Electron holography of Nd–Fe–B nanocomposite magnets

Magnetization distribution in Nd–Fe–B nanocomposite magnets was investigated by electron holography, using a new pole piece apparatus dedicated to observations of nanocrystalline ferromagnetic materials. The exchange coupling between the magnetically soft and hard grains of 20–30 nm was experimentally verified by this microscopic study with improved resolution.     

Effect of Nd content on the microstructure and coercivity of hot-deformed Nd–Fe–B permanent magnets

The microstructure of hot-deformed Nd–Fe–B permanent magnets with different Nd contents was investigated in order to correlate them with the hard magnetic properties. A thick distinct Nd-rich grain boundary (GB) layer was observed in a high Nd content sample by scanning electron microscopy and transmission electron microscopy. Three-dimensional atom probe results showed a significant increase in the Nd content in the GB as the overall Nd content in the alloy increased. We found a clear correlation between the Nd concentration in the GB layer and the coercivity. The mechanism of the coercivity increase is discussed based on the microstructure characterization and micromagnetic simulation results.     

Succession law of Nd–Fe–B alloys with different coercivities

In order to establish a succession law of every phase in sintered Nd–Fe–B magnets marked as 38/38H/38SH/38 UH, four alloys of Nd33-xDyxAl0.7Nb0.6Cu0.1B1.05 Fe bal.(at%) were investigated after smelting processing, sintering processing, high-temperature tempering processing, and highand low-temperature tempering processing. It is found that the four phases: the Nd2Fe14B matrix phase, Nd-rich phase,B-rich phase, and defect phase can be inherited by means of the subsequent processing. These phases might have the special constitution and appearance in the different states.Magnetic properties also have succession law. In every processing except smelting one, the values of remanence and maximum energy product hardly alter, but the value of coercive force increases gradually.     

Hot deformation behavior and microstructure evolution of a Mg–Gd–Nd–Y–Zn alloy

The hot deformation behavior of homogenized Mg–6.5Gd–1.3Nd–0.7Y–0.3Zn alloy was investigated during compression at temperatures of 250–400 ℃ and at strain rates ranging from 0.001 to 0.100 s~(-1). Microstructure analyses show that the flow behaviors are associated with the deformation mechanisms. At the lower temperatures(250–300 ℃), deformation twinning is triggered due to the difficult activation of dislocation cross-slip. Dynamic recrystallization(DRX) accompanied by dynamic precipitation occurs at the temperature of 350 ℃ and influences the softening behavior of the flow.DRX that develops extensively at original grain boundaries is the main softening mechanism at the high temperature of 400 ℃ and eventually brings a more homogeneous microstructure than that in other deformation conditions. The volume fraction of the DRXed grains increases with temperature increasing and decreases with strain rate increasing.     

Serrated flow and tensile properties of a Mg–Y–Nd alloy

Serrated flow in WE54 alloy during tensile deformation is reported. The observed static strain ageing effect and negative strain rate sensitivity suggest that the serrated flow is due to interactions between dislocations and solute atoms, known as dynamic strain ageing (DSA). The tensile properties are analysed in relation to the DSA effect.     

High-coercivity Nd–Fe–B thick films without heavy rare earth additions

The magnetic properties and microstructures of two Nd–Fe–B thick films with different Nd contents have been studied. The films were deposited in the amorphous state and were crystallized by post-deposition annealing. Both films show a strong 〈0 0 1〉 fibre texture out-of-plane. The film with the higher Nd content has a large room temperature coercivity of 2.7 T, while the one with the lower Nd content has a room temperature coercivity of only 0.7 T. The difference in coercivity may be explained by the fact that the film with the higher Nd content exhibits a continuous Nd-rich grain boundary phase, giving better isolation of the Nd₂Fe₁₄B grains with respect to magnetic exchange interactions. The extrusion of Nd-rich liquid to the top surface of the film with high Nd content during post-deposition annealing led to the formation of ripples in the Ta capping layer, indicating that the films are under compressive stress. This stress-induced flow of the Nd-rich material up through the film explains the excellent distribution of the Nd-rich grain boundary phase. Atom probe tomography has revealed the presence of Cu in the Nd-rich grain boundary phase, explaining the formation of the liquid phase at the relatively low temperature of 550 °C due to the eutectic reaction of Nd and Cu.     

Corrosion behaviors for peak-aged Mg–7Gd–5Y–1Nd–0.5Zr alloys with oxide films

The corrosion behaviors of T5 (225 °C, 6.5 h) and T6 (460 °C, 2 h + 225 °C, 12 h) peak-aged Mg–7Gd–5Y–1Nd–0.5Zr alloys with oxide films were investigated by optical microscope (OM), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The weight loss rates and electrochemical tests were also analyzed. The thicknesses of T5 and T6 oxide films are roughly 0.6 and 1.0 μm, respectively. The components of oxide films mainly consist of O, Mg, Y, Nd, and Gd, and the T6 oxide film results in surfaces with larger peaks than T5 oxide film. In addition, Y, Nd, and Gd peaks are all higher than those of Mg–7Gd–5Y–1Nd–0.5Zr alloys, but Mg peak is consistently far below than that of the alloys. The specimens could be arranged in decreasing order of corrosion rates and corrosion current densities: T6 oxide film < T5 oxide film < T6 without oxide film < T5 without oxide film. The oxide films are compact to increase the corrosion resistance for Mg–7Gd–5Y–1Nd–0.5Zr alloys, which will provide a guiding insight into the corrosion and protection of Mg–RE alloys in atmospheric environments.     

