Effect of cobalt substitution on structure and magnetic properties of Nd_(0.4)Zr_(0.6)Fe_(10-x)Co_xSi_2(x =0-3) alloys and their ribbons

This study reports the stabilization of the RFe_(12)-type based compounds where part of R and Fe are substituted with Zr and Co and Si, respectively, in order to examine whether these rare-earth-lean materials are suitable for applications as permanent magnets. Structural and magnetic characterization of the family of alloys with the general formula Nd_(0.4) Zr_(0.6) Fe_(10-x)Co_xS_i2(x = 0 -3) and their melt-spun ribbons were carried out using X-ray diffraction and M€ossbauer spectroscopy. The ThMn_(12)-type structure is obtained for all samples as the majority phase with a minority a-Fe(CoSi) phase(less than 5 wt%) as it was estimated by XRD for x = 1 and 2. The Curie temperature increases linearly with Co substitution from 561 K for x = 0 to 712 K for x = 3. The saturation magnetization decreases slightly from 130.5(x =1)to 129.1 A·m~2/kg(x=3), while the anisotropy field is following the same trend.     

Magnetic properties and magnetic entropy change of perovskite manganites La_(0.9-x)Eu_xSr_(0.1)MnO_3(x=0.000,0.075) by experimental method and numerical fitting

Polycrystalline samples La_(0.9-x)EuxSr_(0.1)MnO_3(x = 0.000, 0.075) were prepared by the standard solid-state reaction method. The results show that the samples preform a characteristic of clusters spin-glass state at low temperature. The samples show a characteristic of ferromagnetism(FM) characteristic in the temperature range of 15-125 K and 15-150 K respectively; the samples show preformed clusters in the temperature range of 125-343 K and 150-325 K, respectively, the samples show paramagnetism(PM)characteristic above 343 and 325 K, respectively. The second-order transitions are found at 118 and 135 K for undoped and doped sample, respectively. When the applied magnetic field is 7 T, the maximum magnetic entropy change |△S_M| value of the samples is near the Curie temperature(Tc), and the value of|△S_M| reaches 2.76 and 3.03 J/(K kg), respectively. In addition, the relative cooling power(RCP) is found to be 425.28 and 443.53 J/kg. The numerical fitting data fit well with experimental data. These results indicate that both the samples have the potential to realize magnetic refrigeration in the high temperature region(T 77 K).     

Microstructure and magnetic properties of bulk magnets Nd_(14-x)Fe_(76+x)Co_3Zr_1B_6(x=0,0.5,1) prepared by spark plasma sintering

Melt-spun ribbons with nominal composition of Nd14-xFe76+xCo3Zr1B6(x=0,0.5,1) were consolidated into isotropic bulk magnets by spark plasma sintering method.It was found that the Nd content and sintering temperature had significant influence on the density and magnetic properties of the sintered magnets.Homogeneous microstructure and fine grain(50-100 nm) were obtained when sintering below 700 ℃,and the initial magnetization curve showed that the coercivity was controlled by the pinning mechanism.However,ab...     

Effect of PdO_x structure properties on catalytic performance of Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst for CO,HC and NO_x elimination

Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst was pretreated in different atmosphere respectively, and characterized by CO chemical adsorption, XPS, HR-TEM, H_2-TPR, Raman, OSC and in situ DRIFTS to investigate the effect of the structure properties of PdO_x species on the catalytic performance for CO, HC and NO_x elimination. The results show that Pd/CZ catalyst pretreated in air atmosphere has higher oxidation activity of HC due to having high Pd dispersion and strong interaction between PdO_x and CZ support. Pd/CZ-H catalyst pretreated in reducing atmosphere exhibits better catalytic performance of NO_x elimination because of having relatively big Pd particle size, more Pd species in metallic state and higher concentration of oxygen vacancies. While for the Pd/CZ-RG catalyst pretreated in reactant atmosphere, strong adsorption of HC species on the surface of catalysts would lead to a part of active sites being covered, which inhibits HC and NO conversions.     

