Effects of rapid quenching on microstructures and electrochemical properties of La0.7Mg0.3Ni2.55Co0.45Bx（x=O-0.2） hydrogen storage alloy

In order to improve the electrochemical performances of La-Mg-Ni based electrode alloys with PuNi3-type structure, a trace of boron was added in La0.7Mg0.3Ni2.55Co0.45 alloy. The La0.7Mg0.3Ni2.55Co0.45Bx（a=0, 0.05, 0.1, 0.15 and 0.2） alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were investigated. The effects of rapid quenching on the microstructures and electrochemical performances of the above alloys were investigated. The results show that the as-cast and quenched alloys are composed of （La, Mg）Ni3 phase, LaNi5 phase and LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloys containing boron, and the Ni2B phase in the B-contained alloys nearly disappears after rapid quenching. Rapid quenching increases the amount of the LaNi2 phase in the B-free alloy, but it decreases the amount of the LaNi2 phase in the boron-containing alloys. The effects of rapid quenching on the capacities of the boron-containing and boron-free alloys are different. The capacity of the B-free alloy monotonously decreases with increasing quenching rate, whereas the capacities of the B-contained alloys have a maximum value with the change of the quenching rate. The rapid quenching can improve the stability of La-Mg-Ni based electrode alloy but lowers the discharge plateau voltage and decreases the plateau length. The effect of rapid quenching on the activation capabilities of the alloys was complicated.     

The electrochemical hydrogen storage performances of Si-added La–Mg–Ni–Co-based A_2B_7-type electrode alloys

In order to improve the electrochemical cycle stability of the RE–Mg–Ni-based A2B7-type electrode alloys, a small amount of Si has been added into the alloys.The casting and annealing technologies were adopted to fabricate the La0.8Mg0.2Ni3.3Co0.2Six(x = 0–0.2) electrode alloys. The impacts of the addition of Si and annealing treatment on the structures and electrochemical performances of the alloys were investigated systematically. The results obtained by XRD and SEM show that all the as-cast and annealed alloys are of a multiphase structure, involving two main phases(La, Mg)2Ni7and La Ni5 as well as a residual phase La Ni3. Both adding Si and the annealing treatment lead to an evident change in the phase abundance and cell parameters of(La, Mg)2Ni7and La Ni5 major phases of the alloy without altering its main phase component. Moreover, the annealing treatment has the composition of the alloy distributed more homogeneously overall and simultaneously causes the grain of the alloy to be coarsened obviously. The electrochemical measurements indicate that adding Si and the annealing treatment give a significant rise to the influence on the electrochemical performances of the alloys. In brief, the cycle stability of the as-cast and annealed alloys evidently increases with the rising of Si content, while their discharge capacities obviously decrease under the same circumstances. Furthermore, the electrochemical kineticproperties of the electrode alloys, including the high rate discharge ability, the limiting current density(IL), hydrogen diffusion coefficient(D), and the charge-transfer resistance, first augment and then decline with the rising of Si content. Similarly, it is found that the above-mentioned electrochemical properties first mount up and then go down with the rising annealing temperature.     

Electrochemical Performance of Nanocrystalline and Amorphous Mg–Nd–Ni–Cu-Based Mg_2Ni-type Alloy Electrodes Used in Ni-MH Batteries

Nanocrystalline and amorphous Mg2Ni-type(Mg24Ni10Cu2)100–xNdx(x = 0, 5, 10, 15, 20) alloys were prepared by melt-spinning technology. The structures of as-cast and spun alloys were characterised by X-ray diffraction,scanning electron microscopy and transmission electron microscopy. Electrochemical performance of the alloy electrodes was measured using an automatic galvanostatic system. The electrochemical impedance spectra and Tafel polarisation curves of the alloy electrodes were plotted using an electrochemical work station. The hydrogen diffusion coefficients were calculated using the potential step method. Results indicate that all the as-cast alloys present a multiphase structure with Mg2 Ni type as the major phase with Mg6 Ni, Nd5Mg41 and Nd Ni as secondary phases. The secondary phases increased with the increasing Nd content. The as-spun Nd-free alloy exhibited nanocrystalline structure, whereas the as-spun Nd-doped alloys exhibited nanocrystalline and amorphous structures. These results suggest that adding Nd facilitates glass formation of Mg2Ni-type alloys. Melt spinning and Nd addition improved alloy electrochemical performance, which includes discharge potential characteristics, discharge capacity, electrochemical cycle stability and high-rate discharge ability.     

