Thermal and radiative characteristics of oxyfluoride glass singly doped with lanthanide ions

Rare earths-doped oxyfluoride glasses based on germanium oxide and lead fluoride were prepared from commercial raw materials. The glasses with general composition of 50GeO2-(50-x-y)PbO-yPbF2-xLnF3 (Ln=Pr3+-Yb3+), contained different concentrations of optically active dopants (x=0.2 mol.% and 2 mol.%) and PbF2 (y≤15 mol.%). The differential thermal analysis (DTA) was used to determine both thermal characteristic and thermal stability properties of the glasses in the function of the kind of dopant, its concentration, and a glass composition. Characteristic glass temperatures such as glass transition temperature (Tg), glass crystallization temperature (Tc) and temperature corresponding to the maximum of the crystallization rate (Tpc) were evaluated. On the basis of obtained results, the thermal stabilities of glasses under study were evaluated using various thermal stability criteria (Dietzel factor ?T, Saad-Poulain factors H' and S). It was found that the increase in rare earth fluoride contents influenced thermal characteristics when the characteristic temperatures of the individual glass was shifted towards higher values. The effect of the PbF2 content and the kind of rare earth impurity on the glass stability was observed. Absorption spectra of lanthanide-doped glasses were measured at room temperature and used to determine the phenomenological intensity parameters Ωt and next, to estimate radiative properties of lanthanide ions in this matrix. Radiative transition probabilities of luminescent states of Ln3+, branching ratios and radiative lifetimes were determined. The variation of the Ωt along the lanthanide series was presented and discussed.     

Process optimization of electroless copper plating and its influence on electrochemical properties of AB5-type hydrogen storage alloy

The amount of Cu coating by chemical plating was investigated based on quadratic regression orthogonal experimental design being adapted to the variation law of temperature,pH value and Ni2+concentration,and the relevant regression equation was expressed as y=2.1609+0.5295×10-3T2-0.0342P2-0.0265N2+0.0023TP+0.0020TH+0.0199PN-0.0959T+0.3814P-0.2073N.The results showed that the deposition rate augmented with the increasing in temperature,pH value and Ni2+concentration.The experimental parameters of the optimal coating were temperature 75 ℃,pH value 8.5 and Ni2+concentration 1.2 g/L.The electrochemical tests indicated that the cycle stability increased from 60.66% to 75.58%,indicating that the treated alloy exhibited better corrosion resistance.     

天铁热力风机升级改造方案设计

通过对天铁集团高炉现状、风机现状的分析,提出了对热力厂风机升级改造的规划,确定了实施方案.该方案实施后将彻底改变风机渐进式改造的现象,使新高炉的备用机组发挥更大的作用,可增加现有高炉的风压、风量,使现有高炉的产量、冶炼强度进一步提高.     

Recent progress report on DNA B-Z transition modulated by rare earth-amino acid complex and Alzheimer's disease amyloid beta

Rare earth dements have unique physical, magnetic, luminescent and catalytic properties. They have been successfully used as medicine and probes in luminescent resonance energy transfer (LRET) for bioassays, as well as reagents for diagnosis in magnetic resonance imaging (MRI). In this progress report, we will focus on recent progress on how rare earth amino complexes bind to DNA and change DNA structure, especially on DNA B-Z transition induced by rare earth amino acid complex and its potential impact on Alzheimer's disease (AD).     

Numerical Simulation on Inclusion and Bubble Entrapment in Solidified Shell in Model Experiment and in Mold of Continuous Caster With DC Magnetic Field

A model experiment investigating entrapment of inclusions and bubbles on the solidified shell was performed using molten steel,and the conditions for inclusion and bubble entrapment and mechanism of entrapment were studied.The results were applied to the flow behavior in the casting mold of a continuous caster.At the solid-liquid interface,entrapment of inclusions is greatly reduced by the existence of a low velocity flow,e.g.,0.05m/s.The above-mentioned interfacial flow velocity dependency of inclusion entrapment is considered to be largely influenced by changes in the thickness of the concentration boundary layer,which depend on the interfacial flow velocity.Specifically,bubbles and inclusions which enter the concentration boundary layer are drawn to the solid-liquid interface by a suction force which is several orders larger than the Saffman’s force.In addition to the above-mentioned suction force,the so-called cleaning effect is determined by fluid-dynamic forces such as drag force,etc.which act on particles,and furthermore,by resident time of particles at the solid-liquid interface,which depends on the solidification rate.In a FC mold with a 2-stage electromagnetic brake,flotation of bubbles entrained in the jet flow from the nozzle is accelerated with the large DC magnetic field.This is attributed to the braking effect of the DC field on the nozzle jet and the upward flow by the buoyancy of the bubbles.As a result,the interfacial flow velocity can be normalized by increasing the strength of the magnetic field,and entrapment of large bubbles and inclusions can be reduced.     

