Electrochemical Behavior of Bulk Amorphous Steel Fe55M2Cr12Mo10B6C13Y2（M=Ni, Cu, Nb）

 Fe55Ni2Cr12Mo10B6C13Y2,Fe55Cu2Cr12Mo10B6C13Y2 and Fe55Nb2Cr12Mo10B6C13Y2 alloys with diameter of 4mm were produced by copper mold casting. The role of alloying additions (Ni, Cu or Nb) on corrosion resistance of Fe55Nb2Cr12Mo10B6C13Y2, Fe55Ni2Cr12Mo10B6C13Y2 and Fe55Cu2Cr12Mo10B6C13Y2 alloys were studied by polarization curves and electrochemical impedance spectroscopy (EIS). The results show that Fe55Ni2Cr12Mo10B6C13Y2 and Fe55Cu2Cr12Mo10B6C13Y2 alloys can be cast into bulk metallic glasses. Fe55Ni2Cr12Mo10B6C13Y2 and     

Effect of Rapid Quenching on Microstructures and Electrochemical Performances of La2Mg（Ni0.85Co0.15）9M0.1 （M = B, Cr） Hydrogen Storage Alloys

The La-Mg-Ni-system （PuNi3-type） La2Mg （Ni0.85 Co0.15 ）9M0.1 （ M = B, Cr） hydrogen storage etectrode alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were determined and measured. The effects of rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The obtained results show that the alloys are composed of the （La, Mg） Ni3 phase （PuNi3-type structure） and the LaNi5 phase, as well as the small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloy containing boron, and the Ni2B phase in the alloy nearly disappears after rapid quenching. The relative amount of each phase in the alloys depends on the quenching rate. The rapid quenching technique can greatly improve the electrochemical performance of the alloy, and the effect of rapid quenching on the activation performances of the alloys is minor. Rapid quenching enhances the cycle stability of the alloy, and the cycle life of the alloy increases with the increase of the quenching rate.     

Effect of Ni/（La＋Mg） Ratio on Structure and Electrochemical Performance of La-Mg-Ni Alloy System

As the alloy with the most suitable Ni/(La+ Mg) ratio has higher capacity and good cycle stability,theeffects of Ni/(La+Mg) ratios on the electrochemical performances of the La0.80 Mg0.20 Nix (x= 3.5 to 5.0) alloys have been investigated to find the most suitable Ni/(La+ Mg) ratio.The results of XRD and SEM observations show that the phase composition of the alloys varies with different Ni/(La+Mg) ratios.When Ni/(La+Mg) is notmore than 4.25,all the alloys contain LaNi5 and (La,Mg)2Ni7 phases,in addition,the LaMg and (La,Mg)Ni3 phases exist in the x=3.5 and 3.75 alloys,respectively.The LaMg2Ni9 phase exists in the x=4.25 alloy.There are the LaNi5 and LaMg2 Ni9 phases in the x= 4.5,4.75,and 5.0 alloys.The phase abundance and cell volume change with different Ni content.When the Ni/(La+Mg) ratio is not more than 4.25,the alloys possess excellent activation capability,however,the activation capabilities of the alloys decrease with a further increase in the Ni/(La+Mg)ratio.With increasing the Ni/(La+ Mg) ratio,the maximum discharge capacities,the medium voltages,and the cycle stabilities of the alloys first increase and then decrease.When the Ni/(La+Mg) ratio is 3.75,the corresponding alloyhas the maximum discharge capacity among all the alloys.However,the cycle stability of the Ni/(La+ Mg)= 4.0 alloy is better than that of the others.     

