Structure and oxygen storage capacity of Pr-doped Ce_（0.26）Zr_（0.74）O_2 mixed oxides

Binary Ce-Zr(CZ),Pr-Zr(PZ) and ternary Ce-Zr-Pr(CZP) mixed oxides were prepared by an ammonia-aided co-precipitation method,and were aged in a steam/air flow at 1050 °C.X-ray diffraction(XRD),Raman spectra,X-photon spectra(XPS) and CO temperature programmed reduction(TPR) were carried out to characterize the micro-structure and reducibility of catalysts.The oxygen storage capacity(OSC) was evaluated with CO serving as probe gas.The results showed that a pseudo cubic structure was formed for the Zr-rich ceria-zirconia mixed oxides with Pr doping.The insertion of Pr prevented the phase segregation of the mixed oxides during the hydrothermal ageing.The Pr doped samples showed better redox performances in comparison with CZ,and the sample doped with 5 wt.% Pr showed the most remarkably promoted dynamic oxygen storage capacity.This phenomenon was closely related to both the reducibility and oxygen mobility of the mixed oxides.The introduction of praseodymium into ceria-zirconia could accelerate the oxygen migration by increasing the amount of oxygen vacancies,although it was difficult for Pr3+ ions themselves to participate in the oxygen exchange process.     

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.     

Studies on electrical properties and CO-sensing characteristics of La_（0.9） _（0.1）FeO_3

Semiconducting sensors offer an inexpensive and simple method for monitoring gases. Sensors based on the ABO3-type composite oxides materials have an advantage of high stability. The perovskite structures of these compounds are preserved, when an A-site deficiency of some perovskite structure compounds was formed. However, they exhibit particular physical properties. In this paper, La0.9 0.1FeO3 powder with an orthorhombic perovskite phase was prepared by sol-gel method. The electrical properties and CO-sensing characteristics of the La0.9 0.1FeO3 were also investigated. The results demonstrated that the La0.9 0.1FeO3 was a p-type semiconductor material. Compared with LaFeO3, the conductance of La0.9 0.1FeO3 was better than that of LaFeO3. The sensor based on La0.9 0.1FeO3 showed excellent CO gas-sensing characteristics.     

Physico-chemical properties of 3-methoxy-2-nitrobenzoates of some rare earth elements（Ⅲ）

The complexes of 3-methoxy-2-nitrobenzoates of Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Er(III) and Tm(III) with the formula: Ln(C8H6NO5)3·2H2O, where Ln=lanthanides(III), were synthesized and characterized by elemental analysis, Forier transform irtrared (FTIR) spectroscopy, magnetic and thermogravimetric studies and also by X-ray diffraction (XRD) measurements. The complexes had col- ours typical for Ln(III) ions. The carboxylate groups bound as bidentate chelating. On heating to 1173 K in air they decomposed in the same way, at first, dehydrated in one step to anhydrous salts, and then decomposed to the oxides of respective metals with intermediate formation of the oxycarbonates. The enthalpy values of the dehydration process changed from 133.72 to 44.50 kJ/mol. Their solubility in water at 293 K was of the order of 10-4 mol/dm3. The magnetic moments of analysed complexes were determined by Gouy’s method in the range of 76-303 K.     

Magnetocaloric effect and magnetic properties of La_（0.9）Ce_（0.1）（Fe_（0.99）Mn_（0.01））_（11.6）Si_（1.4）H_（1.6） compound

Magnetocaloric effect and magnetic properties of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4 and its hydride La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 were investigated. The Curie temperature of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4 was increased by hydrogen absorption. XRD patterns showed that the structure of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 remained NaZn13-type. The Curie temperature (TC) of the sample was increased from 174 K to 331 K. The homogeneity of the hydrogen absorption for La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 was proven very well by the random measurement of DSC. The magnetic entropy △SM of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 had peak at 326 K. The peak value of-△SM-was 12.3 and 7.8 J/(kg.K) under magnetic field change of 0-2 T and 0-1 T,respectively,which was comparable with Gd5Si2Ge2. The negative slope and inflection point of the Arrott curve indicated that the first-order magnetic transition of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4 was reserved after hydrogen absorption.     