Recent advances in solid-state LED phosphors with thermally stable luminescence

Phosphor-converted white light-emitting diode(LED) lighting has gained tremendous achievements since the invention of the InGaN blue LED by Nakamura et al., who won the Nobel Physics Prize in 2014.By far, a significant challenge comes from the thermal quenching(TQ) behavior of the present LED phosphors during the high-power LED operation or the updated laser lighting. But systematic research or review on the luminescence quenching character and/or how to realize thermally stable luminescence are lacking. Since TQ is an inherent property of phosphors, it can be diminished by different approaches.This review proceeds from the mechanism of TQ, summarizes previous researches on improving the thermal stability of LED phosphors and also discusses future research opportunities in this field. The developments of the phosphors with properties of high luminance and thermal stability, as well as the improved strategies involved,will benefit the basic researches and applications in high power lighting or high-luminance laser lighting.     

Preparation of Ce~(3+)doped Bi_2O_3 hollow needle-shape with enhanced visible-light photocatalytic activity

Ce~(3+) doped Bi_2O_3 hollow needle-shape with enhanced visible-light photocatalytic activity was successfully prepared via the method of chemical precipitation using Bi(NO_3)·5H_2O and Ce(NO_3)_3·6H_2O as the source of bismuth and cerium, HNO_3 as solvent and NaOH as precipitants, respectively and after calcination at 500 ℃ for 2 h. The morphology and elemental composition,crystal form,purity and specific surface area of the hollow needle Bi_2O_3 were characterized by SEM-EDS, XRD, BET and FT-IR. The photocatalytic properties of the as-obtained samples were measured by UV-vis diffuse reflection spectroscopy and photochemical reactor. As a result, the obtained Bi_2O_3 hollow needle-shape doped with 5 wt% Ce shows good morphology, α-phase, stronger absorbent for visible light and good photocatalytic property. Under the simulated visible light of 300 W, the photodegradation rate of tetracycline over HNBCe can reach to 89.1%,which is higher than that of commercial Bi_2O_3 nanoparticles and Bi_2O_3 hollow needle-shape.     

Phase separation and crystallization of La_2O_3 doped ZnO-B_2O_3-SiO_2 glass

In order to investigate the effect of the La_2O_3 on the phase separation and crystallization of ZnO-B_2O_3-SiO_2 glass, after the occurence of the phase separation and crystallization of glasses by heat treatment, the microstructure morphology and distribution of elements in different sample areas were characterized by the scanning electron microscopy(SEM) and energy dispersive spectroscopy(EDS); the non-isothermal crystallization kinetics of the glass samples was studied by using a differential scanning calorimeter(DSC) and the precipitated crystals of crystallized glass were determined by the X-ray diffraction(XRD). The results suggest that the phase separation and crystallization of 60ZnO-30 B_2O_3-10SiO_2 glass occur at glass surface, and the incorporation of small amount(4 mol%) of La_2O_3 significantly inhibits the glass phase separation and consequently improves the thermal stability of glass.Doping of La_2O_3 accelerates the glass crystallization at the elevated temperature(660 ℃), making the depth of crystal layer thicker and diffraction intensity in XRD patterns stronger. However, due to the precipitation of several crystals that occur simultaneously when La_2O_3 doping amount is 4 mol%, crystallization of the 60ZnO-30B_2O_3-10SiO_2 glass is obviously depressed, the crystallization activation energy Ec and the relative crystallinity X_c of the glass reach the maximum and the minimum values, respectively.Although transition from one-dimensional growth of crystals to two-dimensional growth of crystals results from La_2O_3 addition, the one-dimensional growth of crystals remains dominant in crystallization process. This work can provide some useful information for preparing glass ceramics with nano-crystals precipitated in the glass surface.     

Influence of lanthanum on enhancement of mechanical and electrical properties of Cu-Al_2O_3 composites

Two kinds of Cu-Al_2O_3 composites(with and without La) were prepared via mechanical alloying-spark plasma sintering(MA-SPS) method. Microstructure, mechanical properties and electrical resistivity were investigated systematically using metallography, scanning electron microscopy, transmission electron microscopy, mechanical and electrical properties testing. The results indicate that an appropriate amount of La can homogenize the distribution of Al_2O_3. As such, yield strength, ultimate tensile strength and elongation of Cu-Al_2O_3-La are greatly increased. Some semi-coherent interface between Cu and Al_2O_3 is found, which means a low interface energy. The grain shape of Cu changes to irregular band with the addition of La. This change results in a density decrease of grain boundary and reduces electrical resistance. Lanthanum may exist in the form of La_2O_3.     

