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.     

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.     

Oxygen adsorption/desorption behavior of YBaCo4O7+δ and its application to oxygen removal from nitrogen

A new medium-temperature (200-400℃) adsorbent material for oxygen removal and air separation, YBaCo4O7+β, was prepared by the solid-state reaction method. This new adsorbent could adsorb a large quantity of oxygen in the temperature range of 200-370 ℃. Ad-sorbed oxygen could be released by raising temperature over 400 ℃ or by switching the atmosphere from oxygen to nitrogen. This oxygen adsorption and desorption process had good reproducibility. Taking advantage of this unique oxygen intake/release behavior, a nitrogen puri-fication process was investigated. The results showed that YBaCo4O7+δ material was a promising candidate for the oxygen sorption process and could be used to produce high-purity nitrogen or to remove trace oxygen from other gases.     

Investigation on pumping oxygen characteristics of （Bi2O3）0.73（Y2O3）0.27 solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.     

Investigation on pumping oxygen characteristics of (Bi2O3)0.73(Y2O3)0.27 solid electrolyte

(Bi2O3)0.73(Y2O3)0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 (Y2O3 stabilized) oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10-20-1×10-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10-37-1×10-27 Pa at 1.0 V and 1×10-53-1×10-47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.     

Structure and catalytic property of CeO2-ZrO2-Fe2O3 mixed oxide catalysts for diesel soot combustion： Effect of preparation method

A series of Ce0.5Fe0.30Zr0.20O2 catalysts were prepared by different methods(co-precipitations method, citric acid sol-gel method, impregnation method, physical mixed method, and hydrothermal method) and characterized by X-ray diffraction(XRD), Raman spectroscopy, Brunauer-Emmett-Teller(BET) and H2-TPR measurements. Potential of the catalysts in the soot oxidation was evaluated in a temperature-programmed oxidation(TPO) apparatus. The results showed that all the Fe3+ and Zr4+ were incorporated into ceria lattice to form a pure Ce-Fe-Zr-O solid solution for the co-precipitation sample, but two kinds of Fe phases existed in the Ce-Fe-Zr-O catalysts prepared by other methods: Fe3+ incorporated into CeO2 lattice and dispersed Fe2O3 clusters. The free Fe2O3 clusters could improve the activity of catalysts for soot oxidation comparing with the pure Ce-Fe-Zr-O solid solution owing to the synergetic effect between free Fe2O3 and surface oxygen vacancies. In addition, the activity of catalysts strongly relied on the surface reducibility of free Fe2O3 particles. Holding both abundant free Fe2O3 particles and high oxygen vacancy concentration, the hydrothermal Ce0.5Fe0.3Zr0.2O2 catalyst presented the lowest Ti(251 °C, ignition temperature of soot oxidation) and Tm(310 °C, maximum oxidation rate temperature) for soot combustion(with tight-contact between soot and catalysts) among the five samples. Even after aging at 800 °C for 10 h, the Ti and Tm were still relatively low, at 273 and 361 °C, respectively, indicating high catalytic stability.     

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).     

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.     

Structure and Dielectric Study of Ce3 NbO7＋δ

The structure, phase composition, and migration of oxygen ion in Ce3 NbO7＋δ were reported on the basis of lone-pair substitution concept. X-ray diffraction study revealed that Ce3 NbO7＋δ sample was comprised of Ce3 NbO7＋δ phase and CeNbO4.25 phase. In the dielectric study of Ce3 NbO7＋δ sample, two dielectric loss peaks were observed both in temperature spectra and frequency spectra. Both peaks were shifted towards higher temperature with increase in frequency in temperature spectra and towards higher frequency with increase in temperature in frequency spectra, indicating the relaxation essence of these two peaks. It was suggested that the short distance diffusions of oxygen ions in both Ce3 NbO7＋δ phase and CeNbO4.25 phase gave rise to the two dielectric relaxation peaks.     

Influence of oxygen non-stoichiometry on physical properties of NdSr2Mn2O7±δ

Nd Sr2Mn2O7+δ compounds were synthesized by ceramic method under three different cooling conditions. The Nd Sr2Mn2O7+δ samples were characterized by powder X-ray diffraction(XRD). Oxygen non-stoichiometry data for the studied powders were determined by using gravimetric and X-ray photoelectron spectroscopy(XPS) methods. The correlation of cooling method and oxygen as non-stoichiometry was established. The electroconductivity in samples was studied by using four-point probe method, and the strong correlation with non-stoichiometry was found out. Magnetization measurements were carried out. It was found that the magnetic and transport properties of the samples were also influenced by oxygen non-stoichiometry. The evolution of the magnetic properties could be explained by the formation of magnetic clusters in the vicinity of oxygen vacancies(OV) and strong competition between the superexchange and double exchange interactions.     

