature of 1650℃. The maximum open circuit voltage and short circuit current for single cell is 0.946V and 1.84A, respectively. The maximum output power of single cell is 0.46W at the temperature of 850℃.     

Structural and superconducting properties in Y0.6Gd0.4Ba2（Nb）Cu3O7-y cuprates doped with niobium

Polycrystalline YBa2Cu3O7-y (YBCO) and Y0.6Gd0.4Ba2-xNbxCu3O7-y (YGBNCO) compounds with 0≤x≤0.225 were synthesized using standard solid state reaction technique. The structure for all samples was characterized by X-ray difference (XRD) and scanning electron microscopy (SEM). The transport properties were measured by the (FPP) method in the temperature range from 70 to 130 K. As the Nb content in the samples increased, a diffused phase indicating a niobium perovskite phase and a small amount of unidentified phase appeared. With the increase of Nb content, the superconducting transition temperature Tconset increased slowly with x≤0.125, and then it remained unchanged or slowly decreased with 0.125≤x≤0.225. It could be found that there was a slow decrease of zero-resistance temperature, Tcoffset, with the increase of Nb content. The larger transition width might result from the YBa2NbO6 phase, impurity and unidentified phases of the sample due to the Nb doping.     

Effect of Hf on Stress Rupture Properties of DD6 Single Crystal Superalloy After Long Term Aging

 The specimens of the second generation single crystal superalloy DD6 with different Hf contents were prepared in the directionally solidified furnace with a high temperature gradient. The long term aging of the specimens after full heat treatment was performed at 1040 ℃ for 800 h. The effect of Hf on the microstructure and stress rupture properties under 980 ℃/250 MPa of the alloy after long term aging was investigated. The results show that the γ′ coarsening and rafting and no topologically close packed phase (TCP) are observed in the microstructures of DD6 alloy with different Hf contents after aged at 1040 ℃ for 800 h. It indicates that DD6 alloy with different Hf contents all possesses good microstructure stability. With increasing Hf content the rupture life after long term aging turns shorter and the elongation represents the increasing first and decreasing afterwards. The fracture mechanism of the alloy with different Hf contents at 980 ℃/250 MPa all shows dimple model. The influence of the microstructures on the stress rupture properties of the alloy is also discussed.     

Effect of Tempering Temperature on Microstructure and Mechanical Properties of Steel Containing Ni of 9 %

  Mechanical properties of quenching, intercritical quenching and tempering (QLT) treated steel containing Ni of 9% were evaluated from specimens subject to various tempering temperatures. The detailed microstructures of steel containing Ni of 9% at different tempering temperatures were observed by optical microscope (OM) and transmission electron microscope (TEM). The volume fraction of austenite was estimated by XRD. The results show that high strength and cryogenic toughness of steel containing Ni of 9% are obtained when the tempering temperature are between 540 and 580 ℃. The microstructure keeps the dual phase lamellar structure after the intercritical quenching and there is cementite created in the Ni rich constituents when tempering temperature is 540 ℃. When tempering temperatures are between 560 and 580 ℃, the reversed austenites (γ′) grow up and the dual phase lamellar structure is not clear. The γ′ becomes instable at 600 ℃. When tempered at temperature ranging from 500 to 520 ℃, the increase of dislocation density in the lamellar matrix makes both tensile strength and yield strength decrease. When tempered at 540 ℃ and higher temperature, the yield strength decreases continuously because the C and alloying elements in the matrix are absorbed by the cementite and the γ′, so the yield ratio is decreased by the γ′. There are two toughness mechanisms at different tempering temperatures. One is that the precipitation of cementite absorbs the carbon in the steel which plays a major role in improving cryogenic toughness at lower temperature. Another is that the γ′ and the purified matrix become major role at higher tempering temperature. When the tempering temperature is 600 ℃, the stability of γ′ is decreased quickly, even the transformation takes place at room temperature, which results in a sharp decrease of Charpy V impact energy at 77 K. The tempering temperature range is enlarged by the special distribution of cementite and the lamellar structure.     