Effect of doping of different rare earth (europium,gadolinium, dysprosium and neodymium) metal ions on structural,optical and photocatalytic properties of LaFeO3 perovskites

Different rare earth substituted perovskites LaRE_xFe_(1-x)O_3(where RE=Eu~(3+),Gd~(3+),Dy~(3+),Nd~(3+)and x=0.02,0.04,0.06,0.08,0.1) with orthorhombic structure and narrow band gaps were successfully fabricated via sol-gel autocombustion method.All the substituted perovskites are found to exhibit excellent photocatalytic activity towards the oxidative degradation of dye molecules.An excellent increase in the rate constant values of pure perovskite(LaFeO_3) photocatalytic reactions is observed with the substitution of rare earth metal ions.Best results are obtained for LaNd_(0.1)Fe_(0.9)O_3 which exhibits around 7 times increase in the rate constant values for degradation reaction of SO(1.76×10~(-1) min~(-1))and RBY(1.69×10~(-1) min~(-1)) dyes.     

Double-shell structure of Al3(Zr,Sc) precipitate induced by thermomechanical treatment of Al–Zr–Sc alloy cable

A spheroidal Al₃(Zr,Sc) precipitate with a double-shell structure, comprising a Sc-enriched core enveloped by a Zr-enriched inner shell and a Sc-enriched outer shell (～9 nm in thickness), appears in an Al–0.2Zr–0.1Sc alloy cable after thermomechanical treatment. The average diameter of the spheroidal Al₃(Zr,Sc) precipitate is approximately 80 nm. The double-shelled Al₃(Zr,Sc) precipitate presents three different interfaces and is semi-coherent with the Al matrix. Atom probe tomography (APT) analyses further show that the outer shell of Al₃(Zr,Sc) precipitate is Sc element enrichment. The electrical conductivity of Al–0.2Zr–0.1Sc alloy cable increases by 6.5 MS/m within the aging time from 0.2 to 100 h at 350 °C, with double-shelled Al₃(Zr,Sc) precipitate.     

Effects of grain size and secondary phase on corrosion behavior and electrochemical performance of Mg-3Al-5Pb-1Ga-Y sacrificial anode

Grains with size of 4.5—20.5 μm were studied for their corrosion behavior and electrochemical performance in a Mg-3 Al-5 Pb-1 Ga-Y sacrificial anode using immersion testing,electrochemical measurements and microstructure analysis.The results show that fine-grained microstructure has higher chemical activity and more negative discharge potentials than coarse-grained samples.The sample with the smallest average grain size of 4.5 μm exhibits corrosion current density of 7.473×10~(-5) A/cm~2,and work potentials of-1.721 V at current density of 10 mA/cm~2.The density of grain boundaries and LAGBs increases with grain refinement,which leads to higher rates of dissolution and diffusion for the atoms.The secondary phases promote the occurrence of corrosion and improve the chemical activity of alloy due to their higher potential than the substrate.Higher corrosion rate and discharge activity are directly attributed to the higher density of grain boundaries and LAGBs,as well as the secondary phase.     

Influence of calcination temperature for LaTi_(0.2)Fe_(0.8)O_3 on catalytic pyrolysis of bagasse lignin

LaTi_(0.2)Fe_(0.8)O_3(LTF)was prepared by the sol-gel method,and the effects of calcination temperature on the structure and properties were investigated,A new method of preparing aryl oxygen-containing compounds from bagasse lignin(BL)by the catalytic pyrolysis over LTF was proposed.The results show that LTF has cubic crystal phase and porous structure and its optimal calcination temperature is 800 ℃(LTF-800).In the test for catalytic pyrolysis of BL,with the addition of LTF-800,the yield of liquid product reaches the maximum; the contents of phenolics,guaiacols,syringols,phenylates and furans increase obviously,while those of benzenes,esters and carboxylic acid decrease.The total content of aryl oxygencompounds(including phenolics,guaiacols,syringols and phenylates)in liquid product is more than 74 wt%with the addition of LTF-800,larger than that obtained by single BL pyrolysis(62 wt%).LTF could avoid oxygen-containing functional groups from being excessively destroyed.It has nice regeneration performance by controlled combustion of char even after 5 cycles.     

