Co含量对La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25（x=0～0.4）储氢合金电极性能的影响

采用电磁感应悬浮炉制备La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25(x=0,0.1,0.2,0.3,0.4)系列合金,研究Co含量对合金的相结构、吸放氢性能和电化学性能的影响。研究结果表明,该系列合金主要由LaNi5、Nd2Ni7相组成。当Co含量大于0.2时,合金中出现La2Ni7相。压强-吸氢量-温度(Pressure-Content-Temprature)测试显示在303 K温度下,合金具有良好的吸氢性能,当x=0.4时合金的最大吸氢量为1.29(质量分数,%)。电化学测试表明:随x值变化,合金电极的最大放电容量分别为340.0(x=0.0)、346.6(x=0.1)、370.0(x=0.2)、320.0(x=0.3)和346.6(mA.h)/g(x=0.4);随Co含量增加,合金电极容量保持率不断增加,高倍率放电性能先增加后减小,循环伏安曲线、氢在合金体中的扩散系数D共同反映了合金电极的动力学特性。     

La0.8Mg0.2(Ni2.7Co0.6Al0.1Mn0.1)x贮氢合金的电化学性能分析

采用恒电位法、EIS分析及双电极系统对La0.8Mg0.2(Ni2.7Co0.6Al0.1Mn0.1)x(x=0.9～1.10)系列合金进行电化学性能分析。结果表明,x=1.05的合金具有较好的自放电性能(CR=97.3%),而x=1.10的合金有较高的电化学容量(369 mAh.g-1)。合金电极的电化学阻抗谱(EIS)表明,随着化学计量比x的增大,合金电极的电荷迁移电阻先减小后增大,动力学性能先增强后减弱。线性极化测试表明,随着化学计量比x的增大,合金电极表面的电化学反应速率先增大后减小。通过合金电极阳极电流对时间响应的半对数曲线计算的氢扩散系数D随着化学计量比x的增大先增大后降低,说明合金内部的氢扩散能力先增强后降低。     

Structure and electrochemical hydrogen storage characteristics of the as-cast and annealed La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0-0.4） alloys

In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases: (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability (HRD) first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate (S100) after 100 cycles increased continuously.     

Synergetic migration behavior of La and Ce and related microstructure character of Cr-V-RE co-doped WC-Co alloy

The as-sintered sinter skin and the polished section of WC-11Co-0.4Cr 3 C 2-0.3VC-0.2RE(RE=mischmetal with La/Ce ratio of 0.65) alloy were analyzed.It was shown that the microstructures on the skin and in the inner part of the alloy were all characterized with a WC+β+M structure,where β was a cobalt-based binder phase and M represented a RE-containing phase.There existed an inward diffusion of S atoms,which caught and fixed the Ce atoms in the alloy and an outward diffusion of La atoms during the sintering process.Consequently,the M phase was characterized with the decreased La/Ce ratio(0.59) in the inner part and the increased La/Ce ratio(1.01) on the skin.The M phase on the skin was characterized with a γ-Ce 2 S 3 type structure.To suppress the long range migration of rare earth to the skin,S in the sintering atmosphere had to be eliminated.     

硼的添加对Mg2Ni储氢合金吸放氢性能的影响

镁系储氢合金有着价格低廉、储氢量大等优点,作为机载储氢材料有着广泛的应用前景,但其过高的氢分解温度,过慢的分解速度等缺点制约着实际应用.采用机械球磨制备出Mg2 Ni-xB(x =0％,1％,5％,10％,15％)系列储氢合金.通过XRD分析了合金的物相结构,采用P-C-T测试仪测定了合金的吸放氢性能,研究了添加不同含量的B对Mg2Ni合金吸放氢性能的影响.研究结果表明,B的添加对合金在200和300℃下吸放氢性能的改善作用不明显,但添加B的合金在400℃下的吸氢量均较Mg2Ni高,B的添加量由1％增至15％的合金吸氢量分别为3.09％,3.00％,2.81％,2.84％,而Mg2Ni的吸氢量则只有2.60％.随着B含量的增加,含B合金吸氢量略有降低;在含B的试样中,含5％B的合金吸氢速率最大,仅需180 s便能完成吸氢.所有含B合金的放氢平台均较Mg2Ni高且较为平坦.本次实验表明,B的添加量对合金性能的提升存在一个最优值,本次实验结果显示,添加5％B相对较好地改善合金的储氢性能,提高合金吸氢量和放氢平台压的同时能保持较快的吸氢速率.     

