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).     

Structure and permanent magnetic properties of SmFex （x=3-8） melt spun ribbons during heat treatment

Compounds with the composition SmFex（x=3–8） were prepared by melt spun method at a velocity of 40 m/s and subsequent annealing at temperature between 600–1000 ℃. The crystal structures of the as-quenched and as annealed powders were investigated by XRD methods with following Rietveld analysis. The glass forming ability could be enhanced by the increase of Sm content to x≤5.Metastable Sm5Fe17-type structure existed when 3≤x≤5 and temperature was lower than 800 ℃. SmFe2-type structure could be stable up to 1000 ℃ when x〉3 and temperature was under 800 ℃. The content of SmFe2-type decreased with the increase of x value and increased with temperature lower than 800 ℃, from which SmFe2-type started to bring the transition to SmFe3-type. As for Sm5Fe17-type compounds with x=3.4, the highest coercivity of 33.6 kOe could be obtained under a velocity of 30 m/s and heat treated under 700 ℃×1h.     

Influence of the Erbium Substitution for Gd in Gd5Si1.8Ge2.2Alloys on the Magnetocaloric Effect in Low-Field

The phases and magnetocaloric effect in the alloys (Gd1-xErx)5Si1.8Ge2.2 with x=0,0.1,0.2 and 0.3 were investigated by X-ray diffraction analysis and magnetization measurement. The samples were single phase with the monoclinic Gd5Si2Ge2-type structure. With the increase of Er content, the Curie temperature (Tc) decreased obviously from 253K of the alloy with x=0 to 114K with x=0.3. The maximum magnetic entropy changed in the samples of (Gd1-xErx)5Si1.8Ge2.2 with x=0.0,0.1,0.2 and 0.3 were 6.88,8.32,9.59 and 10.24 J·kg-1·K-1 respectively in the applied field change of 0~2.0T.     

Preparation and Physicochemical Characterization of La1-xCexCoO3+δ Perovskite Catalyst and Its Methane Catalytic Combustion

Perovskite oxide LaCoO3 methane catalytic material was synthesized with citric acid complexation and bubbling method.The effect of doped cerium was studied on the series of La1-xCexCoO3 δ materials by means of BET,XRD and SEM techniques.Their catalytic behaviors were studied with methane catalytic complete combustion as probe reaction.The results show that doped cerium has great effect on crystal phase formation.When doped cerium is less than 0.3 (molar ratio),the crystal phase of oxide has little changed.When doped cerium is up to 0.5,Co3O4 phase is obviously discovered and the perfectibility of LaCoO3 perovskite crystal phase is deteriorated.When x is over 0.7,perovskite crystal phase is weakened or completely disappeared.Considering the crystal phase of oxides,the optimum doped cerium is about 0.3.The perovskite oxides can be formed at a low calcinations temperature of 700 ℃.When x is 0.3,the highest catalytic activity of T10% (390 ℃) and T90% (603 ℃) is obtained on the series of La1-xCexCoO3 δ materials calcined at 800 ℃.     

Ce1–xSmxO2–δ-attapulgite nanocomposites：synthesis via simple microwave approach and investigation of its catalytic activity

Ce1–x Smx O2–δ-attapulgite（ATP） nanocomposites were successfully prepared via a facile microwave approach.This was a facile and rapid process requiring only low power of microwave irradiation（160 W）.The catalytic performance of the Ce1–x Smx O2–δ-ATP nanocomposites with different Sm contents for degradation of methylene blue（MB） was systematically evaluated.The Ce1–x Smx O2–δ-ATP nanocomposites showed enhanced catalytic activities compared with pure CeO2/ATP.Specifically,the catalytic activities of Ce1–x Smx O2–δ-ATP nanocomposites increased with increase in Sm content from x=0.0 to 0.3.The introduction of an optimal amount of Sm3＋into CeO2 contributed to the formation of structure defects and electronic defects in the oxide lattice,which could increase concentration of oxygen vacancies.However,further increasing Sm content to x=0.4 induced the formation of more agglomerates,leading to decreased catalytic activity.It was believed that this facile,rapid microwave-assisted strategy was scalable and could be applied to synthesize other nanocomposites for different applications.     