Microstructure and mechanical properties of A356 alloy with yttrium addition processed by hot extrusion

The effects of the rare earth element yttrium(Y) and hot extrusion on the microstructure and mechanical properties of A356 alloy were investigated by mechanical properties testing and microstructure observation. The results indicate that the addition of Y improves the microstructure of the as-cast alloy. The distribution of primary α-Al is uniform and orderly. The long needle-like eutectic Si phases and β-Fe phases turn to strips and short rods. When the content of Y increases to 0.2 wt%, the mean diameter of aAl(40.3 μm) and the aspect ratio of the eutectic Si phase(2.3) reach the minimum values, which are68.9% and 86.1% lower, respectively, than that of the alloy without Y addition. Under extrusion stress, the shape of the eutectic Si phase is changed from long rod-like to near grain-like after solution treatment.The size of the eutectic Si phase is significantly reduced. The needle-like β-Fe phases are squeezed and broken. The mechanical properties of the as-extruded alloy are significantly improved compared to the as-cast alloy. When the rare earth content is 0.2 wt%, the ultimate tensile strength, hardness and elongation of the alloy reach the maximum values, which are 328.2 MPa, 110.4 HV and 21.3%, respectively, and increase by 42.01%, 37.71% and 481.91%, respectively, in comparison to the as-cast alloy without Y addition.     

Effects of precursor moisture and inert N_2 atmosphere calcinations on structure and properties of alumina modified CeZrLaNd mixed oxides

CeO_2-ZrO_2 mixed oxides are widely used in the three-way catalysts due to their unique reversible oxygen storage and release capacity. Large surface area, high oxygen storage capacity and good thermal stability of cerium zirconium mixed oxides are the key properties for the automotive catalysts so as to meet the strict emission regulations. In this work, alumina modified CeZrLaNd mixed oxides were prepared by a co-precipitation method. The effects of moisture in precursor and inert N2 atmosphere during calcinations on the structure and properties were investigated by Brunauer-Emmett-Teller(BET) surface area measurements, X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), hydrogen temperature-programmed reduction(H_2-TPR), oxygen storage capacity(OSC), Raman spectroscopy, and X-ray photoelectron spectroscopy(XPS). The results show that the moisture in precursor during calcinations increases the crystal grain size of the cerium zirconium mixed oxides, improving the thermal stability. And the aged surface area of sample after being calcined at1000 ℃ for 4 h reaches 68.8 m~2/g(5.7% increase compared with the common sample). The inert N2 atmosphere endows a great pore-enlarging effect, which leads to high fresh surface area of 148.9 m2/g(13.5% increase compared with the common sample) and big pore volume of 0.5705 mL/g. The redox and oxygen storage capacity are also improved by inert N2 atmosphere with high OSC value of 241.06μmolO_2/g(41.3% increase compared with the common calcination), due to the abundant formation of the crystal defects and oxygen vacancies.     

Gaseous hydrogen storage properties of Mg-Y-Ni-Cu alloys prepared by melt spinning

For purpose of promoting the hydrogen absorption and desorption thermodynamics and kinetics properties of Mg-Ni-based alloys, partially substituting Y and Cu for Mg and Ni respectively and melt spinning technique were applied for getting Mg_(25-x)Y_xNi_9 Cu(χ = 0-7) alloys. Their microstructures and phases were characterized with the help of X-ray diffraction and transmission electron microscopy. Their hydrogen absorbing and desorbing properties were tested by a Sievert apparatus, DSC, and TGA, which were connected with a H_2 detector. In order to estimate the dehydrogenation activation energy of alloy hydride, both Arrhenius and Kissinger methods were applied for calculation. It is found that their hydriding kinetics notably declines, however, their hydrogen desorption kinetics conspicuously improves, with spinning rate and Y content increasing. Their hydrogen desorption activation energy markedly decreases under the same constraint, and it is found that melt spinning and Y substituting Mg improve the real driving force for dehydrogenation. As for the tendency of hydrogen absorption capacity,it presents an elevation firstly and soon after a decline with the rising of spinning rate, however, it always lowers with Y content growing. With Y content and spinning rate increasing, their thermodynamic parameters(△H and △S absolute values) visibly decrease, and the starting hydrogen desorption temperatures of alloy hydrides obviously lower.     