Synthesis and electrochemical properties of Ce-doped LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2 cathode material for Li-ion batteries

The layered material of Ce-doped LiNi1/3Mn1/3Co1/3O2 with α-NaFeO2 was synthesized by a co-precipitation method. X-ray diffraction (XRD) showed that Ce-doped LiNi1/3Mn1/3Co1/3O2 had the same layered structure as the undoped LiNi1/3Mn1/3Co1/3O2. The scanning electron microscopy (SEM) images exhibited that the particle size of Ce-doped LiNi1/3Mn1/3Co1/3O2 was smaller than that of the undoped LiNi1/3Mn1/3Co1/3O2. The Ce-doped LiNi1/3Mn1/3Co1/3O2 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram (CV), and electrochemical impedance spectra (EIS). The optimal doping content of Ce was x=0.02 in the LiNi1/3-xMn1/3Co1/3CexO2 samples to achieve high discharge capacity and good cyclic stability. The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through Ce-doping. The improved electrochemical performances of the Ce-doped LiNi1/3Mn1/3Co1/3O2 cathode materials were attributed to the addition of Ce4+ ion by stabilizing the layer structure.     

Synthesis and luminescence properties of Sr3-z（AlxSi1-x）O5-xFx：zCe^3＋phosphors

Sr3-z(Alx,Si1-x)O -5-xFx:zCe3+ phosphors were synthesized by high-temperature solid-state reaction.The structure and luminescence properties of phosphors with various Al/Si ratios and Ce3+ concentrations were characterized using various methods such as X-ray diffraction,photoluminescence excitation and photoluminescence spectra.XRD result displayed that a complete solid solution between Sr3AlO4F and Sr3SiO5 was formed.With the increasing of x value,a broader excitation band and stronger absorption appeared in the blue light region.Moreover,the emission band shifted to a shorter wavelength and the emission intensity reached a maximum at x=0.6.By adjusting the concentration of Ce3+,a widely tunable range of emission wavelength under the excitation of 460 nm was obtained from the green to yellow regions.In addition,the concentration and thermal quenching were also discussed.     

Up-conversion luminescence of Er~（3＋）-doped and Yb~（3＋）/Er~（3＋） co-doped 12CaO·7Al_2O_3 poly-crystals

The optical properties of Er3+-doped and Yb3+/Er3+ co-doped 12CaO·7Al2O3 (C12A7) poly-crystals, synthesized by high temperature solid state method, were investigated in detail. For Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals, two main emission bands centered around 530/550 nm (green) and 660 nm (red) were observed under 980 nm diode laser excitation via an up-conversion process. The intensity of green up-conversion emission had a strong increase in Er3+ (1.0 mol.%, 1.5 mol.%, 3.0 mol.%), and the intensity ratio of red to green up-conversion emission had an increase in Yb3+ (1.0 mol.%, 2.0 mol.%, 10. 0 mol.%)/Er3+ (fixed at 1.0 mol.%). This detailed study of the up-conversion processes allowed us to identify the dominant up-conversion mechanisms in Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals.     

Luminescent properties of MMgP_2O_7：Eu~（3＋）（M=Ca,Sr,Ba） phosphor

A series of red phosphors Eu3+-doped MMgP2O7(M=Ca,Sr,Ba) were synthesized by solid-state reaction method.X-ray powder diffraction(XRD) analysis confirmed the formation of pure CaMgP2O7,SrMgP2O7 and BaMgP2O7 phase.Photoluminescence spectra of MMgP2O7(M=Ca,Sr,Ba):Eu3+ phosphors showed a strong excitation peak at around 400 nm,which was coupled with the characteristic emission(350-400 nm) from UV light-emitting diode.The CaMgP2O7:Eu3+,SrMgP2O7:Eu3+ and BaMgP2O7:Eu3+ phosphors showed strong emission bands peaking at 612,593 and 587 nm,respectively.Due to the difference of the ion sizes between Ba2+(0.142 nm),Sr2+(0.126 nm),Ca2+(0.112 nm),Mg2+(0.072 nm) and Eu3+(0.107 nm),Eu3+ ions were expected to substitute for different sites in CaMgP2O7,SrMgP2O7 and BaMgP2O7 lattice.     