Influence of partial substitution of cerium for lanthanum on magnetocaloric properties of La_(1–x)Ce_xFe_(11.44)Si_(1.56) and their hydrides

The structure and magnetocaloric properties of La1–xCexFe11.44Si1.56 and their hydrides La1–xCexFe11.44Si1.56Hy（x=0, 0.1, 0.2, 0.3, 0.4） were investigated.The samples crystallized mainly in the cubic Na Zn13-type structure with a small amount of α-Fe phase as impurity.The lattice constants and Curie temperature presented the same change tendency with increasing of Ce content.For the hydrides, the influence of Ce content on lattice constants was weakened and the values of H concentration y were approximate to be 1.56.The La1–xCexFe11.44Si1.56 compounds exhibited large values of isothermal entropy change –ΔSm around the Curie temperature TC under a low magnetic field change of 1.5 T.The value of –ΔSm increased and then decreased with increasing Ce content, reached the maximum, 26.07 J/kg·K for x=0.3.TC increased up to the vicinity of room temperature by hydrogen absorption for the Ce substituted compounds, but TC only slightly decreased with increasing Ce content.The first-order metamagnetic transition was still kept in the hydrides and the maximum values of –ΔSm were lower than those of the La1–xCexFe11.44Si1.56 compounds, but still remained large values, about 10.5 J/kg K under a magnetic field change of 1.5 T.The values of –ΔSm were nearly independent of the Ce content and did not increase with increasing x for the hydrides.The La1–xCexFe11.44Si1.56Hy（x=0–0.4） hydrides exhibited large magnetic entropy changes, small hysteresis loss and effective refrigerant capacity covered the room temperature range from 305 to 317 K.These hydrides are very useful for the magnetic refrigeration applications near room temperature under low magnetic field change.     

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.     

Phase and microstructure of TbCuT-type SmFe melt-spun powders

The SmxZr0.3Fe9.1-xCo0.6(x=0.8,0.9,1.0) powders were prepared by melt-spun method with different quenching velocities.The phase and microstructure were studied by X-ray diffraction(XRD),scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The Th2Zn17-type structure of the as-cast state changed to TbCu7-type after quenching to a rotating molybdenum roll under certain velocity,and the formation of TbCu7-type phase was strictly depending on the Sm content and roll speed.The SEM morphology showed that the Fe-rich zone was typically fish-bone structure and TEM diffraction pattern indicated the nano-scale crystal size with TbCu7-structure when x=0.9,and FCC type γ-Fe on the basis of α-Fe formed in the non-equilibrium solidification could be detected by selected area electron diffraction(SAED) indexing in the x=0.8 samples.     

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.     

Phase structure and Cycle Stabilities of Mg2Ni/Mm0.3Ml0.7Ni3.55Co0.75Mn0.4Al0.3 Composite Hydrogen Storage Alloys Prepared by Two-step re-melting

Mm0.3Ml0.7Ni3.55Co0.75Mn0.4-Al0.3 alloy has high chemical activity and favorable plateaus pressure. Mg2Ni is in favor of high hydrogen storage capacity and low weight, but it is difficult to be activated. In order to improve the capacity and cycle performances of hydrogen-storage alloy electrodes, Mm0.3Ml0.7Ni3.55Co0.75Mn0.4-Al0.3-x%Mg2Ni (x=0,5,10,30) composite hydrogen storage alloys prepared by two-step re-melting were investigated in this work. The influences of Mg2Ni content on the cycle stabilities were analyzed by electrochemical methods. It was observed by XRD that the main phase of all the alloys is LaNi5 and the crystal lattice parameters of LaNi5 are changed with the increasing of x value, i. e, α-axis and unit cell volume decrease and c-axis decreases nonlinearly. The c-axis of alloy with x=5 is larger than the others. With the increasing of x value, capacity retentions of the composite hydrogen storage alloys rise from 66.21% while x=0 to 82.04% while x=10, but the capacity retention of the composite alloy with 30% Mg2Ni declines because of its decreasing axial ratio. More over, the composite alloy with 5% Mg2Ni shows the best cycle stability and higher discharge capacity, and it is an appropriate candidate for battery materials.     