Electrochemical properties of cobalt-free La0.80Mg0.20Ni2.85Al0.11M0.53 （M=Ni, Si, Cr, Cu, Fe） alloys

In order to investigate the effect of different B-site additions on phase structure and electrochemical properties of cobalt-free La-Mg-Ni based alloys, La0.80Mg0.20Ni2.85Al0.11M0.53 (M=Ni, Si, Cr, Cu, Fe) hydrogen storage alloys were prepared and studied systemati-cally. X-ray powder diffraction showed that the alloys consisted mainly of LaNi3 phase and LaNi5 phase except that Cr addition caused a minor Cr phase. Electrochemical testing indicated that alloys with additional Ni, Cr, Cu or Fe were activated within only 1-2 cycles, while that with Si addition needed 4 cycles. Adding Si, Cu and Fe increased cycling stability of La-Mg-Ni based alloys. However, maximum discharge capacity decreased from 362 mAh/g to 215 mAh/g in the order of Ni>Fe>Cu>Cr>Si. In addition, electrochemical kinetics of alloy electrodes was also researched by measuring high rate discharge ability (HRD), hydrogen diffusion coefficient (D) and limiting current density (IL).     

Phase Structure and Electrochemical Characteristics of Ml（Ni3.55Co0.75Mn0.40Al0.30）5x （x=0.88, 0.92, 0.96, 1.00） Hydrogen Storage Alloys

The phase structure and electrochemical characteristics of Ml （（Ni3.55Co0.75Mn0.40Al0.30）sx （ x = 0.88, 0.92, 0.96, 1.00） hydrogen storage alloys were studied. The effect of the stoichiometric ratio on the phase structure and electrochemical characteristics was analyzed. The results of XRD reveal that all the alloys consist mainly of LaNi5 phase with the hexagonal CaCu5 structure. But a few of the diffraction peaks of La2Ni7 phase on XRD pattern are observed when x ≤ 0.92, and with decreasing x, the intensity of La2Ni7 diffraction peaks increases and the values of lattice parameters a and cell volume increase, c and c/a of LaNi5 phase decrease gradually. When x≥0.96, La2Ni7 phase disappears and the alloys become single CaCu5-type. The electrochemical tests show that the maximum discharge capacity, high rate dischargeability and low temperature dischargeability are improved to different degrees by adjusting the stoichiometric ratio.     

Effects of Strip Casting and Annealing on Electrochemical Properties of LPCNi3.55Co0.75Mn0.4Al0.3 Hydrogen Storage Alloys

The effect of thickness (1～10 mm) of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the 0.2 C discharge capacity of as-cast LPCNi3.55Co0.75Mn0.4Al0.3 alloy increases with the increase of the thickness of the ingots. As-cast alloy with the thickness of 10 nun shows better activation property, higher 1C discharge capacity and better cyclic stability than others.It is mainly contributed to its larger unit cell volume and less internal stress. Annealed LPCNi3.55Co0.75Mn0.4Al0.3 alloywith the thickness of 3 mm shows much better comprehensive electrochemical properties than as-cast one; The cyclic stability of the alloy with the thickness of 6 mm and the activation properties of the alloys with the thickness of 3～6 mm are improved after annealing. It is mainly owing to the great release of intemal stress and the decrease fo the segregation of Mn in the alloys.     

Crystalline Behavior and Magnetic Properties of Nd60Fe30-x Al10Cox（x = 0,5,10） Bulk Amorphous Alloys

Crystalline behavior and magnetic properties of Nd60Fe30-xAl10Cox( x = 0, 5, 10) bulk amorphous alloys were investigated by differential scanning calorimeter (DSC), X-ray diffraction (XRD) and the vibrating sample magnetometer (VSM). Neither glass transition nor supercooled liquid region before crystallization was observed for the as-cast Nd60Fe30-xAl10Cox ( x = 0,5,10) bulk amorphous alloys. The glass forming ability can be improved significantly by the addition of Co. The as-cast Nd60Fe30-xAl10Cox (x = 0,5,10) alloys show hard magnetic behavior. With the addition of Co content, intrinsic coercivity (iHc) increases while the saturation magnetization(σs) and remanence (σr) decrease. The Curie temperature for the as-cast Nd60Fe30-xAl10Cox alloys increases from 451 K for x =0 to 468 K for x = 10. Some pre-cipitation of crystalline phases does not affect the hard magnetic properties of Nd60Fe30-xAl10Cox(x = 0,5,10) alloys, while the hard magnetic behavior disappears quickly after the alloys being completely crystallized.     