重型燃气轮机用La_2(Zr_(0.7)Ce_(0.3))_2O_7/YSZ双层热障涂层热循环性能研究

重型发电燃气轮机低排放、高效率的发展目标,要求燃气轮机透平的进气温度不断提高。热障涂层作为保护金属热端部件的重要手段,是实现这一目标的关键技术之一。目前世界上最先进的J级燃气轮机的透平进口温度已经达到1600℃,热端部件表面温度超过1250℃,传统的YSZ热障涂层已经不能满足这一发展需求,因此迫切需要开发温度更高、热导率更低的新型热障涂层。本文对La_2(Zr_(0.7)Ce_(0.3))_2O_7(以下简称LZ7C3)热障涂层在重型发电燃气轮机中的应用进行了初步验证。结果表明,LZ7C3涂层具有比常规YSZ热障涂层更低的热导率(0.79～0.48Wm~(-1)K~(-1),相对传统YSZ涂层下降30%以上),且在1250℃的高温火焰台架试验中表现出优良的热循环寿命( 7370次),具有良好的应用前景。     

Study on thermal expansion behavior of Dy2O3 - Al2O3 - SiO2 glass

Employing Dy2O3, Al2O3, and SiO2 as starting materials, several series of Dy2O3-Al2O3-SiO2 sealing glass were prepared. The relationship between their coefficients of thermal expansion and the contents of Dy2O3, Al2O3, and SiO2 were studied respectively. Experimental results showed that Dy2O3 and Al2O3 had a positive effect on the coefficient of thermal expansion of glass, whereas, SiO2 had a negative effect. The coefficient of thermal expansion of glass showed an apparent linear relation to the contents of these three raw materials, from which an estimation model was built, to calculate the coefficient of thermal expansion of sealing glass. Relative errors of the calculating results to testing results were no more than 2%, which suggested that the estimation model was reasonable. This study provides a good theory reference for the practical utilizing of this sealing material, through which a proper glass composition for good sealing could be easily found.     

Thermal conductivity of （Sm1-xLax）2Zr2O7 （x=0, 0.25, 0.5, 0.75 and 1） oxides for advanced thermal barrier coatings

Pyrochlore oxides of general compositions, A2Zr2O7, where A is a 3+ cation (La to Lu), are promising candidate materials for ap-plications 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, (Sm0.75La0.25)2Zr2O7, (Sm0.5 La0.5)2Zr2O7, (Sm0.25La0.75)2Zr2O7 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 ma-terials were analyzed by X-ray diffractometer (XRD) and fourier transform infrared spectroscopy (FT-IR) methods, respectively. The micro-structure was observed by scanning electronl 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)2Zr2O7 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 poten-tial to be used as candidate materials for TBCs.     

Preparation of La（OH）3 and La2O3 with Rod Morphology by Simple Hydration of La2O3

Lanthanum hydroxide with rod-like morphology was synthesized with simple hydration processing via the hydration of its bulk oxide in normal water solution at boiling temperature. An XRD pattern shows the formation of the hexagonal phase of La（OH）3, indicating that the hydration process is very rapid. The as-prepared La（OH）3 is almost entirely with a needle- or rod-like shape with a width of 2 - 3 μm and a length of 5 - 8 μm. The mechanism of the formation of La（OH）3 with rod-like morphology was preliminarily presented. It is easier to expand the simple hydration process on a large scale than the hydrothermal process.     

Phase structure and electrochemical properties of non-stoichiometric La0.7Ce0.3(Ni3.65Cu0.75Mn0.35Al0.15(Fe0.43B0.57)0.10)x hydrogen storage alloys