Influence of impurities on damping properties of ZK60 magnesium alloy

The influence of impurities on damping capacities of ZK60 magnesium alloys in the as-cast, as-extruded and T4-treated states was investigated by dynamically mechanical analyzer at room temperature. Granato and Lucke dislocation pinning model was employed to explain damping properties of the alloys. It is found that reducing impurity content can decrease the amount of second-phase particles, increase grain size and improve damping capacity of the as-cast alloy slightly. The as-extruded alloy with lower impurity content is found to possess obviously higher damping capacity in the relatively high strain region than that with higher impurity concentration, which appears to originate mainly from different dislocation characteristics. The variation tendency of damping property with change of impurity content after solution-treatment is also similar to that in the as-extruded and as-cast states. Meanwhile, the purification of the alloy results in an evident improvement in tensile yield strength in the as-extruded state.     

Influence of rapid quenching on hydrogen storage characteristics of nanocrystalline Mg2Ni-type alloys

Nanocrystalline Mg2Ni-type alloys with nominal compositions of Mg20Ni10–xCux(x=0,1,2,3,4,mass fraction,%) were synthesized by rapid quenching technique.The microstructures of the as-cast and quenched alloys were characterized by XRD,SEM and HRTEM.The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system.The hydriding and dehydriding kinetics of the alloys were measured using an automatically controlled Sieverts apparatus.The results show that all the as-quenched alloys hold the typical nanocrystalline structure and the rapid quenching does not change the major phase Mg2Ni.The rapid quenching significantly improves the electrochemical hydrogen storage capacity of the alloys,whereas it slightly impairs the cycling stability of the alloys.Additionally,the hydrogen absorption and desorption capacities of the alloys significantly increase with rising quenching rate.     

Enhanced Electrochemical Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Mg20Ni10-xCox (x=0-4) Alloys by Melt Spinning

In order to improve the electrochemical hydrogen storage performances of the Mg2Ni-type alloys, Ni in the alloy was partially substituted by element Co. The nanocrystalline and amorphous Mg20Ni10-xCox (x=0, 1, 2, 3, 4) alloys were prepared by melt-spinning technology. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. The electrochemical hydrogen storage characteristics of the alloys were measured. The results show that the substitution of Co for Ni leads to the formation of secondary phase MgCo2 without altering the major phase of Mg2Ni. No amorphous phase is detected in the as-spun alloy (x=0), whereas the as-spun alloy (x=4) holds a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni significantly increases the glass forming ability of the Mg2Ni-type alloy. The substitution of Co for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, including the discharge capacity and the cycle stability, for which the increased glass forming ability by Co substitution is mainly responsible     

Effects of Cu addition on microstructure and mechanical properties of as-cast Mg-6Zn magnesium alloy

The application of Mg-Zn binary alloys is restricted due to their developed dendritic microstructure and poor mechanical properties. In this study, an alloying method was used to improve the mechanical properties of Mg-Zn alloy. The Mg-6Zn magnesium alloys microalloyed with varying Cu content(0, 0.8, 1.5, 2.0 and 2.5wt.%) were fabricated by permanent mould casting, and the effects of Cu content on the microstructure and mechanical properties of as-cast Mg-6Zn alloys were studied using OM, SEM, XRD and tensile tests at room temperature. The obtained results show that the addition of Cu not only can refine the grains effectively, but also can modify the eutectic morphology and improve the mechanical properties of the alloys. The main phases of the studied alloys include α-Mg, MgZn_2, Mg_2Cu and CuMgZn. When the content of Cu exceeds 0.8wt.%, Mg_2Cu phase appears. Meanwhile, the eutectic morphology is modified into dendritic shape or lamellar structure, which has an adverse effect on the tensile properties. Furthermore, among the investigated alloys, the alloy containing 0.8% Cu shows an optimalultimate tensile strength of 196 MPa, while the alloy with 1.5wt.% Cu obtains an excellent elongation of 7.22%. The experimental alloys under different Cu contents show distinguishing fracture behaviors: the fracture of the alloy with 0.8wt.% Cu reveals a mixed mode of inter-granular and quasi-cleavage, while in other investigated alloys, the fracture behaviors are dominated by cleavage fracture.     