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.     

Chemical interaction of Ce-Fe mixed oxides for methane selective oxidation

Chemical interaction of Ce-Fe mixed oxides was investigated in methane selective oxidation via methane temperature programmed reduction and methane isothermal reaction tests over Ce-Fe oxygen carriers. In methane temperature programmed reduction test, Ce-Fe oxide behaved complete oxidation at the lower temperature and selective oxidation at higher temperatures. Ce-Fe mixed oxides with the Fe content in the range of 0.1–0.5 was able to produce syngas with high selectivity in high-temperature range(800–900 °C), and a higher Fe amount over 0.5 seemed to depress the CO formation. In isothermal reaction, complete oxidation occurred at beginning following with selective oxidation later. Ce1–xFexO2–δ oxygen carriers(x≤0.5) were proved to be suitable for the selective oxidation of methane. Ce-Fe mixed oxides had the well-pleasing reducibility with high oxygen releasing rate and CO selectivity due to the interaction between Ce and Fe species. Strong chemical interaction of Ce-Fe mixed oxides originated from both Fe*activated CeO2 and Ce3+ activated iron oxides(FeOm), and those chemical interaction greatly enhanced the oxygen mobility and selectivity.     

Magnetic and Transport Properties of La0.5-x Ndx Ba0.5 CoO3 Compounds

Substituting effects of Nd for La in La0.5Ba0.5CoO3 compounds were studied systematically. The results show that Nd doping does not change the itinerant properties of the Co3d electrons. The molecular magnetic moment of the mate-rials decreases monotonically with increasing Nd dopant. When Nd content x ≥0.45, a magnetic phase separation appears in the materials. When x ≤0.45, the Curie temperature decreases monotonically with increasing Nd dopant. This is due to the size effects of the rare earth ions. The electric resistance measurements show that in the studied temperature range, the conduction of the materials belongs to the thermo-diffusion conduction below the Curie temperature, while it belongs to the variable range hopping conduction of polarons over the Curie temperature.     

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.     

Substituting Effect of Y in La0.5Ba0.5 CoO3

La0.5-xYxBa0.5CoO3 polycrystals were prepared by solid state reaction. The substituting effects of Y for La on the magnetic and transport properties of the materials were studied systematically. The results indicate that substitution of Y induces two effects. Firstly, the charge transfer from Y to 3d orbital of Co happens. This causes the molecular magnetic moment to decrease. Secondly, the antiferromagnetic exchange interaction of Co ions appears. When the content of Y is less than or equal to 30%, the non-colinear structure of spins in materials is observed. When the content of Y is greater than 30%, the materials transit from predominant ferromagnetic state to predominant antiferromagnetic one. The conductive mechanism for the materials with different content of Y belongs to the variable range hopping conduction of polarons.The resistivity of materials increases sharply with increasing Y content.     

Study on white-light emission and light-emitting mechanism of hydrothermally synthesized YVO_4:1 mol.%Dy~(3+),x mol.%Eu~(3+) phosphor powders

