Effect of melt spinning on gaseous hydrogen storage characteristics of nanocrystalline and amorphous Nd-added Mg_2Ni-type alloys

Nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of(Mg_(24)Ni_(10)Cu_2)_(100-x)Nd_x(x=0, 5, 10, 15, 20) were prepared by melt spinning technology and their structures as well as gaseous hydrogen storage characteristics were investigated. The XRD, TEM and SEM linked with EDS detections reveal that the as-spun Nd-free alloy holds an entire nanocrystalline structure but a nanocrystalline and amorphous structure for the as-spun Nd-added alloy, implying that the addition of Nd facilitates the glass forming in the Mg_2Ni-type alloy. Furthermore, the degree of amorphization of the as-spun Nd-added alloy and thermal stability of the amorphous structure clearly increase with the spinning rate rising. The melt spinning ameliorates the hydriding and dehydriding kinetics of the alloys dramatically. Specially, the rising of the spinning rate from 0(the as-cast was defined as the spinning rate of 0 m/s) to 40 m/s brings on the hydrogen absorption saturation ratio(R_5~a)(a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increasing from 36.9% to 91.5% and the hydrogen desorption ratio(R_(1 0)~d)(a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) rising from 16.4% to 47.7% for the(x=10) alloy, respectively.     

硼及快淬工艺对La-Mg-Ni系贮氢合金的微观结构及电化学容量的影响

用铸造及快淬工艺制备了La-Mg-Ni系(PuNi3型)贮氢合金La2Mg(Ni0.85Co0.15)9Bx(x=0,0.05,0.1,0.15,0.2),分析测试了铸态及快淬态合金的微观结构与电化学容量,研究了硼及快淬工艺对合金微观结构及电化学容量的影响.结果表明,铸态合金具有多相结构,包括(La,Mg)Ni3相(PuNi3型)、LaNi5相,一定量的LaNi2相和微量的Ni2B相,经快淬处理后Ni2B相消失.硼的加入对铸态及快淬态合金的容量产生不同的影响,铸态合金的容量随硼含量的增加而单调下降,而快淬态合金的容量随硼含量的增加有一极大值.快淬处理对含硼及不含硼合金的容量也有不同的影响,随淬速的增加,不含硼合金的容量单调下降,而含硼合金的容量可以获得一个极大值.     

Hydriding and dehydriding kinetics of nanocrystalline and amorphous MgzNi1-xMnx （x=0-0.4） alloys prepared by melt spinning

A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys.The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xMnx(x=0,0.1,0.2,0.3,0.4) alloys were synthesized by the melt-spinning technique.The structures of the as-cast and spun alloys were studied by X-ray diffractometry(XRD),scanning electron microscopy(SEM) and high resolution transmission electron microscopy(HRTEM).The hydrogen absorption and desorption kinetics of the alloys ...     

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg_(12)-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg_(12)-type LaMg_(11)Ni + x wt% Ni(x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter(DSC) connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability(HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.     

Formation and Mechanical Properties of Zr-Nb-Cu-Ni-Al-Lu Bulk Glassy Alloys with Superior Glass-Forming Ability

Glass-forming ability(GFA) and mechanical properties of(Zr_(0.58)Nb_(0.03)Cu_(0.16)Ni_(0.13)Al_(0.10))_(100-x)Lu_x(x= 0-3 at%) alloys have been investigated.The GFA of Zr_(58)Nb_3Cu_(16)Ni_(13)Al_(10) alloy is dramatically enhanced by adding Lu.The(Zr_(0.58)Nb_(0.03)Cu_(0.16)Ni_(0.13)Al_(0.10))_(98)Lu_2 alloy possesses the highest GFA in the studied Zr-Nb-Cu-Ni-Al-Lu alloys,with its critical diameter for glass formation reaching 20 mm by copper-mould casting method,while that of the Lu-free Zr_(58)Nb_3Cu_(16)Ni_(13)Al_(10) alloy is 7 mm.The critical diameters of(Zr_(0.58)Nb_(0.03)Cu_(0.16)Ni_(0.13)Al_(0.10))_(100-x)Lu_x(x =1 at%and 3 at%) alloys are 15 mm and 12 mm,respectively.The Lu addition to Zr_(58)Nb_3Cu_(16)Ni_(13)Al_(10) alloy induces the change of initial crystallization phases from face-centred-cubic Zr_2Ni and tetragonal Zr_2Ni phases for the Lu-free Zr_(58)Nb_3Cu_(16)Ni_(13)Al_(10) alloy to an icosahedral quasi-crystalline phase for the Lu-doped alloys,which may be the origin for the enhanced GFA of the Lu-doped alloys.The compressive fracture strength and plastic strain of the bulk glassy(Zr_(0.58)Nb_(0.03)Cu_(0.16)Ni_(0.13)Al_(0.10))_(98)Lu_2 alloy are1 610 MPa and 1.5%,respectively.     