铈镧混合稀土对AZ91D压铸镁合金显微组织和蠕变性能的影响

研究了不同含量Ce/La(x=0,0.1,0.5,1.0)对AZ91D镁合金显微组织及蠕变性能的影响。通过X射线衍射(XRD)、金相显微镜(OM)、扫描电镜(SEM)及能谱分析(EDX)观察与分析表明,压铸AZ91D镁合金中添加Ce/La后,除了α-Mg,β-Mg17Al12相之外,还生成了新的稀土化合物Al11RE3(RE=Ce/La)化合物,并且细化了合金显微组织、提高了合金室温和高温力学性能。生成的Al11RE3(RE=Ce/La)高温热稳定相使AZ91D+xCe/La(x=0,0.1,0.5,1.0)合金在150℃,50MPa下的蠕变抗力优于AZ91D镁合金,1%Ce/La的合金与AZ91D相比,蠕变延伸率低了0.2%,最小蠕变速率从2.30×10-8s-1降低到2.02×10-8s-1。蠕变试样的微观组织结构分析表明:AZ91D合金的蠕变机制主要以晶界滑移方式为主,Al11RE3(RE=Ce/La)热稳定相在晶界处延缓和阻碍了晶界断裂的过程。     

Phase Structure and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

The rare earth based hydrogen storage alloys MmxM1 1 - x ( Ni3.55 Co0.75 Mn0.4 A10.3 ) ( x = 0 ～ 0.5 ) were investigated in this work.Adjusted Ml: Mm ratio to change the content of La,Ce,Pr and Nd in the alloys and then to change the phase structure, the influences of phase structure on the electrochemical properties were analyzed.The results indicate that the main phase of all alloys is LaNi5 with CaCu5 type structure and the crystal lattices constants of LaNi5 are changed with increasing x value, i.e, decreased a-axis, increased c-axis and axis ratio and nonlinear decreased crystal volume.The crystal volume of the alloy with x = 0.3 is larger than others.There is second phase A1LaNi4 in alloys when x≥0.3, which decrease the discharge capacity, but increase the cycling stability and high rate discharge ability.Compared comprehensively, the alloy with x = 0.3 shows the higher discharge capacity and the better cycling stability.     

Hydriding and dehydriding characteristics of nanocrystalline and amorphous Mg20-xLaxNi10（X=0-6） alloys prepared by melt-spinning

In order to improve the hydrogenation and dehydrogenation performances of the Mg2Ni-type alloys, Mg was partially substituted by La in the alloy, and melt spinning technology was used for the preparation of the Mg20-xLaxNi10 (x=0, 2, 4, 6) hydrogen storage alloys. The structures of the alloys were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). It was found that no amorphous phase formed in the as-spun La-free alloy, but the as-spun alloys containing La held a major amorphous phase. When La content x≤2, the major phase in the as-cast alloys was Mg2Ni phase, but with further increase of La content, the major phase of the as-cast alloys changed into LaNi5+LaMg3 phase. Thermal stability of the as-spun alloys was studied by differential scanning calorimetry (DSC), showing that spinning rate was a negligible factor on the crystallization temperature of the amor-phous phase. The hydrogen absorption and desorption kinetics of the as-cast and as-spun alloys were measured using an automatically con-trolled Sieverts apparatus, confirming that the hydrogen absorption and desorption capacities and kinetics of the as-cast alloys clearly in-creased with rising La content. For La content x=2, the as-spun alloy displayed optimal hydrogen desorption kinetics at 200 ℃.     

Ce对热浸镀铝HP40Nb钢氧化行为及组织的影响研究

通过SEM,EDS和XRD研究了Ce对HP40Nb热浸镀铝层组织结构和高温抗氧化性能的影响.结果表明,热浸镀过程中添加质量分数1％Ce促进了镀层外层中Fe2Al5和Fe4Al3Ce相的生成,抑制了内层Fe2Al5相长大;在1 000 ℃/4 h扩散处理过程中,Ce促进了γ向α相的转变以及α相中Ni3Al相的析出,并在渗层内层中生成富Ce相;800C/360 h氧化后,Ce促使渗层外层生成少量Fe2Al5和Cr3Si相,并使渗层外层组织均匀致密;1000℃/360 h氧化后,Ce促使α相长大导致渗层中生成大量的σ相.800℃氧化实验发现1％Ce使渗层组织致密,提高了渗层高温抗氧化性;1 000℃氧化实验发现1％Ce促进了渗层中σ相的生成,阻碍了Al原子的内扩散,保证了氧化过程中渗层表面生成α - Al2O3所需铝含量.     

