Crystal structure and hard magnetic properties of TbCu_7-type Sm_(0.98)Fe_(9.02–x)Ga_x nitrides

The compound Sm0.98Fe9.02–xGaxNδ(x=0, 0.25, 0.5, 0.75, 1) were prepared by melt-spun method and subsequent annealing and nitriding. The Rietveld analysis showed that the lattice expansion played an important role in improving the Curie temperature. An obvious development of the Curie temperature was obtained with the increased Ga content from x=0–1(ΔTc=90 oC). The optimum coercivity of nitrides was obtained at x=0.25 with the value Hcj=652 kA/m(8.15 kOe) after annealing, which corresponded to a reasonable distribution of grain sizes of both TbCu7-type SmFe9Nδ and α-Fe. However, an excess of Ga doping might lead to an abnormal growth of α-Fe, which in turn deteriorated the magnetic properties. It was concluded that a moderate Ga content was very effective in raising the coercivity and Curie temperament in the TbCu7-type Sm-Fe-N.     

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.     

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.     

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.     

Effect of samarium filling on the lattice thermal conductivity of skutterudite materials

Sm-filled skutterudites SmxCo4Sb12 (x=0.1, 0.2, 0.5) were synthesized via high pressure and high temperature (HPHT) technique. The temperature dependences of electrical resistivity, Seebeck coefficient and thermal conductivity were measured on these compounds in the range of 300-723 K. All samples showed n-type conduction. The thermal conductivity of SmxCo4Sb12 was significantly depressed as com-pared to unfilled CoSb3. It was believed that Sm atoms "rattled" in the voids of structure and substantially affected the phonon propagation through the lattice. The dimensionless thermoelectric figure of merit, ZT, increased with increasing temperature and reached a maximum value of 0.81 for Sm0.5Co4Sb12 at 723 K.     

Magnetic properties and magnetic exchange interactions in Gd_(1–x)RE_x(RE=Pr,Nd) alloys

The effect of Pr,Nd addition on the magnetic properties and magnetic exchange interaction of gadolinium alloys was systematically studied.Curie temperature T_C and magnetic moment of Gd_(1–x)RE_x(RE=Pr,Nd)systems with x0.05 were investigated.When x0.05,Pr and Nd formed respectively with Gd continuous solid solution which has the crystalline structure HCP.Study on the magnetic behavior indicated that at near room temperature,the simple ferromagnetism prevailed in these two systems of alloy.The Curie temperature and magnetic moment of Gd_(1–x)RE_x alloy decreased with RE(RE= Pr,Nd)content x increasing.The de Gennes factor of Gd_(1–x)RE_x alloy which was associated with the exchange interaction between magnetic spin components also decreased with RE content increasing.The above results showed that the magnetic exchange interaction between magnetic atoms in gadolinium could be effectively changed by the Pr,Nd addition.     

Synthesis of photocatalytic La(1-x)AxTiO3.5-δ(A=Ba,Sr, Ca) nano perovskites and their application for photocatalytic oxidation of congo red dye in aqueous solution

A-site substituted La0.8A0.2TiO3.5–δ(A=Ba, Sr, Ca) nano perovskites were prepared by sol-gel method and characterized using thermogravimetry/differential thermal analysis(TGA/DTA), X-ray diffraction(XRD), ultraviolet-visible(UV-Vis) spectroscopy and transmission electron microscopy(TEM). XRD analysis showed that the La0.8A0.2TiO3.5–δ(A=Ba, Sr, Ca) nano perovskites derived after calcination at 800 oC were in single phase with orthorhombic structure. The particle size of all nano perovskites was found to be ~20 nm. The synthesized nano perovskites were tested for the photocatalytic decomposition of an azo dye, Congo red. The sequential behavior of La0.8A0.2TiO3.5–δ(A=Ba, Sr, Ca) nanoperovskites for photocatalytic decomposition of congo red in aqueous solution by visible light at room temperature was studied at various time intervals and the efficiency of degradation of the nanoperovskites was compared. Among all the A-site substituted La0.8A0.2TiO3.5–δ(A=Ba, Sr, Ca) nano perovskites, Ba substituted compound showed the highest dye degradation.     