Tb对Ni50Mn29Ga21合金的组织和磁感生应变的影响

运用X光衍射的方法研究了稀土元素Tb对形状记忆合金Ni50Mn29Ga21金相组织的影响.结果表明,稀土元素Tb的加入可以明显地减小合金的晶粒尺寸,提高马氏体在合金中的含量,但是也使得合金的磁感生应变在经历一段上升后发生回落.     

LaNi_（3.8）Co_（1.1）Mn_（0.1）/TiMn_（1.5）贮氢合金的结构和性能

为了探索一种新的掺杂方式对AB5型贮氢合金贮氢性能的影响,采用熔炼掺杂方法制备La-Ni3.8Co1.1Mn0.1/TiMn1.5（TiMn1.5质量分数为4%、8%）贮氢合金,利用PCTPro-2000气体吸附测量仪研究了合金的气态储氢性能。XRD和SEM分析显示,熔炼掺杂后合金主相为LaNi5相,出现少量（NiCo）3Ti相。P-C-T测试结果表明,（NiCo）3Ti相的出现对合金气态贮氢性能有较大影响,熔炼掺杂后合金吸放氢平台压和滞后效应降低,贮氢容量减少。掺杂TiMn1.5使得合金的氢化物的生成焓由原始合金的-27.35kJ/mol降至-29.14kJ/mol（掺杂质量分数8%的TiMn1.5）,较高温度有利于合金中氢的释放,同时掺杂形成的（NiCo）3Ti相改善了合金吸/放氢动力学性能。     

Electrochemical behavior of Mg-Al-Pb alloy in 3.5% NaCl solution

An investigation on electrochemical behavior of Mg-5%Pb alloy, Mg-6%Al alloy and Mg-6%Al-5%Pb alloy(mass fraction) in 3.5% Na Cl(mass fraction) solution was conducted using electrochemical measurements and corroded morphology observation, in which solid solution and the as-aged state of each alloy were compared to discuss the influence mechanism of lead and aluminium on the electrochemical properties of alloys. The X-ray diffraction(XRD) analysis was performed to make microstructure characterization. The electrochemical results indicate that the corrosion of Mg-5%Pb alloy is predominated by homogeneous pitting and dissolution of PbCl_2 film due to Cl ions attack, while corrosion crevice propagates along grain boundaries in solid solution of Mg-6%Al alloy and the micro galvanic corrosion also plays vital role in Mg_(17)Al_(12) phase containing experimental alloys. The co-existence of lead and aluminium in magnesium alloy increases corrosion current density and electrochemical activity as well. The comparison between solid solution and the as-aged state demonstrates that Mg_2 Pb and Mg_(17)Al_(12) somewhat increase corrosion resistance but lighten anodic polarization by facilitating corrosion product flaking off.     

快凝合金La(NiMn)5.6的贮氢性能

借助X-ray及吸放氢性能测试装置研究了非化学计量比快凝合金La(NiMn)5.6的结构和贮氢性能以及A端、B端元素替代对合金的影响,测试了不同温度下合金的PCT曲线.结果表明,快速凝固(35 m/s)条件下合金La(NiMn)5.6均可获得过饱和CaCu5型单相组织.A端以Ce取代La,使平台压力增大,最大吸氢量减小,但滞后降低;B端以Sn取代Ni,改善了合金的活化特性,并使平台降低,吸放氢滞后减小.     

Influence of substituting Ni with Co on hydriding and dehydriding kinetics of melt spun nanocrystalline and amorphous Mg2Ni-type alloys

In order to improve the hydriding and dehydriding kinetics of the Mg₂Ni-type alloys, Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1−x Co _x (x=0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg₂Ni but results in the formation of secondary phase MgCo₂. No amorphous phase is detected in the as-spun Co-free alloy, but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However, it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4, the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy, and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).     