Phase structure and electrochemical characteristics of Co-free La0.7Ce0.3(Ni3.65Cu0.75Mn0.35Al0.15(Fe0.43B0.57)0.10)x (0.90≤x≤1.10) al-loys were investigated. When x was 0.90, the alloy was composed of LaNi5, La3Ni13B2 and Ce2Ni7 phases. The Ce2Ni7 phase disappeared, and the abundant of La3Ni13B2 phase decreased when x increased to 0.95. When x was 1.00 or higher the alloys consisted of LaNi5 phase. The lat-tice parameter a and the cell volume V of the LaNi5 phase decreased, and the c/a ratio of the LaNi5 phase increased with x value increasing. Maximum discharge capacity of the alloy electrodes first increased and then decreased with x value increasing from 0.90 to 1.10, and the highest value was obtained when x was 1.00. High-rate dischargeability at the discharge current density of 1200 mA/g increased from 50.7% (x= 0.90) to 64.1% (x=1.10). Both the charge-transfer reaction at the electrode/electrolyte interface and the hydrogen diffusion in the alloy were responsible for the high-rate dischargeability. Cycling capacity retention rate at 100th cycle (S100) gradually increased from 77.3% (x= 0.90) to 84.6% (x=1.10), which resulted from the increase in Ni content and the c/a ratio of the LaNi5 phase with x value increasing.     

Growth and interface of amorphous La2Hf2O7/Si thin film

Amorphous La2Hf2O7 thin films were deposited on Si(100) substrate by pulsed laser deposition (PLD) method under different con-ditions. The interfacial states of the La2Hf2O7/Si films were studied by synchrotron X-ray reflectivity (XRR) and X-ray photoelectron spec-troscopy (XPS). When grown under vacuum condition, silicate, silicide and few SiOx were formed in the interface layer. However, the Hf-silicide formation could be effectively eliminated by the ambient oxygen pressure during film growth. The result revealed that the La2Hf2O7/Si interlayer was intimately related with growth condition. Insufficient supply of oxygen would cause Hf-silicide formation at the interface and it could be most effectively controlled by the ambient oxygen pressure during film growth.     

Effect of rare earth doping on thermo-physical properties of lanthanum zirconate ceramic for thermal barrier coatings

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.     

Luminescence Properties of Sm^3＋ doped Bi2ZnB2O7

The phosphors of （Bi1- x Smx ） 2ZnB2O7 （ x = 0. 01, 0. 03, 0. 05, 0. 07, and 0. 09） were synthesized by conventional solid state reaction. The purity of all samples was checked by X-ray powder diffraction （XRD）. XRD analysis shows that all these compounds are of a single phase of Bi2ZnB2O7, indicating that the Bi^3＋ in Bi2ZnB2O7 can be partly replaced by the Sm^3＋ without the change of crystal structure. The excitation and emission spectra at room temperature show the typical 4f-4f transitions of Sm^3＋ . The dominant excitation line is around 404 nm due to ^6H5/2→^4K11/2 and the emission spectrum consists of a series of lines at 563, 599, 646, and 704 nm due to ^4G5/2→^6H5/2, ^6H7/2, ^6H9/2, and ^6H11/2, respectively. The optimal concentration of Sm^3＋ in Bi2ZnB2O7 is about 3mol% （relative to lmol Bi^3＋ ） and the critical distance Rc was calculated as 2.1 nm. The temperature dependence of the emission intensity of Bi1.94Sm0.06ZnB2O7 was examined in the temperature range between 100 and 450 K. The quenching temperature where the intensity has dropped to half of the initial intensity is 280 K. The lifetime for Sm^3＋ in Bi1.94Sm0.06ZnB2O7 is fitted as a value of 0.29 and 1.03 ms.     

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.     

Microstructure and Properties of Lao.7 Sr0.3 MnO3 Films Deposited on LaAlO3 （100）, （110）, and （111） Substrates

A comparative study of the crystalline structure, magnetic properties, and transport properties of LSMO films grown on （100）-, （110）-, and （111） LaAlO3（LAO） substrates was carried out. Using atomic force microscopy, round, rectangle, and dot surface morphologies were observed in （ 100）-, （ 110）-, and （ 111 ）-oriented LSMO films, respectively. Electrical and magnetic characterizations were performed on LSMO films of different orientation to provide evidence for the effect of strain on the magnetotransport properties. The （ 111 ）-oriented LSMO film has higher saturation magnetization and lower resistance compared with the （100）- and （110）-oriented LSMO films, which results from the smaller elastic deformation due to the larger elastic modulus along the 〈 111 〉 crystallographic direction.