Thermal expansion anomaly and spontaneous magnetostriction of Gd2Fe17 compound

Materials with negative thermal expansion have many practical applications. However, these materials are known in only several oxide systems, and when the negative thermal expansion occurs, the contraction is usually small and limited to a narrow temperature range beyond room temperature. For obtaining a compound with negative thermal expansion in broad temperature range, the structural and magnetic properties of Gd2Fe17 compound were investigated by means of X-ray diffraction and magnetization measurements. The Gd2Fe17 compound annealed at 1050 oC had a Th2Zn17-type structure. There existed an anisotropic strong spontaneous magnetostriction and a negative thermal expansion in Gd2Fe17 compound. The average thermal expansion coefficients was =-7.40×10-6/K in the temperature range of 294-453 K and =-1.80×10-5/K in 453-534 K, respectively. The spontaneous magnetostrictive deformation ωS decreased from 4.34×10-3 to near zero with temperature increasing from 294 to 572 K. The spontaneous linear deformation λc was much larger than λa at the same temperature below about 500 K.     

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.     

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.     

Effects of Cobalt Content and Preparation on Electrochemical Capacity of AB5-Type Hydrogen Storage Alloys at Different Temperature

The effects of Co as a substituent for Ni on microstructure and electrochemical capacity of hydrogen storage alloys MI(NiCoMnAl)5.4 at -30～ 80 ℃, in which the content of Co was 0, 1.31%, 2.63%, 3.94%, 5.25%, and 6.56% (mass fraction), respectively, were reported. All of the alloys were prepared by vacuum induction melting followed by melt-spinning. It is found that the electrochemical capacity of alloys at different temperature depends upon the compositions and preparation methods. The electrochemical capacity of alloys increases at higher temperature (40 ～ 80 ℃ )and decreases at lower temperature ( - 30 ～ 0 ℃ ) with an increasing cobalt content. With an increasing temperature,melt-spinning is more favorable for improved capacity of the alloys than casting. Analyses of the charging/discharging potential curves illustrate that higher cobalt content and melt-spinning techniques are more effective to increase the capacity at higher temperature because of the higher hydrogen evolution potential. On the contrary, the capacity of alloys at lower temperature can be increased by decreasing cobalt content and casting, which is ascribed to higher hydrogen evolution potential and delayed hydrogen evolution reaction, as well as reduced potential drop in the charging/discharging process.XRD patterns confirm that all of the specimens present a single hexagonal CaCu5-type structure and an increased lattice parameters with increasing Co content. The FWHM of the main peak of melt-spun ribbons reduces because of more homogeneous composition and less lattice strain defects.     

Thermogravimetric Study on Oxygen Adsorption/Desorption Properties of Double Perovskite Structure Oxides REBaCo2O5+δ (RE= Pr, Gd, Y)

The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5+δ, GdBaCo2O5+δ, and YBaCo2O5+δ were investigated by the thermogravimetry (TG) method in the temperature range of 400～900 ℃. The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides, such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ, whereas, the oxygen permeation flux was comparable to that of the latter, which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere (Δδ/Vmol) in these double perovskite structure oxides. The large oxygen adsorption/desorption rate constants of GdBaCo2O5+δ and PrBaCo2O5+δ made them nice catalyst coating materials, on other membrane surfaces, to improve the oxygen permeability.     