Grain boundary segregation and its influences on ionic conduction properties of scandia doped zirconia electrolytes

Solid oxide fuel cell is a promising energy conversion system which converts chemical energy into electrical energy directly. Electrolyte is the key component and determines the working temperature. In this paper,ceria and scandia co-doped zirconia electrolytes sintered from 1300 to 1550 ℃ were chosen as research objects. Scanning electron microscopy, X-ray diffraction and transmission electron microscopy were performed to characterize the ceramic samples. The effects of grain size and grain boundary element segregation on the electrical conductivity were focused. Electrochemical impedance spectroscopy was used to calculate the bulk, grain boundary and specific grain boundary conductivity. Results show that the bulk and grain boundary ionic conductivity increases with the increasing grain size.However, the specific grain boundary conductivity decreases with the increasing grain size. This is explained by the fact that Sc~(3+) is segregated at the grain boundary, which leads to higher oxygen vacancy concentration when sintered at lower temperature.     

Effect of preparation method on physicochemical properties and catalytic performances of LaCoO_3 perovskite for CO oxidation

Perovskite oxides LaCoO_3 prepared by templating, co-precipitation and sol-gel method with different complexants were systematically characterized and its catalytic performances for CO oxidation were investigated. The samples were characterized by X-ray diffraction, thermogravimetry analysis and differential scanning calorimetry, N_2 physisorption, transmission electron microscopy, temperature program reduction of hydrogen, temperature program desorption of oxygen and X-ray photoelectron spectroscopy measurement, results of which show that the properties of LaCoO_3, such as surface morphology, surface area, surface compositions, redox capability, oxygen vacancy, as well as the calcination temperature and formation mechanism, depend intimately on the preparation method. Catalytic tests indicate that the sample prepared by carbon templating method shows the best activity for CO oxidation, with full CO conversion obtained at 135 ℃. In particular, the catalyst can be activated and significant increase of activity can be obtained with the increase of reaction time. The cyclic and longterm stability of catalysts were discussed and compared.     

Controllable synthesis of Eu~(3+) ions doped Zn(OH)F and ZnO micro-structures:Phase,morphology and luminescence property

Eu~(3+) ions doped Zn(OH)F and ZnO micro-structures with specific morphologies were synthesized by a simple hydrothermal method only through altering the addition amount of NH_4F and hexamethylenetetramine(HMT). The phase structure, morphology and luminescence properties of the as-prepared samples were characterized by X-ray powder diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), photoluminescence(PL) spectra and lifetime. The results indicate that the obtained Zn(OH)F:Eu~(3+) samples possess net-like and dandelion-like morphologies,which have an identical orthorhombic phase structure. It is found that the addition amount of raw materials such as NH_4F and HMT plays a critical role for the formation of Zn(OH)F:Eu~(3+). If the addition amounts of NH_4F or HMT are reduced by half, the hexagonal ZnO:Eu~(3+) sample with peanut-like morphology can be obtained. Under the excitation of UV light, both the as-prepared Zn(OH)F:Eu~(3+)and ZnO:Eu~(3+) samples exhibit the characteristic emission of the doped Eu~(3+).     

Effect of synthesis time on morphology of CeO_2 nanoparticles and Au/CeO_2 and their activity in oxidative steam reforming of methanol

Ceria(CeO_2)supports,synthesized by hydrothermal treatment with different synthesis time(CeO_2-X h,where X is the synthesis time in h)in the presence of the surfactant cetyltrimethyl ammonium bromide,were used as supports for gold(Au)catalysts.The synthesis time significantly affects the morphological structure and crystallite size of CeO_2,where CeO_2-2 h has the smallest crystallite size with coexisting nanorods and nanoparticles.Transmission electron microscopy analysis confirms the morphology of CeO_2 with distinctive(110),(100)and(111)planes,in agreement with interplanar spacings of 0.19,0,27 and 0.31,respectively.However,the morphology of CeO_2-8 h and CeO_2-48 h is mainly a truncated octahedral with crystal planes(111)and(100)accompanied by an interplanar spacing of 0.31 and0.27 nm,respectively.The CeO_2-X h supports and those with a 3 wt%Au loading(Au/CeO_2-X h)were investigated in the oxidative steam reforming of methanol at temperatures between 200 and 400 ℃.The Au/CeO_2-2 h gave the highest methanol conversion level and hydrogen yield at a low temperature of 250 ℃.This superior catalytic performance results from the good interaction between the metal and support and the well-distributed Au species on the CeO_2 support.