Effects of Heat Treatment and Thermal Cycling on Martensitic Transformation Behavior of Ni59Al11Mn30 High Temperature Shape Memory Alloy

A reversible martensitic transformation (MT) takes place during cooling and heating in the solution quenched and the solution quenched plus aged Ni59Al11Mn30 alloy. The MT temperature increases with increasing solution temperature. The excellent MT characteristics can be obtained from a process of 1000℃ solution quenched plus 400℃ aged. Follow this process, the MT start temperature (Ms) and the reverse MT finish temperature (Af) are 469℃ and 548℃,respectively. The martensitic stabilization effect in the solution quenched and aged Ni59Al11Mn30 alloy is observed as an increase in the Af temperature of the first reverse MT during thermal cycles. This stabilization effect vanishes from the second thermal cycle. Thermal cycling can enhance the stability of the reversible MT. The microstructure of the quenched Ni59Al11Mn30 alloy consists of martensite (M) and gamma phase. The volume fraction of gamma phase is about 40%. The substructure of M and gamma phase is twins and dislocations, respectively. The hardness of M is higher than that of gamma phase. After aging treatment the basic phases of alloy do not change, but the hardness of the phases increases.     

Influence of impurities on microstructure and mechanical properties of ZK60 magnesium alloy

The influence of impurity content on the microstructure and mechanical properties of ZK60 magnesium alloys was investigated by optical microscopy, scanning electron microscopy and tensile test. ZK60 alloys were prepared by changing holding time of alloy melt during semi-continuous casting in order to control the content of impurity elements. The alloy with lower purity content is found to have less second precipitates and larger grain size in the as-cast state. However, in the as-extruded state, reducing impurities brings about a decrease in grain size and an increase in yield strength from 244 MPa to 268 MPa, while the elongations in the as-extruded alloys with different contents of impurities are almost the same. After T5 treatment, impurity content is found to have more obvious effect on the yield strength of ZK60 alloy. The yield strength of ZK60-45 alloys with low impurity content is increased up to 295 MPa after T5 treatment.     

Changes of microstructure of different quench sensitivity 7,000 aluminum alloy after end quenching

The quench sensitivity and their influential factors of 7,021, 7,085, and 7,050 alloys were investigated by the end quenching test method and the measurement of electrical conductivity, hardness, and microstructure after aging. The results indicate that 7,050 alloy has the largest changes with hardness decreasing from HV 199 to HV 167,and electrical conductivity increases from 16.6 to18.2 MS m-1when the distance from quenched end increases from 2 to 100 mm. Alloys 7,085 and 7,021 have relatively smaller changes. According to the relationship between the hardness and electrical conductivity of a supersaturated solid solution, 7,050 alloy has higher quench sensitivity than 7,085 and 7,021 alloys. The microstructure of 7,050 alloy with higher major alloy element(Zn + Mg + Cu) addition and Cu element addition is mostly affected by the changes of distance from quenched end. In 7,050 alloy, the size of intragranular precipitates is from about 10–200 nm, and the(sub) grain boundary precipitates are about 20–300 nm. Alloy 7,085 with lower Cu content is moderately affected, while 7,021 is least affected. It is found that with the increase of distance from quenched end, quenched-induced precipitate preferentially nucleates and grows in the(sub) grain boundary and then on the pre-existing Al3 Zr particles.     

La0.7Mg0.3Ni2.55-xCo0.45Alx(x=0～0.4)贮氢合金的循环稳定性

为了提高La-Mg-Ni系贮氢合金的循环稳定性,以Al部分替代Ni,采铸造及快淬工艺制备了La0.7Mg0.3Ni2.55-xCo0.45Alx(x=0,0.1,0.2,0.3,0.4)电极合金,研究了Al替代量及快淬工艺对合金微观结构及电化学循环稳定性的影响。X射线衍射分析结果表明:铸态及快淬态合金具有多相结构,包括(La,Mg)Ni3相、LaNi5相和一定量的LaNi2相;Al替代使铸态合金中LaNi2相的量显著增加,但对快淬态合金中LaNi2相的相丰度影响不显著。电化学测试结果表明:随Al替代量的增加,合金的循环寿命大幅度提高;快淬处理可以提高合金的循环寿命,但随Al替代量的增加,淬速对循环寿命的影响减小。     

Influences of the substitution of Fe for Ni on structures and electrochemical performances of the as-cast and quenched La0.7Mg0.3Co0.45Ni2.55−xFex (x = 0–0.4) electrode alloys