Thermal and transport properties of La_(2–x)Nd_xMo_2O_9

Single-phase La_(2–x)Nd_xMo_2O_9(0≤x≤1.8) compounds were prepared using solid-state reaction technique. Their structural and thermal p roperties were characterized by room and high temperatures X-ray diffraction(XRD), thermo gravimetric analysis-differential scanningcalorimetry(TG-DSC), and high temperature Raman spectra. The transport properties were investigated using D.C. four-probe technique and Hebb-Wagner polarization method. The substitution limit of Nb~(3+) in La_(2–x)Nd_xMo_2O_9 was determined to be in the range of 1.8x1.9, and the cubic lattice parameter of La_(2–x)Nd_xMo_2O_9 decreased linearly with the increasing of x. When the Nb~(3+) substitution content x was larger than 0.6, the α/β phase transition could be depressed to such a great degree that the phase transition thermal enthalpy was not detected by DSC. The temperature dependence of electrical conductivities for La_(1.4)Nd_xMo_2O_9 below 873 K and that for LaNdMo_2O_9 below 923 K obeyed the Arrhenius law, while above 873 and 923 K Vogel-Tammann-Fulcher(VTF) model could describe the conduction behaviors satisfactorily. The transition of transport mechanism from Arrhenius to VTF was caused by the change of structure, which was supported by the high temperature XRD and Raman results. The ionic transport number of La_(1.4)Nd_xMo_2O_9 in air was larger than 0.99 at 1073 K, and with the increasing of temperature it was close to 0.98 at 1173 K. In view of the phase transition, thermal expansion and conductivity properties, La_(1.4)Nd_xMo_2O_9 should be a promising electrolyte material in La_(2–x)Nd_xMo_2O_9 series.     

Research on Thermal Wear of Cast Hot Forging Die Steel Modified by Rare Earths

Thermal wear of cast hot-forging die steel modified by rare earths（RE） was studied and compared with commercially used die steels. The function of RE and the mechanism of thermal wear of cast steel modified by RE were discussed. The results showed that with increasing content of RE, the wear rate of cast steel reduced at first and then increased. By adding 0.05% （mass fraction） RE, the cast hot-forging die steel with optimum thermal wear resistance was obtained, which was better than that of H13 and 3Cr2WSV. The large amount of coarse inclusions, （RE）2O2S, resulted from excessive RE, which obviously deteriorated thermal wear resistance. The mechanism of thermal wear of the modified cast die steel is oxidation wear and oxide fatigue delamination. The wear debris are lumps of Fe2O3 and Fe3O4.     

Thermogravimetric Study on Oxygen Adsorption/Desorption Properties of Double Perovskite Structure Oxides REBaCo2O（5＋δ）（RE= Pr,Gd,Y）

The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5＋δ,GdBaCo2O5＋δ,and YBaCo2O5＋δ were investigated by the thermogravimetry（TG）method in the temperature range of 400~900 ℃.The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides,such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ,whereas,the oxygen permeation flux was comparable to that of the latter,which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere（Δδ/Vmol）in these double perovskite structure oxides.The large oxygen adsorption/desorption rate constants of GdBaCo2O5＋δ and PrBaCo2O5＋δ made them nice catalyst coating materials,on other membrane surfaces,to improve the oxygen permeability.     

Sealing Glass of Barium-Calcium-Aluminosilicate System for Solid Oxide Fuel Cells

Glass-ceramic materials were developed as a sealant in the solid oxide fuel cell （SOFC） in the temperature range of 800 -850 ℃. The glass materials were based on the glass and glass-ceramic in the BaO-CaO-Al2O3-SiO2-La2O3-B2O3 system. The thermal expansion coefficient （TEC） decreased with lower Ba^2＋ content and higher Ca^2＋ content, but the glass transition temperature and crystallization temperature increased greatly with an increase in Ca^2＋ content and a decrease in Ba^2＋ content, when the other components in the sealant were invariable. The TEC of the sealant with Ba^2＋ content of 25.4% was 10.8 × 10^-6 K^- 1（temperature range from 25 to 850℃）, and its softening temperature was 950 ℃. The TEC of the sealant accorded well with that of La0.9Sr0.1Ga0.5Mg0.2o3- 6（LSGM） with a mismatch of only 3%. The sealant had superior stability and compatibility with the LSGM electrolyte during the process of operation in SOFC. The weight loss of the sealant with Ba^2＋ content of 25.4% was approfimately zero after heat-treated at 800℃ for 500 h in H2 and O2 atmosphere, respectively.     