Effect of annealing treatment on hydrogen storage properties of La-Ti-Mg-Ni-based alloy

The present study dealt with investigations on the effects of annealing on the hydrogen storage properties of La 1.6 Ti 0.4 MgNi 9 alloys.The experimental alloys were prepared by magnetic levitation melting followed by annealing treatment.For La 1.6 Ti 0.4 MgNi 9 alloys,LaNi 5,LaNi 3 and LaMg 2 Ni 9 were the main phases,Ti 2 Ni phase appeared at 900℃.Annealing not only enhanced the maximum and effective hydrogen storage capacity,improved the hydrogen absorption/desorption kinetics,but also increased the discharge capacity.The cyclic stability had been improved markedly by annealing,e.g.,when the discharge capacity reduced to 60% of maximum discharge capacity,the charge/discharge cycles increased from 66(as-cast) to 89(annealed at 800℃) and 127 times(annealed at 900℃).La 1.6 Ti 0.4 MgNi 9 alloy annealed at 900℃ exhibited better electrochemical properties compared to the other two alloy electrodes.     

锌基热镀合金的流动性能分析

采用金属型螺旋线试样测量纯锌及锌基热镀合金的流动性,以10℃为一个温度梯度,测量了420-510℃之间的流线长度数值。分析了液态金属流动性的影响因素,在锌液中加入0．3％（质量分数）的稀土合金,探讨了合金成分对流动性的影响。研究发现加入0．3％的稀土合金后,在相同温度下,合金的流动性比纯锌有明显提高。     

Structure and electrochemical hydrogen storage characteristics of Ce-Mg-Ni-based alloys synthesized by mechanical milling

The substituting Mg with Ni and milling as-cast alloy with Ni were adopted to obtain nanocrystalline/amorphous CeMgnNi+x wt.%Ni(x=100,200) alloys and promote the electrochemical hydrogen storage performances of CeMg_(12)-type alloys.Analyzing the structural features of the alloys provided a mechanism for ameliorating the electrochemical hydrogen storage properties.The electrochemical tests demonstrated that all the alloys just needed one cycle to be activated.Rising Ni proportion had an obvious role on charge-discharge reaction.The discharge capacities of the as-milled(60 h) alloys increased sharply from 182.0 mAh/gfor x=100 alloy to 1010.2 mAh/gfor x=200 alloy at current density of 60 mAh/g.Furthermore,milling time largely determined the performances of electrochemical reaction.The discharge capacity continued to grow along with prolonging milling time,while the cycle stability obviously decreased for x=100 alloy,and first declined and then augmented for the x=200 alloy with milling time extending.In addition,there was an optimal value with milling time varying for the high rate discharge abilities(HRD),which was 80.3%for x=100 alloys and 86.73%for x=200,respectively.     

Microstructures and hydrogen storage properties of as-cast and copper-mould-cast LaMg4Ni alloys

Phase compositions, morphologies and hydrogen storage properties of the as-cast and copper-mould-cast LaMgaNi alloys were studied. The dehydriding onset temperature of the as-cast alloy hydride was about 500 K, which was at least 50 K higher than that of the copper-mould-cast one, and the copper-mould-cast alloy hydride had a faster dehydriding rate compared with as-cast one. Additionally, the copper-mould-cast alloy could uptake 2.85 wt.% hydrogen, which was 95.0% of saturated hydrogen storage capac- ity at room temperature. While only 1.80 wt.% hydrogen （60% of saturated capacity） was absorbed for the as-cast alloy under the same conditions. The reversible hydrogen storage capacities and plateau hydrogen pressures of the two alloys were close. X-ray dif- fractions and scanning electron microscopy results indicated that similar thermodynamic property of the two alloys should be ascribed to the same hydrogen storage phase, Mg and MgzNi. The better hydrogen sorption kinetics of copper-mould-cast alloy should be as- cribed to the more uniform phase distribution compared with that of the as-cast one.     

瞬间液相扩散复合法生产钢质蜂窝夹芯减振板

 采用瞬间液相扩散复合原理生产钢质蜂窝夹芯减振板的关键问题之一是中间夹层助复剂的选择和配制。采用正交设计方法设计了一种以铜为基体元素、锌为主要合金元素，再添加微量元素和稀土铈，以降低熔点，提高润湿性和塑性，并可在中低温下使用的助复剂。利用瞬间液相扩散复合原理及特点，使用这种自制的助复剂对蜂窝夹芯减振板进行了复合，并测试了其力学性能和减振性能。结果表明，设计的蜂窝夹芯减振板可满足力学性能要求并提高了减振性能。     

Microstructures and Electrochemical Properties of Cobalt-Free LaNi4.0Al0.2Fe0.4Cu0.4-x Snx (x = 0 ～ 0.4) Electrode Alloys Prepared by Casting

The microstructure, hydriding performance, and electrochemical properties of LaNi4.0Al0.2Fe0.4Cu0.4- x Snx(x = 0 ～ 0.4) hydrogen storage alloys prepared by casting were investigated using XRD, SEM, pressure-composition isotherms, and electrochemical measurements. Substitution of Sn for Cu leads to the precipitation of LaNiSn phase. With increasing amount of tin substitution, cell volume, plateau pressures, and discharge capacities of the alloys decrease,whereas the cycle life of the alloys improves.     