In order to improve the cycle stability of the La–Mg–Ni system PuNi₃-type hydrogen storage electrode alloys, Ni in the alloy was partially substituted by Fe. The La_0.7Mg_0.3Co_0.45Ni_2.55−xFe_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the substitution of Fe for Ni on the structures and electrochemical performances of the as-cast and quenched alloys were investigated in detail. The results of the electrochemical measurement indicate that the substitution of Fe for Ni obviously decreases the discharge capacity, high rate discharge capability (HRD) and discharge potential of the as-cast and quenched alloys, but it significantly improves their cycle stabilities, and its positive impact on the cycle life of as-quenched alloy is much more significant than on that of the as-cast one. The microstructure of the alloys analyzed by XRD, SEM and TEM show that the as-cast and quenched alloys have a multiphase structure which is composed of two major phases (La, Mg)Ni₃ and LaNi₅ as well as a residual phase LaNi₂. The substitution of Fe for Ni helps the formation of a like amorphous structure in the as-quenched alloy. With the increase of Fe content, the grain sizes of the as-quenched alloys significantly reduce, and the lattice constants and cell volumes of the alloys obviously increase.     

Investigation on Gaseous and Electrochemical Hydrogen Storage Kinetics of As-Quenched Nanocrystalline Mg2Ni-type Alloys

为了改善Mg2Ni型合金气态及电化学贮氢动力学性能,用Cu部分替代合金中的Ni,用快淬技术制备Mg2Ni1-xCux(x=0,0.1,0.2,0.3,0.4)合金,用XRD、SEM、HRTEM分析铸态及快淬态合金的微观结构;用自动控制的Sieverts设备测试合金的气态贮氢动力学性能,用程控电池测试仪测试合金的电化学贮氢动力学.结果表明,所有快淬态合金均具有纳米晶结构,无非晶相形成.Cu替代Ni不改变合金的主相Mg2Ni,但使合金的晶粒显著细化.快淬处理及Cu替代均显著地提高合金的气态及电化学贮氢动力学性能.当淬速从0m/s(铸态被定义为淬速0 m/s)增加到30 m/s时,Mg2Ni0.8Cu0.3合金在5 min内的吸氢饱和率从57.2％增加到92.87％,20 min的放氢率从21.6％增加到49.6％,高倍率放电能力(HRD)从40.6％增加到73.1％,氢扩散系数(D)从1.02×10-11 cm2/s增加到4.08×10 -11 cm2/s,极限电流密度(IL)从113.0 mA/g增加到715.3 mA/g.     

Fe替代Ni对铸态及快淬态La0.7Mg0.3Co0.45Ni2.55-xFex (x = 0-0.4)电极合金循环稳定性的影响

用铸造及快淬工艺制备了La0.7Mg0.3Co0.45Ni2.55-xFex(x=0,0.2,0.3,0.4)电极合金,研究了Fe替代Ni对合金循环稳定性及微观结构的影响。结果表明,Fe替代Ni显著地改善合金的循环稳定性,且Fe替代Ni对快淬态合金的循环稳定性具有更加显著的作用。试验合金具有多相结构,包括2个主相(La,Mg)Ni3和LaNi5以及1个残余相LaNi2。Fe替代Ni促进快淬态合金形成类非晶结构,随Fe含量的增加,快淬态合金的晶粒显著细化,合金的晶格常数及晶胞体积显著增大。     

快淬纳米晶/非晶Mg2-xLaxNi (x=0~0.6)合金的电化学贮氢性能

用铸造及快淬工艺制备Mg2Ni型Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金。用XRD、SEM、HRTEM分析铸态及快淬态合金的微观结构。结果发现,在快淬无La合金中没有出现非晶相,但快淬含La合金显示了以非晶相为主的结构。用DSC研究快淬合金的热稳定性,表明La的含量及快淬对非晶相的晶化温度影响很小。电化学测试结果表明,铸态合金的放电容量随La含量的增加而增加,快淬态合金的放电容量随La含量的变化有极大值。La替代Mg显著地提高了铸态及快淬态合金的循环稳定性。     