Effect of Calcination Temperature on Structure and O2 Desorption Properties of CexPr1-xO2-δ Mixed Oxides

A series of CexPr1-xO2-δ (x=0,0.5,0.9,1.0) mixed oxide calcined at different temperatures were synthesized by sol-gel method and characterized by Raman, XRD and O2-TPD techniques. When x=0.9, only a cubic phase CeO2 is observed. When x=0.5, the compound was combined by Pr6O11 and CeO2 mixed oxides. For CexPr1-xO2-δ (x=0.5,0.9) samples 465cm-1 Raman peak is attributed to the Raman active F2g mode of Ceo2. The broad peak at about 570cm-1 can be linked to lattice defects resulting in oxygen vacancies. The crystallite size of the samples increased as increasing the calcined temperature. But the increased value of Ce0.9Pr0.1O2-δ and Ce0.5Pr0.5O2-δ is smaller than single CeO2 and Pr6O11 obviously. It reveals that the insertion of Pr atom into the ceria lattice could enhance the sintering resistance and thermal stability of the mixed oxides. Calcination temperatures had great effect on the peak intensity for CeO2 but less effect on Ce0.8Pr0.2O2-δ in Raman spectra, and it may be caused by the colors transformation of the mixed oxidfs. The result of O2-TPD experiment indicates that the formation of solid solution has elevation the stabilization and thermal stability of the mixed oxides.     

Low Temperature Phase Transition Behavior of Ca-Doped Lanthanum Chromites

Phase transition of LaCrO3 and doped-LaCrO3 was studied by DSC, TG and XRD, and thermal expansion during the transition was analyzed. It is found that phase transition of LaCrO3 begins at about 240℃ and ends at about 265 ℃. Temperatures of phase transition rise obviously with increasing Ca^2＋ content. The transition of LaCrO3 and Ca-doped LaCrO3 from orthorhombic to rhombohedral is accompanied with endothermic reaction. No obvious change occurs in mass, but remarkable shrinkage occurs during phase transition.     

Influence of zirconium addition on microstructure, magnetic properties and thermal stability of nanocrystalline Nd12.3Fe81.7B6.0 alloy

Effect of Zr addition on microstructure, magnetic properties and thermal stability of Nd12.3Fe81.7B6.0 (x=0-3.0) ribbons melt-spun and annealed was investigated. Magnetic measurement using vibrating sample magnetometer (VSM) revealed that Zr addition was significantly effective in improving the magnetic properties at room temperature. The intrinsic coercivity Hci of the optimally processed rib-boris increased monotonically with increasing Zr content, from 751.7 kA/m for x=0 to 1005.3 kA/m for x=3.0. Unlike the coercivity, the re-manence polarization Jr increased first with Zr addition, from 0.898 T up to 1.041 T at x=1.5, and then decreased with further Zr addition.The maximum energy product (BH)max behaved similarly, increasing from 103.1 KJ/m3 to a maximum of 175.2 kJ/m3 at x=1.5. Microstruc-ture studies using atomic force microscopy (AFM) and transmission electron microscopy (TEM) had shown a significant microstructttre re-finement with Zr addition. The absolute values of temperature coefficients of induction and coercivity were significantly increased with in-creasing Zr content, indicating that Zr was detrimental to thermal stability of the melt-spun Nd2Fe14B-type material.     

Effects of Chromium Addition on Preparation and Properties of Bulk Cementite

Bulk cementites with the Cr contents of 0,3.01,6.03,8.22,and 11.51mass% were prepared by mechanical alloying(MA)and spark plasma sintering(SPS).The results indicated that when the Cr content was low(3.01mass%),the phases were composed of cementite with a small amount ofα-Fe at a sintering temperature of 1 173 K,but the microstructure became single-phase alloyed cementite as the Cr content was further increased.It showed that microaddition of Cr was beneficial for promoting the formation of cementite.Furthermore,the mechanical performance of cementite can be greatly affected by the variation of Cr content.The hardness,elastic modulus and elastic recovery presented a remarkably increasing tendency with the addition of Cr,and the maximum micro-hardness and elastic modulus values reached 1 070.74 HV and 199.32 GPa,respectively,which were similar to the precipitation phase(cementite)obtained by melting and casting techniques.Moreover,when the Cr content was below 11.51mass%,the crystal structure of Fe_3C-type cementite would not change with increasing the Cr content.A Cr atom replaced an Fe atom in the lattice of the cementite,and voids appeared when Cr was doped into the cementite at content of about11.51mass%,causing the relative density to decrease.