Influence of Controlled Rolling and Cooling Process on the Mechanical Properties of Low Carbon Cold Forging Steel

In the present paper,controlled rolling and cooling processing was conducted by using a laboratory hot rolling mill.The influence of different processing parameters on the mechanical properties of low carbon cold forging steel was investigated.The results show that the faster cooling after the deformation (especially in low temperature rolling conditions) leads to the refinement of the ferrite grain.The specimen exhibits very good mechanical properties owing to the finer ferrite grains.The pearlite morphologies can also affect the mechanical properties of low carbon cold forging steel.The mechanical properties increase with decreasing final cooling temperature within the range from 650℃ to 570 ℃ due to the finer interlamellar spacing of pearlite colony.The mechanical properties of the specimens with fast cooling after the conventional rolling are not only better than those of the specimens with slow cooling after low temperature rolling,but also almost similar to those of the specimens with fast cooling after low temperature rolling.It is suggested that fast cooling after high temperature rolling (the conventional rolling) process would be of important industrial value.     

The LIMMCAST Program at HZDR:Modelling of Fluid Flow and Transport Phenomena in the Continuous Casting Process

Model experiments with low melting point liquid metals are an important tool to investigate the flow structure and related transport processes in melt flows relevant for metallurgical applications.We present the new experimental facility LIMMCAST for modelling the continuous casting process of steel using the alloy SnBi at temperatures of200-400℃.The parameters of the facility and the dimensions of the test sections will be given,and the possibilities for flow investigations in tundish,submerged entry nozzle and mould will be discussed.In addition,the smaller set-up Mini-LIMMCAST will be presented,which works with the room-temperature liquid alloy GaInSn.The main value of cold metal laboratory experiments consists in the capabilities to obtain quantitative flow measurements with a reasonable spatial and temporal resolution.New ultrasonic and electromagnetic techniques for measuring the velocity in liquid metal flows came up during the last decade allowing for a satisfying characterisation of flow quantities in the considered temperature range up to 400℃.First results from LIMMCAST and Mini-LIMMCAST will be presented covering the following phenomena:fully contacfless electromagnetic tomography of the flow in the mould,flow monitoring by a multitude of ultrasonic sensors,and analysis of the flow in the mould under the influence of an electromagnetic brake:intensification of the flow turbulence contrary to the expected flow damping,injection of argon bubbles through the stopper rod:occurrence of pressure oscillations.     

汽车零件强度、寿命与可靠性分析与模型

The elasto-plastic stress/strain behavior of an automobile rear axle was analyzed by three-dimension finite element method.Based on the stress in critical area where fatigue crack appears,the fatigue life of the welded structure was predicted using the critical shear stress plane criterion.To improve the fatigue property of the rear-axle,the welding-seam was strengthened by both pellet spraying and plasma melting,and evident improvement was experimentally illustrated.Based on the viewpoint that a complex component is also a system in the respect of reliability assessment and statistical dependence among component failures(i.e.the so call"common cause failure")is inherent for system under stochastic load environment,a system-level load-strength interference model was presented and the reliability of the rear axle was estimated as a system,instead of a component.     

铝土矿、氧化铝和电解铝产业链市场及利润流向

本文主要介绍近几年铝土矿、氧化铝和电解铝产业链的市场和利润流向演变以及未来发展形势.     

提高轧制重轨BS75A成材率的措施

介绍了武钢大型厂生产重轨BS75A时,利用现有设备,通过不断研究,找到了一条提高重轨(BS75A)生产成材率的方法,并取得了较好的经济效益.     

Zirconia modified monolithic macroporous Pt/CeO2/Al2O3 catalyst used for water-gas shift reaction

Monolithic macroporous Pt/CeO2/Al2O3 and zirconia modified Pt/CeO2/Al2O3 catalysts were prepared by using concentrated emulsions synthesis route. The catalytic performances over the platinum-based catalysts were investigated by water-gas shift (WGS) reaction in a wide temperature range (180-300 oC). The samples were characterized with thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and temperature programmed reducti...     