Effect of CoO Addition on Electrochemical Properties of La0.7Mg0.3 （Ni0. 85 Co0. 15 ） 3.5 Hydrogen- Storage Alloy

In order to improve the cycling stability of La-Mg-Ni-Co hydrogen storage alloys, the La0.7Mg0.3 （Ni0.85Co0.15）3.5 alloy was prepared by inductive melting under argon atmosphere. The effect of additive CoO on electrochemical properties of La0.7Mg0.3（Ni0.85 Co0.15）3.5 alloy, which is used as an electrode material was studied. When the addition of CoO is 5 %, both the discharge capacity at high-, low- and room-tem- perature and charge-discharge cycling stability at room temperature can be significantly improved. Electro- chemical measurements and X-ray diffraction （XRD） analyses suggest that CoO improves the electrochemical properties of the La0.7Mg0.3（Ni0.85Co0.15）3.5 alloy by promoting the electrochemical reaction of another phase in the alloy and by self electrochemical reversible reaction occurring during the charge-discharge process.     

A Comparative Study on Dwell Fatigue of Ti-6Al-2Sn-4Zr-xMo (x = 2 to 6) Alloys on a Microstructure-Normalized Basis

The dwell effects of Ti624x (x = 2 to 6) alloys, including dwell fatigue life debit, fracture mode and strain accumulation, were characterized and compared. With increasing Mo content, the dwell fatigue life debit decreases quickly, and dwell fatigue fracture exhibits a transition from subsurface to surface initiation. Accompanying these changes, the accumulated strain decreases, and the pattern of secondary cracks loses morphological features typical of dwell cracks. These variations in the fatigue behavior of Ti624x were attributed on the fundamental level to the dual effects of Mo: It decreases the β transus of titanium and, as a slow diffuser, reduces the rate of phase transformation from β to α. A higher Mo content encourages nucleation of multiple variants of α laths and promotes the transition from aligned colonies to basketweave microstructure during cooling after β forging. As a result both the grain size and microtexture intensity of α grains in the two-phase processed and heat treated microstructure are reduced. Smaller grain size of the alloys with higher Mo content produces smaller slip band spacing and reduces accumulated strain during dwell fatigue, thus reducing propensity for crack initiation. Microtexture was shown to be the direct cause of dwell sensitivity, and their relationship was described with the aid of a two-region redistribution model based on a previous two-element redistribution model proposed by Bache.     

Electrochemical Behavior of Lao. 7Mgo. 3 （ Ni1-x Cox ） 3.5 （ 0≤x≤0.5 ）Hydrogen Storage Alloys

The low-temperature phase transformation of LaCrO3 and doped-LaCrO3 was studied by DSC andXRD, and thermal expansion during phase trans formation was measured. It is found that the phase transformation of LaCrO3 begins near 240℃ and ends up to 265℃. The phase transformation temperature range obviously raises as the Ca content increases. The low temperature transformation changes the crystal structure of LaCrO3 and Ca-doped LaCrO3 from orthorhombic to rhombohedral and is a heat-absorbing reaction.There is no weight change but shrink of the sample happened during transformation.     

Zr基大块非晶的研究

利用射流成型法制备出Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅大块非晶.该合金系统具有很强的玻璃形成能力和宽的过冷区,其玻璃转化温度T_g=650.63K,晶化温度T_x=721.90K,过冷区△T_x=T_x-T_g=71.27K.Vicker硬度为558kg/mm²压缩断裂强度1730GPa,弹性模量82GPa.观察其断口有大量纹络状河流花样,并有融化的液滴存在.该合金系统大的玻璃形成能力应归功于合金组元的多样性、组元间大的原子半径比率、组元间大的混合负热及在冷却过程中过冷区粘度的急剧上升等因素.     

Influence of crystallization on corrosion resistance of Al86Ni6La6Cu2 amorphous alloy

The influence of crystallization on the corrosion behavior of Al86Ni6La6Cu2 amorphous alloy in 0.01 M NaCl solution was investigated by electrochemical techniques. The Al86Ni6La6Cu2 amorphous alloy was prepared by melt spinning method, and the partially and fully crystallized states were obtained by controlled annealing. The evolution of the crystallization process after annealing was characterized by differential scanning calorimeter （DSC） and X-ray diffraction. The polarization curves revealed that all samples exhibited spontaneous passivation. The fully amorphous Al86Ni6La6Cu2 sample exhibited the best corrosion resistance. Partial and full crystallization resulted in deterioration of corrosion resistance in comparison with that of the as-spun amorphous state.     