White light-emitting YVO_4:1 mol.%Dy~(3+),x mol.%Eu~(3+) phosphor powders with order morphology and well crystallization were hydrothermally synthesized at 180°C. The microstructure, white-light emission, and light-emitting mechanism of the powders were carefully studied using X-ray diffractometry, scanning electron microscopy and photoluminescence spectra. The excitation and emission spectra of the phosphor powders indicated the coexistence of efficient energy transfer from Eu~(3+) to Dy~(3+) and inefficient energy transfer from Dy~(3+) to Eu~(3+) besides the energy transfer from VO_4~(3–) to Eu~(3+). Increasing the Eu~(~(3+)) concentration initially enhanced and then weakened the luminescent intensity of Dy~(3+). The white-light emissions of YVO_4:1 mol.%Dy~(3+),x mol.%Eu~(3+) phosphor powders were both related to the energy transfer between VO_4~(3–) and Dy~(3+)/Eu~(3+), as well as between Eu~(3+) and Dy~(3+). The inefficient energy transfer from Dy~(3+) to Eu~(3+) was first found.     

Preparation and Physicochemical Characterization of La1-x Cex Co03＋δ Perovskite Catalyst and Its Methane Catalytic Combustion

Perovskite oxide LaCoO3 methane catalytic material was synthesized with citric acid complexation and bubbling method. The effect of doped cerium was studied on the series of La1-x,Ce,CoO3 8 materials by means of BET, XRD and SEM techniques. Their catalytic behaviors were studied with methane catalytic complete combustion as probe reaction.The results show that doped cerium has great effect on crystal phase formation. When doped cerium is less than 0.3(molar ratio), the crystal phase of oxide has little changed. When doped cerium is up to 0.5, Co3O4 phase is obviously discovered and the perfectibility of LaCoO3 perovskite crystal phase is deteriorated. When x is over 0.7, perovskite crystal phase is weakened or completely disappeared. Considering the crystal phase of oxides, the optimum doped cerium is about 0.3. The perovskite oxides can be formed at a low calcinations temperature of 700℃. When x is 0.3, the highest catalytic activity of T10%(390℃) and T90%(603℃) is obtained on the series of La1-xCexCoO3 δ materials calcined 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 cerium on the cleanliness of spring steel used in fastener of high-speed railway

The effects of Ce addition on the quantity, size, distribution of inclusions and the content of oxygen, sulfur and other hazardous residual elements in spring steel used as fastener in high speed railway were investigated by metallographic examination, SEM-EDS and composition analysis. The results indicated that the contents of oxygen decreased with the addition of Ce([Ce]0.1%) and the content of sulfur continually decreased with increasing content of Ce([Ce]1.2%). However, with the further increase of Ce element addition, the content of [O] and T[O] began to increase. The content of Ce corresponding to the lowest [O] and T[O] lied in the range of 0.10%–0.13% and 0.045%–0.065%, respectively. The addition of Ce in spring steel resulted in the formation of rare earth oxides/oxysulfides and decreased the size of inclusions to less than 3 μm in globular or spheroid shape. Moreover, the residual harmful elements(As, P, Pb and Sn) were found to exist in the Ce-containing inclusions, which had proved that the Ce addition could capture the residual elements and suppress their precipitation behaviors in the grain boundary.     

Effect of rare earths on microwave absorbing properties of RE-Co alloys

The powders of RE2Co17(RE=Y, Ce, Nd, Ho, Er) and Ho x Co100–x(x=6, 8, 10, 12) alloys were prepared by the arc melting method and high-energy ball mill process. The compositions and morphologies of the alloys were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM), and the microwave absorbing properties were studied by a vector network analyzer. The results showed that the alloy of Y2Co17 had better absorbing properties at low frequencies and its lowest reflectivity value was –9.5 d B at 3.8 GHz. The lowest reflectivity value of Ho2Co17 alloy was –13.7 d B at 7.02 GHz and it obtained large absorbing bandwidth. Reflectivity value less than –5 d B was from 5.1 to 10.2 GHz. When x=6 and x=8, the alloys of Ho x Co100–x consisted of Ho2Co17 phase and Co phase. They had good radar absorbing properties. With increase in Ho content, the minimum reflectivity value worsened and the absorbing peak frequency shifted toward higher frequencies. But when x=12, the absorbing peak frequency shifted toward lower frequencies but the minimum reflectivity value worsened.