高活性PtMo_2C/Al_2O_3催化剂的研究进展

叙述了高活性PtMo2C/Al2O3催化剂的制备、性能和在水气位移反应中的应用。由于制备出的PtMo2C/Al2O3催化剂中,其铂离子呈几个纳米分散态显微结构,分布十分均匀,它比传统的催化剂如CuZn/Al2O3、Pt/C、Pt/Al2O3和PtCeO2等的催化活性高,选择性好,WGS速率高,反应温度低。     

Synergetic catalysis of ceria and titania for selective reduction of NO

The promotional effect of the interaction between titania and ceria on the catalytic performance for selective reduction of NO was studied.The catalysts,CeO 2,TiO 2,CeO 2 /TiO 2 and Ti x Ce 1-x O 2,were synthesized and tested in NH 3-Selective catalytic reduction(SCR) of NO,and the samples were characterized by the Brunaller,Emmett and Teller(BET absorbed gas N 2),X-ray diffraction(XRD),high resolution transmission electron microscopy(HR-TEM),and temperature programmed desorption(TPD NH 3) techniques.The improvement mechanism of the interaction between the titania and ceria had been explored and discussed from two aspects of micro-structure and surface acidity.The interaction between the titania and ceria greatly improved the catalytic activity but had little effect on the active temperature.It was first reported that the acid amount determined the catalytic activity and the acid strength determined the active temperature for NH 3-SCR of NO.     

Effect of tungsten oxide on ceria nanorods to support copper species as CO oxidation catalysts

In this work,tungsten oxide with different concentrations(0,0.4 at%,2.0 at% and 3.2 at%) was introduced to the ceria nanorods via a deposition-precipitation(DP) approach,and copper species of ca.10 at% were sequentially anchored onto the modified ceria support by a similar DP route.The aim of the study was to investigate the effect of the amount of tungsten oxide(0,0.4 at%,2.0 at%,and 3.2 at%) modifier on the copper-ceria catalysts for CO oxidation reaction and shed light on the structure-activity relationship.By the aids of multiple characterization techniques including N_2 adsorption,high-resolution transmission electron microscopy(HRTEM),powder X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),and temperature-programmed reduction by hydrogen(H_2-TPR) in combination with the catalytic performance for CO oxidation reaction,it is found that the copper-ceria samples maintain the crystal structure of the fluorite fcc CeO_2 phase with the same nanorod-like morphology with the introduction of tungsten oxide,while the textural properties(the surface area,pore volume and pore size) of ceria support and copper-ceria catalysts are changed,and the oxidation states of copper and tungsten are kept the same as Cu~(2+)and W~(6+)before and after the reaction,but the introduction of tungsten oxide(WO_3)significantly changes the metal-support interaction(transfer the CuO_x clusters to Cu-[O_x]-Ce species),which delivers to impair the catalytic activity of copper-ceria catalysts for CO oxidation reaction.     

Effect of yttrium addition on water-gas shift reaction over CuO/CeO2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction (XRD), Raman spectroscopy, H2-TPR, cyclic voltammetry (CV) and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity (CO conversion reaches 93.4% at 250℃) and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak y of H2-TPR profile (I.e., the reduction of surface copper oxide (crystalline forms) interacted with surface oxygen vacancies on ceria), and the area of peak C2 and A1 (Cu0→Cu2+ in cyclic voltammetry process), respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.     

Influence of cobalt on performance of Cu-CeO_2 catalysts for preferential oxidation of CO

Copper and cobalt oxides supported on CeO_2 were investigated for preferential oxidation of carbon monoxide(CO-PROX) in the presence of excess hydrogen and CO_2.(Cuo)_(1-x)(Co_3 O_4)_(x/3)-(CeO_2)_(2.5)(x=0,0.25,0.50,0.75,0.85 and 1) catalysts were prepared by coprecipitation method.These mixed oxide catalysts were characterized by several physicochemical techniques,such as BET surface area(S_(BET)),X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),temperature programmed reduction(TPR) and X-ray photoelectron spectroscopy(XPS).XRD studies show the peaks related to CuO and Co_3 O_4 phases in copper and cobalt containing CeO_2 catalysts.The average particle size of the CeO_2 crystallites is in the range of 8-10 nm as evaluated from HRTEM studies.XPS studies demonstrate that Cu,Co and Ce in(cuO)_(1-x)(Co_3O_4)_(x/3)-(CeO_2)_(2.5) catalysts are presented in+2 and +1,+3 and +2 and +4 and +3 oxidation states,respectively.The catalyst with x=0.75 shows better activity and selectivity towards CO-PROX.Though the catalyst with only copper(CuO-CeO_2,x=0) shows good activity but reverse water gas shift(RWGS) reaction is noticed at high temperature.On the other hand,RWGS reaction is suppressed on the cobalt containing CuO-ceO_2 catalyst.Cobalt on CeO_2 with x=1 shows hardly any activity for PRoX reaction at low temperatures.No methanation activity is observed on CuO-CeO_2 or Co_3O_4-CeO_2 catalysts.In contrast,combination of copper and cobalt on CeO_2 shows methanation of CO where enhanced activity is observed with increasing in cobalt content.     