煤和废塑料混熔燃烧过程的动力学研究

The combustion-dynamic experiments of blend-melt samples of blending pulverized coal and waste plastic are carried out in different proportions at different combustion temperatures. The experiment shows that all of correlation coefficients for fitting straight lines of curve F(a)-1/T of the blend-melt samples are above 0.95, which indicates that the combustion of samples conforms to the rules of first order reaction. The experiment also shows that the activation energy is the lowest and the combustion becomes easier with the mix proportion of 20%-25% at 200 ℃.     

Coercivity enhancement of nanocrystalline hot-deformed Nd-Fe-B magnets by low-melting eutectic MM-Cu(MM=La,Ce,Pr,Nd) alloys addition

MM_(85)Cu_(15)(MM = La,Ce,Pr,Nd) eutectic alloys were added into the hot-deformed Nd-Fe-B magnets to enhance the coercivity.It is found that three endothermic peaks occur on the differential scanning calorimetry curve of the MM-Cu melt-spun ribbons at 432.2,451.1 and 516.5℃.The peaks substantially correspond to three types of MM-Cu low-melting eutectic phase.The coercivity of magnets increases when the MM-Cu content is lower than 4 wt%,and then keeps almost no change with the content further increasing to 5 wt%.The coercivity of the hot-deformed magnets with 4 wt% and without MM-Cu addition is 948 and 683 kA/m,respectively.Nearly all the platelet-shaped grains are isolated by the thickened intergranular phase after MM-Cu addition.Moreover,the average grain size of the magnets with MM-Cu addition decreases compared with that of the magnet without MM-Cu addition.Scanning electron microscopy images show that the areal fraction of the RE-rich grain boundary phase increases from 8.6% to 15.1% after MM-Cu addition.The La,Ce together with Cu and Ga aggregate at the grain boundary regions separating neighboring grains and smoothing the grain boundaries.Therefore,both the thickened grain boundary and decreased mean grain size result in the enhancement of coercivity after MM-Cu eutectic alloy addition.     

Coercivity enhancement of Ce-containing hot-deformed magnets by grain boundary diffusion of DyF3

The samples with full density were prepared by hot pressing the the melt-spun powders mixed with DyF₃powders of different mass fractions followed by hot-deformation process.The magnetic properties and temperature dependence of coercivity were obtained by BH tracer and VSM,respectively.The microstructure were analyzed by scanning electron microscopy(SEM)and transmission electron microscopy(TEM).The coercivity of Ce-containing hot-deformed magnets is increased from 1.41 to 1.95 T by grain boundary diffusion of 3 wt%DyF₃,and is further enhanced to 2.05 T after annealing treatment.The thermal stability of coercivity and remanence is improved.The annealing condition in this work crucially plays a role in thickening the grain boundary phase.Microstructure analysis reveals that the continuous and thick grain boundary phase formed after DyF₃diffusion can weaken the magnetic coupling between grains,and suppress the platelet shaped grain size and the aspect ratio.The Dycontaining shell structure formed by the partial diffusion of Dy into the main phase can increase the magnetic anisotropy field,which is the main reason for the coercivity improvement.After optimizing the structure by DyF₃diffusion,the"dendritic-like"reverse domain is transformed into the"dot scatteredlike"reverse domain.     

Magnetic Properties of La1-xSrxCoO3 （0 ≤ x ≤ 0. 5）

The measurements of temperature dependence of the magnetic susceptibility of La1-xSrxCoO3 perovskite oxides at different Sr doping （0 ≤x ≤0.5） and annealing temperature were presented. For the sample with x = 0.1, a shoulder was observed around 150 K, and a peak which is one feature of spin glass appeared around 50 K in the curve of susceptibility versus temperature. The high-temperature （250 - 420 K）susceptibility fits well with Curie-Weiss law for all samples. Weiss constant and effective magnetic moment were determined and their variations with Sr doping and oxygen annealing condition were obtained. The Weiss constant increases monotonously with Sr content for x 〉 0.2. The values of effective moments were interpreted with the spin state of cobalt ions. Studies on the susceptibilities of the samples with x = 0.2 under different preparation temperatures and annealing temperatures show that the rising of sintering temperature and annealing temperature will increase the para-ferromagnetic transition temperature, and reduce the effective moment to normal value. Our result shows that both Co^3＋ and Co^4＋ ions should be in IS state after annealing and the oxygen annealing causes the transition of Co^3＋ spin state from HS to IS.