Paramagnetic Anisotropy of CdGd2(WO4)4-δ Single Crystal

CdGd2(WO4)4-δ single crystal was grown using the Czochralski's method. The crystal structure was tetragonal scheelite with lattice parameters a=b=0.5203 nm and c=1.1359 nm. There were vacancies of (WO4)2-, therefore, there were some Gd2+ ions. Langevin paramagnetism and anisotropy were observed from the σ-T curves at room temperature. The susceptibility χ// was 3.5018×10-3, and χ⊥ was 3.4403×10-2. The anisotropy was also observed in the electron spin resonance (ESR) experiments. The anisotropic Landé factors were g//=2.1333 and g⊥=2.8411. The direction of easy magnetization was in the a-b plane. Anisotropic paramagnetic Curie constants C// and C⊥ were not only related to macroscopic σ that was observed through the experiment, but were also related to J⊥ and J//, which were the microscopic quantum numbers of the Gd2+ and Gd3+ ions. Based on the detailed analyses, the proportion of 36.8% of Gd3+ ions to 63.2% of Gd2+ ions in the Gd ions of the CdGd2(WO4)4-δ crystal was calculated, and δ was 0.638 in the single crystal.     

Oxidation of Silicon and Boron in Boron Containing Molten Iron

 A new process of directly smelting boron steel from boron containing pig iron has been established. The starting material boron containing pig iron was obtained from ludwigite ore, which is very abundant in the eastern area of Liaoning Province of China. The experiment was performed in a medium frequency induction furnace, and Fe2O3 powder was used as the oxidizing agent. The effects of temperature, addition of Fe2O3, basicity, stirring, and composition of melt on the oxidation of silicon and boron were investigated respectively. The results showed that silicon and boron were oxidized simultaneously and their oxidation ratio exceeded 90% at 1 400 ℃. The favorable oxidation temperature of silicon was about 1 300-1 350 ℃. High oxygen potential of slag and strong stirring enhanced the oxidation of silicon and boron.     

Electrical Properties and Microwave Synthesis of Mixed Rare Earth Oxide Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ

In order to lower the raw materials cost and develop a novel cathode materials for intermediate temperature solid oxide fuel cell(ITSOFC), using mixed rare earth replacing the expensive pure La2O3 as the raw materials, the powders of Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ (Ln=the mixed rare earth, x=0.05, 0.10, 0.15) for the applications as the cathode materials were prepared by microwave sintering process. The crystal structure and the particles morphology of the obtained powders were characterized by XRD and SEM, the electrical conductivity of all samples sintered at 1200 ℃ for 3 h was also measured as the function of the temperature from 100 to 800 ℃ by DC four-probe method in air. The experimental results show that due to the influence of mixed rare earth the powders of Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ synthesized at 1200 ℃ for 0.5 h with the mean particle size of 1～20 μm was of perovskite and cubic fluorite phase as well a little SrO phase, the electrical conductivity of the samples decreases with the adding Ca2+ content, and are all higher than 100 S·cm-1 from 500 to 700 ℃ when x≤0.10. Ln0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ. Can meet the demand of the electrical properties for the cathode materials in ITSOFC.     

Effect of Calcium Treatment on Non-Metallic Inclusions in Ultra-Low Oxygen Steel Refined by High Basicity High Al2O3 Slag

 The influence of calcium treatment on non-metallic inclusions had been studied when control technology of refining top slag in ladle furnace was used in ultra-low oxygen steelmaking. A sufficient amount aluminium was added to experimental heats for final deoxidizing during BOF tapping, and the refining top slag with strong reducibility, high basicity and high Al2O3 in ladle furnace was used to produce ultra-low oxygen steel and the transformation of non-metallic inclusions in molten steel was compared by calcium treatment and no calcium treatment. The results show that the transformation of Al2O3→MgO·Al2O3 spinel→CaO-MgO-Al2O3 complex inclusions has been completed for aluminum deoxidation products and calcium treatment to molten steel is unnecessary when using the control technology of ladle furnace refining top slag to produce ultra-low oxygen steel, and the complex inclusions are liquid at the temperature of steelmaking and easily removable to obtain very high cleanliness steel by flotation. Furthermore, the problems of nozzle clogging in casting operations do not happen and the remaining oxide inclusions in steel are the relatively lower melting point complex inclusions.     

Electroreduction Kinetics for Molten Oxide Slags

 The oxygen ion conductor, the reducing agent, and the molten oxide slag containing electroactive matter were used as constituent of a galvanic cell. Metal was directly electroreduced from molten slag using a short circuit galvanic cell. The following galvanic cell was assembled in the present experiment: graphite rod, [O]Fe C saturated｜ZrO2(MgO)｜Cu(l)+(FeO)(slag), and molybdenum wire. The FeO electroreduction reaction was studied through measuring short circuit current by controlling factors such as temperature, the FeO content in molten slags, and the external circuit resistance. An overall kinetics model was developed to describe the process of FeO electroreduction. It was found that the modeled curves were in good agreement with the experimental values. The new oxide reduction method in the metallurgy with controlled oxygen flow was proposed and the metallurgical theory with controlled oxygen flow was developed.     