Effects of Si and Ce on the microstructure and hydrogen storage property of Ti_(26.5)Cr_(20)V_(45)Fe_(8.5)Ce_(0.5) alloy

In this paper, the effects of Si and Ce on the microstructure and hydrogen storage property of Ti26.5 Cr20V45Fe8.5Ce0.5 alloy were studied, respectively. First of all, effects of Si on the microstructure and hydrogen storage properties of Ti26.5Cr20(V45Fe8.5)1?xSixCe0.5 (x = 0, 0.5, 1.0, 1.5 and 2.0 at%) alloys were studied by X-ray diffraction, scanning electron microscopy and P-C isotherm measurements. As the Si addition increases, the hydrogen absorption capacities of alloys decrease but the equilibrium pressure increases, due to the formation of Laves phase. Secondly, the effect of Ce on Ti26.5Cr20 (V45Fe8.5)0.98Si2 alloy was studied. It was found that Ce addition is an effective way to eliminate the effect of Si on the hydrogen storage properties of the alloy.     

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg<Subscript>12</Subscript>-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg₁₂-type LaMg₁₁Ni + x wt% Ni (x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter (DSC) connected with a H₂ detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability (HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.     

熔炼掺杂对AB5型贮氢合金的结构和性能影响

为了探索一种新的掺杂方式对AB5型贮氢合金性能的影响,采用熔炼掺杂方法,研究了掺杂适量TiMn1.5合金(掺杂量为4％、8％的TiMn1.5)对成分为La0.7Ni2.65Co0.75Mn0.1的AB5型贮氢合金的结构及性能影响.XRD测试结果证实:掺杂后合金的主相仍为LaNi5相,生成了少量(NiCo)3 Ti相.(...     

Corrosion Behavior of Mg65Cu25-xZnxGd10 (x=0, 5) Metallic Glass

The effect of substitutional element Zn on corrosion behavior of Mg65Cu25Gd10 glass was investigated. The amorphous structure of Mg65Cu25-xZnxGd10(x=0, 5) alloys were examined by X-ray diffractometry and differential scanning calorimetry (DSC). The dissolution rates of Mg65Cu25-xZnxGd10(x=0,5) metallic glasses in a 5 wt% NaCl solution with pH value of 7 were determined by a hydrogen evolution testing method. The corrosion behavior of these alloys was characterized using dipping tests with 5 wt% NaCl, in combination with electrochemical measurements and scanning electron microscopy (SEM). Results show that the anti-corrosion ability of Mg65Cu25Gd10 alloy is significantly improved due to the addition of Zn. Possible mechanism responsible for the improvement is discussed.     

Influences of melt spinning on electrochemical hydrogen storage performance of nanocrystalline and amorphous Mg2Ni-type alloys

In order to improve the electrochemical hydrogen storage performance of the Mg₂Ni-type electrode alloys, Mg in the alloy was partially substituted by La, and the nanocrystalline and amorphous Mg₂Ni-type Mg_20−x La _x Ni₁₀ (x=0, 2) alloys were synthesized by melt-spinning technique. The microstructures of the as-spun alloys were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical hydrogen storage properties of the experimental alloys were tested. The results show that no amorphous phase is detected in the as-spun Mg₂₀Ni₁₀ alloy, but the as-spun Mg₁₈La₂Ni₁₀ alloy holds a major amorphous phase. As La content increases from 0 to 2, the maximum discharge capacity of the as-spun (20 m/s) alloys rises from 96.5 to 387.1 mA·h/g, and the capacity retaining rate (S ₂₀) at the 20th cycle grows from 31.3% to 71.7%. Melt-spinning engenders an impactful effect on the electrochemical hydrogen storage performances of the alloys. With the increase in the spinning rate from 0 to 30 m/s, the maximum discharge capacity increases from 30.3 to 135.5 mA·h/g for the Mg₂₀Ni₁₀ alloy, and from 197.2 to 406.5 mA·h/g for the Mg₁₈La₂Ni₁₀ alloy. The capacity retaining rate (S ₂₀) of the Mg₂₀Ni₁₀ alloy at the 20th cycle slightly falls from 36.7% to 27.1%, but it markedly mounts up from 37.3% to 78.3% for the Mg₁₈La₂Ni₁₀ alloy.     

Influence of rare earth (Ce and La) addition on the performance of Al-3.0 wt%Mg alloy

The influences of rare earth elements (cerium and lanthanum) on the microstructure and phases of Al-3.0 wt%Mg alloys used for electromagnetic shielding wire were characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The mechanical properties and electrical resistivity were also investigated. The results indicated that a certain content of rare earth could improve the purification of the aluminum molten, enhance the strength, and reduce the electrical resistivity of Al-3.0 wt%Mg alloys. The strength reached the top value when RE content was 0.3 wt% while the alloy with 0.2 wt% RE addition had the smallest electrical resistivity. The elongation varied little when RE addition was no more than 0.2 wt%. But the excessive addition of rare earth would be harmful to the microstructure and properties of Al-3.0 wt%Mg alloys.     