Effect of Aluminium Addition on Glass Forming Ability of Nd55-x Al10＋x Fe15 Co20 （x = 0, 5, 10） Alloys

Nd55-x Al10＋x Fe15 （x =0, 5, 10） bulk glass-forming alloys with distinct glass transition in differential scanning calorimetry （DSC） traces were obtained by suction casting, The glass forming ability （GFA） of the alloys was investigated. It was found that the reduced glass transition temperature （Trg） and the parameter γ of the alloys increased with the increasing concentration of Al. The glass formation enthalpy of the alloys was calculated based on Miedema＇s model, and it was suggested that the GFA of the alloys could be enhanced by the decrease of the glass formation enthalpy with Al additions.     

Amorphous forming ranges of Al-Fe-Nd-Zr system predicted by Miedema and geometrical models

A method based on the semi-empirical Miedema model and a geometrical model was used to study the glass forming abilities(GFA) and the amorphous forming ranges of Al-Fe-Nd-Zr system and its constituent ternary systems.The amorphous forming composition ranges were analyzed based on different criteria such as ΔGam-ss and PHSS(PHSS=ΔHchem(ΔSC/R)(ΔSσ/R)) for Al-Fe-Nd system.The predicted amorphous forming range was in good agreement with the experimental results.The results showed that the criterion of ΔGam-ss was more accurate,and agreed well with the experiment results.The Gibbs free energy difference ΔGam-ss and parameter PHSS were then used to predict the amorphous forming composition range for the rest of the constitutive ternary systems of Al-Fe-Nd-Zr.In addition,the amorphous forming composition ranges of the(Al-Fe-Zr)100–x Ndx(x=50,60,70) systems were predicted by ΔGam-ss and the modified parameter PHSS.The Gibbs free energy of Al10(Fe1–x Zrx)30Nd60 were also calculated.The GFA parameter PHSS indicated that the composition with the highest GFA was Al33.5Fe13.5Zr3Nd50 for the(Al-Fe-Zr)50Nd50 system,Al28.8Fe10Zr1.2Nd60for the(Al-Fe-Zr)40Nd60 system and Al22.8Fe6.9Zr0.3Nd70 for the(Al-Fe-Zr)30Nd70 system,and the results suggested that those alloys with high content of Al had higher GFA.The appropriate content of neodymium and zirconium resulted in the lower value of PHSS and increased the GFA obviously.     

Effects of Microalloying on Glass Forming Ability and Thermodynamic Fragility of Cu-Pr-Based Amorphous Alloys

The effects of microalloying of Ti and B on the glass formation of Cu60Pr30Ni10Al10-2xTixBx（x = 0, 0.05% （atom fraction）） amorphous alloys was investigated using differential scanning calorimetry （DSC） and X-ray diffraction （XRD）. XRD analysis showed that mieroalloying with 0.05% Ti and 0.05% B improved the glass forming ability （GFA）. The smaller difference in the Gibbs free energy between the liquid and crystalline states at the glass transition temperature （△G1-X（Tg）） and the smaller thermodynamic fragility index （△Sf/Tm, where ASf is the entropy of fusion, and Tm is the melting temperature） after mieroalloying correlated with the higher GFA.     

Luminescent properties of amorphous phosphor 1.4YeO3·2.5Al2O3·0.1Tb2O3 prepared by sol-gel method

Amorphous phosphor 1.4YeO3·2.5Al2O3·0.1Tb2O3 （the same composition as Y2.8Tb0.2Al5O12） was prepared via a sol-gel method at relatively low temperature （i.e., below 650℃）, which is much lower than that for the preparation of polycrystalline Y3Al5O12：Tb^3＋ （above 1400℃）. The amorphous phosphor prepared in the optimized conditions showed a bright green-yellowish luminescence, the intensity of which was comparable with that of polycrystalline sample and the emissions of which were assigned to 5D4 → 7Fj transitions of Tb^3＋. Besides the emissions of Tb^3＋, the amorphous samples prepared at temperatures below 500 ℃ presented a weak blue emission band around 420 nm.     