Perovskite type lanthanum manganite: Morpho-structural analysis and electrical investigations

Perovskite-type oxides of LaMnO_3 were synthesized by means of the sol-gel method, in the presence of citric acid as gelling agent. The precursors used were Mn(NO_3)_2·H_2O, La_2O_3, and NaOH,mixed in the stoichiometric ratio to obtain perovskite materials. The obtained gel was heat-treated at 400, 600 and 800 ℃ respectively, for 6 h. X-ray diffraction and FT-IR spectroscopy were used to analyze the phase transformation as a function of temperature, and the Rietveld refinement was used in order to characterize the materials obtained structurally. The average crystallite size of the products was calculated from XRD data and the average particle size was measured from the TEM micrographs. At 600 ℃, the synthesized compound is well-crystallized, showcases a perovskite structure(Pm-3m space group), and exhibits uniform and homogeneous hexagonally-shaped particles, with sizes in the 20-50 nm range.Complex impedance measurements in the 20-2 × 10~6 Hz frequency range were carried out at different temperatures(26-115 ℃), and the electrical conduction mechanism is discussed.     

Synthesis, Electrical and Magnetic Properties of Fe304 Doped by Dy^3＋

The Dy^3＋ -doped Fe3O4 samples were synthesized by sol-gel method, and the effects of dopant on the electrical and magnetic properties were investigated. According to XRD analysis, the high concentration doping of dysprosium ions in Fe3O4 can not be obtained due to the difference of ionic radius, and Fe^3 ＋ ions are replaced by only a small amount of dysprosium ions. The magnetic property was characterized by VSM. The substitution results in the change of saturation magnetization, which may be due to the complex effects of increasing magnetization resulted from Dy^3＋ substitution and decreasing magnetization resulted from the impurity. The electrical property was characterized by four-probe method. With the increasing eoped content, magnetoresistance also increases, then decreases, and increases again. The spin-polarization of doped samples is lower than that of Fe3O4. Lower spin-polarization results in lower tunneling magnetoresistance. Fortunately, barrier was obtained by the second phase at the same time when sample was synthesized. The increase of appropriate barrier height leads to the change of tunneling magnetoresistance.     

Paramagnetic Anisotropy of CdGd2（WO4） 4-δ Single Crystal

CdGd2 （WO4）4 -δ single crystal was grown using the Czochralski＇s method. The crystal structure was tetragonal seheelite with lattice parameters a = b = 0.5203 nm and c = 1. 1359 nm. There were vacancies of （WO4）^2- , therefore, there were some Gd^2＋ ions. Langevin paramagnetism and anisotropy were observed from the δ-T curves at room temperature. The susceptibility X//was 3.5018×10^-3, and X⊥ was 3.4403× 10^-2. The anisotropy was also observed in the electron spin resonance （ESR） experiments. The anisotropic Land6 factors were g//= 2. 1333 and g~ = 2. 8411. The direction of easy magnetization was in the α-b plane. Anisotropic paramagnetic Curie constants C//and C⊥ were not only related to macroscopic a that was observed through the experiment, but were also related to J⊥ and J//, which were the microscopic quantum numbers of the Gd^2＋ and Gd^3｜ ions. Based on the detailed analyses, the proportion of 36.8% of Gd^3＋ ions to 63.2% of Gd^2＋ ions in the Gd ions of the CdGd2（WO4）4-δ crystal was calculated, and δ was 0.638 in the single crystal.     

Synthesis and Property of H2La2Ti3O10/CdS Layered Nanocomposite Photocatalyst

H2La2Ti3O10/CdS nanocomposite with er photoactivity was synthesized by a stepwise exchange process from H2La2Ti3O10, which was obtained by H^＋ -exchanging reaction of H2La2Ti3O10 with HCl other than the normally used HNO3. The pillaring process was investigated by XRD, TEM, FT-IR and BET methods. The photocatalytic decomposition of aniline was used as the model system to evaluate the photochemical properties of H2La2Ti3O10/CdS,H2La2Ti3O10 and K2La2Ti3O10. It is found that the photoactivity of layered H2La2Ti3O10 is greatly improved by the intercalation of CdS in the interlayer. In general, the excellent photoactivity of the H2La2Ti3O10/CdS nanocomposite might be attributing to the extremely small particle size of incorporated CdS and good contact between CdS and La2Ti3O10^2- layers. On the other hand, the coupling of two semiconductor particles with different energy gap is useful to achieve effective charge separation. In H2La2Ti3O10/CdS, a photo-generated electron can transfer from CdS to the La2Ti3O10^2- layer, while the holes remain in the CdS particles. This helps to diffuse the electrons and holes before reaching the interface, and the holes and electrons can be effectively captured by the electrolyte in the solution. Simuhaneously, the optimal operating condition of photodecomposition aniline was investigated.     

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.