Fe替代Co对AB5型贮氢合金循环稳定性的影响

用铸造及快淬的方法制备了稀土基AB5型Mm（NiMnSiAl）4．3Co0.6-xFex（x=0，0．1，0．2，0．3，0．4，0．5，0．6）贮氢合金，用XRD。TEM及SEM观测了铸态及快淬态的微观结构，测试了合金在铸态及快淬态下的电化学循环稳定性。研究了Fe替代Co对铸态及快淬态贮氢合金微观结构及循环稳定性的影响。研究结果表明，Fe替代Co对铸态及快淬态合金的相结构没有明显影响，但对合金的循环稳定性产生显著影响。Fe替代Co能不同程度地改善铸态及快淬态合金的循环稳定性，但对快淬态合金循环寿命的改善更加显著，导致这一结果的主要原因是Fe替代Co使快淬态合金的微观组织显著细化。     

硼对稀土系AB5型贮氢合金微观结构及电化学性能的影响

测试分析了稀土系AB5型贮氢合金MmNi3.8Co0.4Mn0.6Al0.2Bx(x=0, 0.1, 0.2, 0.3, 0.4)的微观结构及电化学性能, 研究了硼含量x对贮氢合金电化学性能及微观结构的影响.结果表明, 铸态贮氢合金具有双相组织, 主相为CaCu5型相, 还有少量CeCo4B第二相, 第二相的相丰度随x的增加而增大.对合金进行了不同淬速的快淬处理, 合金中第二相的量随淬速的增加而减少.硼的加入使合金的电化学容量下降, 但活化性能及循环寿命明显提高.特别是对于快淬态合金, 硼对因促进非晶的形成而显著提高循环寿命.     

Cycle stabilities of the La0.7Mg0.3Ni2.55−xCo0.45Mx (M = Fe, Mn, Al; x = 0, 0.1) electrode alloys prepared by casting and rapid quenching

In order to improve the cycle stability of La–Mg–Ni system (PuNi₃-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe, Mn and Al, and the electrode alloys La_0.7Mg_0.3Ni_2.55−xCo_0.45M_x (M = Fe, Mn, Al; x = 0, 0.1) were prepared by casting and rapid quenching. The effects of the substitution of Fe, Mn and Al for Ni and rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Mn obviously raises the amount of the LaNi₂ phase. The substitution of Al and Fe leads to a significant refinement of the as-quenched alloy's grains. The substitution of Al strongly restrains the formation of an amorphous in the as-quenched alloy, but the substitution of Fe is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Mn and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive influence of the substitution elements on the cycle stabilities of the as-cast alloys is in proper order Al > Fe > Mn, and for as-quenched alloys, the order is Fe > Al > Mn. Rapid quenching engenders an inappreciable influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.     

Effects of rapid quenching on structure and electrochemical characteristics of La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx （x=0-0.4） electrode alloys

The La-Mg-Ni system PuNi3-type La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx (x=0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the rapid quenching on the structure and electrochemical characteristics of the alloys were studied. The results obtained by XRD, SEM and TEM indicate that the as-cast and quenched alloys mainly consist of two major phases, (La,Mg)Ni3 and LaNi5, as well as a residual phase LaNi. The rapid quenching does not exert an obvious influence on the phase composition of the alloys, but it leads to an increase of the LaNi5 phase and a decrease of the (La, Mg)Ni3 phase. The as-quenched alloys have a nano-crystalline structure, and the grain sizes of the alloys are in the range of 20-30 nm. The results by the electrochemical measurements indicate that both the discharge capacity and the high rate discharge(HRD) ability of the alloy first increase and then decrease with the variety of quenching rate and obtain the maximum values at the special quenching rate which is changeable with the variety of Mn content. The rapid quenching significantly improves the cycle stabilities of the alloys, but it slightly impairs the activation capabilities of the alloys.     

快淬La—Mg—Ni系贮氢合金的电化学性能及微观结构

采用铸造及快淬工艺制备了La—Mg-Ni系（PuNi3型）贮氢合金La0.7Mg0.3Ni2.55-Co0.45Cux（x=0～0．4），分析测试了铸态及快淬态合金的电化学性能与微观结构，研究了Cu替代Ni及快淬工艺对合金微观结构及电化学性能的影响。结果表明：铸态及快淬态合金具有多相结构，包括（La，Mg）Ni3相和LaNi5相和一定量的LaNi2相。快淬处理对合金的相组成没有影响，但使合会的衍射峰趋于均匀一致。Cu替代Ni使合金的电化学容量下降，但使合金的循环稳定性及放电电压特性得到改善。快淬可提高合金的循环稳定性，但使合金的容量下降。