A2B7型La0.75Mg0.25Ni3.5-xCrx(x=0～0.3)贮氢合金相结构及电化学性能研究

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCrx(x=0,0.05,0.1,0.2,0.3)四元贮氢合金,系统地研究了合金B端Cr元素对Ni部分替代对合金相结构及电化学性能的影响.X衍射(XRD)分析表明,La0.75Mg0.25Ni3.5合金是由La2Ni7相组成.随着Cr元素的加入,该类合金中出现LaNi5相及LaNi3相,且随着Cr含量的增加而增多.电化学测试表明,随Cr含量的增加,合金电极活化次数变化不大,最大放电容量逐步降低,合金的最大放电容量由x=0.05时的383.43 mAh/g下降到x=0.3时的348.40 mAh/g;而合金的高倍率放电性能呈现先增后减的趋势,当电流密度为900 mA/g时,合金的高倍率放电性能由83.66%(x=0)增加到92.57%(x=0.05)然后减小到83.9%(x=0.3);循环稳定性先增加后下降,当x=0.1时合金电极的循环寿命达到最大(S100=74.71%).     

Microstructure, cold rolling, heat treatment, and mechanical properties of Mg-Li alloys

The magnesium-lithium (Mg-Li) alloy exhibits two phase structures between 5.7wt% and 10.3wt% Li contents, consisting of the α (hcp) Mg-rich and the β (bcc) Li-rich phases, at room temperature. In the experiment, Mg-5Li-2Zn, Mg-9Li-2Zn, Mg-16Li-2Zn, Mg-22Li-2Zn, Mg-5Li-2Zn-2Ca, Mg-9Li-2Zn-2Ca, Mg-16Li-2Zn-2Ca, and Mg-22Li-2Zn-2Ca (wt%) were melted. During the melting process, the flux, which was composed of lithium chloride (LiCl) and lithium fluoride (LiF) in the proportion of 3:1 (mass ratio) and argon gas were used to protect the alloys from oxidation. The microstructure, mechanical properties, and cold-rolling workability of the wrought alloys were studied. The crystal grain of the alloys (adding Ga) is fine. The hardness of the studied alloys decreases with an increase in element Li. The density of the studied alloys is in the range of 1.187 to 1.617 g/cm3. The reduction of the Mg-16Li-2Zn and Mg-22Li-2Zn alloys can exceed 85% at room temperature. The Mg-9Li-2Zn-2Ca alloy was heat treated at 300°C for 8, 12, 16, and 24 h, respectively. The optimum heat treatment of the Mg-9Li-2Zn-2Ca alloy is 300°C×12h by metallographic observation and by studying the mechanical properties of the alloys.     

Effect of VFe addition on hydrogen storage behavior of TiMn1.5-based alloys

The hydrogen absorption and desorption behavior of TiMn1.25Cr0.25 alloys with VFe substitution for partial Mn was investigated at 273, 293 and 313 K. It is found that VFe substitution increases their hydrogen storage capacity, decreases the plateau pressure and the hysteresis factor of their pressure-composition-temperature (PCT) curves. After annealing treatment at 1223 K for 6 h, TiMn0.95Cr0.25(VFe)0.3 alloy exhibits a lower hydrogen desorption plateau pressure (0.27 MPa at 313 K) and a smaller hysteresis factor (0.13 at 313 K); the maximum and effective hydrogen storage capacities (mass fraction) are 2.03% and 1.12% respectively, which can satisfy the demand of hydrogen storage tanks for proton exchange membrane fuel cells (PEMFC).     

Co部分替代Ni对La_(0.4)Er_(0.4)Mg_(0.2)Ni_(3.3-x)Co_xAl_(0.2)(0.1≤x≤0.4)储氢合金结构和电化学性能的影响

为了改善储氢合金La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)的结构和综合电化学性能,采用Co部分替代Ni的方法,实验采用高频感应炉制备La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)储氢合金。通过X射线衍射技术和电化学测量方法研究储氢合金的晶体结构和电化学性能。XRD图谱显示样品储氢合金主要由LaNi5和La2Ni7相组成,电化学实验表明,随着Co含量的增高,储氢合金电极的最大放电容量和50次循环后的容量保持率S50基本呈现增加状态,放电容量从x=0.1时的225mA·h/g升高到x=0.4时的254.9mA·h/g,容量保持率S50从57.11%(x=0.1)增加到66.10%(x=0.4),但高倍率性能不断下降。通过交流阻抗(EIS)和线性扫描(LS)对Co替代Ni的合金动力学性能分析发现,Co替代Ni后合金的表面电荷转移能力先降低后升高。