Influence of Additives Ceria and Lanthana on Performance of Pd／Al／Monolith Honeycomb Catalysts

The effects of ceria and lanthana additives on activity and thermal stabilization of the catalysts for CO oxidation were studied. The results show that the addition of CeO2 clearly improves the catalytic activity, which may derive from the synergic effect between CeO2 and PdO. The catalysts were characterized by means of temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) measurements. The XPS results of a slight increase in metal oxidation state reflect that the charge transfers from metal to ceria and ceria is slightly reduced, which leads to a decrease of the Ce-O bond strength. Pd-Ce synergism affects the reduction behavior of the catalysts. The TPR results show that the CeO2 ad-dition lowers the reduction temperature of PdO, while palladium facilitates the reduction of the ceria. For PdO/La2O3/Al2O3/monolith honeycomb catalysts, the aging test measurements at 1050 ℃ and the XRD results show that the formation of LaAlO3 which neutralizes the surface alumina defects inhibits the sintering of alumina.     

离子交换树脂对Pt/C催化剂耐久性的影响

离子交换树脂（Ionomer）是质子交换膜燃料电池催化层的重要组成部分,它在催化层中的主要作用是作为质子传导相传导质子。本文采用旋转圆盘电极法（RDE）,在模拟燃料电池真实的运行环境（模式一）和模拟燃料电池启停环境（模式二）两种模式下,研究了Ionomer对铂碳催化剂电压循环耐久性的影响。通过相同位置透射电镜分析法（IL-TEM）,分析了铂碳催化剂经历模式二耐久性测试后的结构变化。研究发现Ionomer的存在可以提高铂碳催化剂的耐久性。在模式一的测试中:添加Ionomer后,其氧还原半波电位下降值?E从23 mV下降至11 mV;没有发生碳的腐蚀,Pt颗粒的长大是催化剂性能下降的主要原因;Ionomer的存在延缓了Pt电化学比表面积（ECSA）的降低从而有利于保持Pt的活性。在模式二的测试中:添加Ionomer后,其氧还原半波电位下降值?E从25 mV下降至5 mV,除了铂颗粒长大外还发生了载体碳的腐蚀;Ionomer的存在同样可以保持Pt的活性;IL-TEM分析可以看到明显的铂颗粒长大和碳腐蚀,碳载体的腐蚀造成铂的严重流失和团聚。含Nafion的催化剂中铂颗粒平均粒径从2.7 nm增加到了3.76 nm,不含Nafion的催化剂中的铂颗粒平均粒径从2.44 nm增加到了4.19 nm。      

Preparation and characterization of Ce_(1-x)Pr_xO_2 supports and their catalytic activities

In this work, the addition of praseodymium(Pr) into ceria as a mixed oxide support in a form of Ce_(1-x)Pr_xO_2(x = 0.01,0.025, 0.050, 0.075 and 0.10) was prepared using a co-precipitation method. The structural and textural properties of the synthesized supports were characterized by X-ray diffraction(XRD), N_2 adsorption-desorption, Raman spectroscopy, H_2-temperature programmed reduction(H_2-TPR) and H_2-chemisorption. Upon addition of Pr, XRD patterns and Raman spectra indicated an enlargement of ceria unit cell and the characteristics Raman broad peak at 570 cm~(-1) which was attributed to the existence of oxygen vacancies in the ceria lattice. This indicated that some Ce~(4+) ions in ceria were replaced by larger Pr~(3+) cations. To evidence the incorporation of Pr~(3+) cations into ceria lattice,X-ray absorption near edge structure(XANES) was employed. The results showed that the oxidation states of Ce in mixed oxide supports were slightly lower than 4+ while those of Pr were still the same as a precursor salt. Therefore, the incorporation of Pr~(3+) into ceria lattice would lead to strain and unbalanced charge and result in oxygen vacancies. The reducibility of Ce_(1-x)Pr_xO_2 mixed oxide supports was investigated by H_2-TPR and temperature-resolved X-ray absorption spectroscopy experiment under reduction conditions. XANES spectra of Ce L_3 edges showed a lower surface reduction temperature(Ce~(4+)to Ce~(3+)) of Ce_(0.925)Pr_(0.075)O_2 than that of CeO_2 which agreed with H_2-TPR results. H_2-chemisorption indicated that Pr promoted the dispersion of the metal catalyst on the mixed oxide support and increased the adsorption site for CO. For WGS reaction, 1% Pd/mixed oxide support had higher WGS activity than 1%Pd/ceria. The increase of WGS activity was due to the increase of Pd dispersion on the support and the existence of oxygen vacancies produced from incorporation of Pr into the ceria lattice.     

Reverse water gas shift reaction over Co-precipitated Ni-CeO2 catalysts

The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.