Study on thermal expansion behavior of Dy2O3 - Al2O3 - SiO2 glass

Employing Dy2O3, Al2O3, and SiO2 as starting materials, several series of Dy2O3-Al2O3-SiO2 sealing glass were prepared. The relationship between their coefficients of thermal expansion and the contents of Dy2O3, Al2O3, and SiO2 were studied respectively. Experimental results showed that Dy2O3 and Al2O3 had a positive effect on the coefficient of thermal expansion of glass, whereas, SiO2 had a negative effect. The coefficient of thermal expansion of glass showed an apparent linear relation to the contents of these three raw materials, from which an estimation model was built, to calculate the coefficient of thermal expansion of sealing glass. Relative errors of the calculating results to testing results were no more than 2%, which suggested that the estimation model was reasonable. This study provides a good theory reference for the practical utilizing of this sealing material, through which a proper glass composition for good sealing could be easily found.     

微量元素Y、Ag对Cu基非晶合金玻璃形成能力的影响

采用单辊旋淬法制备了Cu50Zr42Al8,Cu46 Zr47-xAl7Yx(x=2,5),Cu43Zr42AlsAg7和Cu43Zr42Al8Ag5 Y2非晶合金薄带,利用X射线衍射和差示扫描量热分析研究了合金样品的玻璃形成能力和热稳定性.结果表明,在Cu50Zr42Al8中添加适量的Ag、Y后使得非晶合金的短程有序结构发生改变.合金Cu46Zr47-xAl7Yx(x=2,5)的过冷液相区宽度ΔTx分别比Cu50 Zr42 Al8增加了19K、30K,约化玻璃转变温度Trg从0.565分别增加到0.579和0.566,参数γ从0.402分别增加到0.418和0.420,说明Y的添加提高了非晶合金的热稳定性和玻璃形成能力.合金Cu43Zr42 Al8Ag7和Cu43Zr42Al8Ag5Y2与Cu50Zr42Al8相比,约化玻璃转变温度Trg及参数γ均有了明显的提高,达到了0.619、0.416和0.609、0.411,表明Ag的添加、Ag和Y的同时添加均提高了Cu - Zr -Al系非晶合金的玻璃形成能力,但Ag的效果更加显著.     

Synthesis and Crystal Structure of A Bimetallic Terbium Complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3 （THF）3

The reaction of 2, 6-^iPr2CbH3NHSiMe3 with Tb（CH2SiMe3）3（THF）2 in benzene at room temperature afforded a binuclear terbium complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3（THF）3. X-ray diffraction revealed that Tb atoms were bridged by three methylene units. One Tb atom was six-coordinated by two nitrogen atoms, three methylene carbons, and one THF molecule, while the other Tb atom was six-coordinated by one nitrogen atom, three methylene carbons, and two THF molecules. Both Tb atoms adopted a distorted trigonal prism geometry.     

Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd2[C6（COO）6] （H2O）6} and {Ho2[C6（COO）6]（H2O）6}

Two novel 3-D coordination compounds, Nd2[C6（COO）6]（H2O）6 （1）and Ho2[C6（COO）6]（H2O）6 （2）, were hydrothermaily synthesized from mellitic acid and neodymium perchlorate （or holmium perchlorate） in the alkaline aqueous solution and characterized with elemental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the orthorhombic system, space group Pnnm, with a=1.3531 （4） nm, b=0.6687 （2） nm, c=1.0224（3） nm, V=0.92523（5） nm^3, Z=4, D=2.630 g/cm^3, F（000）=696.0, Goof=1.052. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0195, wR2=0.0382 for 1; a=1.3411 （2） nm, b=0.6586（1） nm, c=1.0116（2） nm, V=0.8935（3） nm^3, Z=4, D=2.877 g/cm^3, F（000）=724.0, Goof=1.061. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.