高容量稀土基贮氢合金的研究

以金属RE、La、Ni、Co、Mn、Al作为稀土基贮氢合金的原料,制备了一系列不同成分的贮氢合金,进行了相应的组织结构分析及电化学性能的测试,研究了不同La、Co添加量对合金相结构与电化学性能的影响,选择确定了合适的合金配方,为生产高容量Ni-MH电池的负极材料提供了依据.     

Effect of cerium content on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex（x=0-1.0） alloys

Effect of Ce addition on microstructure and hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex (x=0, 0.5at.%, 0.8at.% and 1.0at.%) alloys was studied by X-ray diffraction, scanning electron microscopy and P-C-isotherm measurements. The results indicated that Ce addition was a useful way to improve the flatness of the plateau and increase hydrogen storage capacity of Ti24Cr17.5V50Fe8.5 alloy. It was indicated that both homogenization of composition and increase of hydrogen diffusion coefficient were the main reasons for improving the hydrogen storage performance of Ti24Cr17.5V50Fe8.5Cex alloys.     

微量稀土Ce对金合金铸态组织及其硬度的影响

文中研究了微量稀土元素Ce在金合金中的分布情况,观察了稀土元素Ce不同添加量对金合金铸态组织及其硬度的影响.研究发现:在添加Ce的金合金中,Ce部分固溶,部分作为异质点Ce-Si化合物存在,基本没有Ce的偏聚;添加0.075?金合金铸态组织就可以达到较好的晶粒细化效果,分析其作用机理是添加Ce的金合金以高熔点的Ce-Si化合物和氧化物作为异质点,起到异质晶核的作用而细化组织;在低于Ce的金合金固溶度时,铸态合金的硬度随Ce含量增加而升高,过量Ce对金合金的铸态硬度影响不大;利用时效处理,能显著地提高金合金的硬度,Ce主要强化机制在于固溶强化.     

Effect of Rare Earth on Microstructure of γ-TiAl Intermetallics

The rare earth (RE) elements (Ce, La) were added to binary Ti-47% Al alloys (atomic fraction) by Induction Skull Melting. The element Ce of 1.0 atomic percent was added individually, and La of 0.2 atomic percent was added individually. This article studied the influences of rare earth metal (Ce, La) on microstructure of as-cast TiA1 based alloy by XRD, SEM, EMPA and TEM measurement methodology. The results show that most of rare earth-rich phases (AlCe, Al-La) are uniformly distributed in grain boundary in the shape of discontinuous network, and some particles of rare earthrich phases within the grains are mainly ellipsoids. In addition, rare earth element can obviously refine the grain size and the lamellar thickness of as-cast TiAl based alloy samples. The grain size of Ti-47Al-1.0Ce-0.2La alloy reaches about 30～80μm, and the lameUar thickness of its γ phase and α2 phase are less than 200 and 20nm, respectively.     

Electrochemical performance of Gd-Co-Mn alloys

The Gd-Co-Mn alloys with compositions of Gd33.3Co66.7,Gd33.3Mn66.7,Gd22.2Co74.8Mn3 and Gd25Co70Mn5 were prepared and examined by X-ray diffractometer.The electrochemical properties of these alloys such as discharge capacity,cycling performance and high rate dischargeability were investigated by battery testing instruments in alkaline electrolyte.The discharge capacity of Gd22.2Co74.8Mn3 was the highest among these alloys at the same discharge current density,and the maximum value was 376.7 mAh/g discharged at 150 mA/g.The discharge capacities of the alloys Gd33.3Co66.7 and Gd33.3Mn66.7 reached their maxima(about 225 and 325 mAh/g)at discharge current density of 150 mA/g.A comparison of the electrochemical performance of the Gd-Co-Mn alloys revealed that the alloy Gd22.2Co74.8Mn3 possessed better electrochemical performance and had better discharge capacity,cycle stability,while the alloy Gd25Co70Mn5 had a better high rate discharge ability.In general,the electrochemical performance of ternary alloys was better than binary alloys in this case.