纳米晶Mg2-xTixNi0.8Cr0.2四元合金的气态储氢性能

纳米晶Mg2-xTixNi0.8Cr0.2(x=0.05,0.10,0.15,0.20)四元合金由纯Mg,Ti,Ni,Cr粉在773 K经4h烧结后机械球磨而成.该合金具有良好的活化性能和吸氢动力学性能.合金在393 K,4.0 MPa氢压条件下,2min内便可以完成总吸氢量的75%(质量分数)以上,Mg1.95Ti0.05Ni0.8C0.2最大吸氢量可达到3.35%.在493 K,0.1 MPa条件下可快速放氢,Mg1.80Ti0.20Ni0.8Cr0.2在18 min内便可完成放氢过程,总放氢量为2.17%.所有合金具有良好的低温吸氢性能,353 K时Mg1.85Ti0.15Ni0.8Cr0.2合金最大吸氢量可达到2.08%.XRD分析结果显示,Ti替代Mg后,合金中主要存在Mg2Ni与Ni两相,另外,还有微量的Mg与TiNi相,TiNi相弥散分布在合金中,对合金的吸放氢性能有一定的催化作用.     

Effects of Ni Content and Ball Milling Time on the Hydrogen Storage Thermodynamics and Kinetics Performances of La–Mg–Ni Ternary Alloys

The effects of Ni content and ball milling time on the hydrogen storage thermodynamics and kinetics performances of asmilled La_5Mg_(95-x)Ni_x(x = 5, 10, 15) ternary alloys have been investigated.The evolution of microstructure and phase of experimental alloys in the absorption/desorption process has been characterized by XRD, SEM and HRTEM.The hydrogen storage kinetics and thermodynamics performances and PCI curves have been tested using the Sievert apparatus.It is found that the rising of Ni content remarkably improves the hydrogen storage kinetic performance, but reduces hydrogen storage capacity.And with the increase in milling time, hydrogen desorption activation( E_a) value decreases firstly and then increases; the minimum value is 47.6 kJ/mol, and the corresponding milling time is 10 h for La_5Mg_(85)Ni_(10) alloy.As for the thermodynamics properties, the hydrogenation enthalpy(Δ H) and hydrogenation entropy(Δ S) both decrease firstly and then increase with the rising of Ni content and milling time.The composite La_5Mg_(85)Ni_(10)alloy milled for 10 h exhibits the best thermodynamics and kinetics performances, the lowest E_a of 47.6 kJ/mol, absorption of 5.4 wt.% within 5 min and desorption of 5.2 wt.% within 3 min at 360 ℃ and the lowest Δ H and Δ S of 72.1 kJ/mol and 123.2 J/mol/K.     

Gaseous and electrochemical hydrogen storage behaviors of nanocrystalline and amorphous Nd-added Mg_2Ni-type alloys

Melt spinning technology was used to prepare the Mg2Ni-type(Mg24Ni10Cu2)100-xNdx(x = 0, 5, 10, 15,20) alloys in order to obtain a nanocrystalline and amorphous structure.The effects of the spinning rate on the structures and gaseous and electrochemical hydrogen storage behaviors of the alloys were investigated.The analysis of X-ray diffraction(XRD), transmission electron microscope(TEM), and scanning electron microscope(SEM) linked with energy-dispersive spectroscopy(EDS)reveals that all the as-cast alloys hold a multiphase structure, involving the main phase Mg2 Ni and some secondary phases such as Mg6 Ni, Nd5Mg41, and Nd Ni.The as-spun Nd-free alloy displays an entire nanocrystalline structure,whereas the as-spun Nd-added alloys hold a nanocrystalline and amorphous structure, and the amorphization degree visibly increases with the spinning rate increasing.The melt spinning ameliorates the hydrogen storage performances of the alloys dramatically.When the spinning rate rises from 0(the as-cast was defined as the spinning rate of 0 m s-1) to 40 m s-1, the discharge capacity increases from 86.4 to 452.8 m Ah g-1, the S20(the capacity maintain rate at 20 th cycle) value increases from53.2 % to 89.7 %, the hydrogen absorption saturation ratio(Ra5, a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increases from36.9 % to 91.5 %, and the hydrogen desorption ratio(Rd10,a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) increases from16.4 % to 47.7 % for the(x = 10) alloy, respectively.     

Hydrogen storage behavior of nanocrystalline and amorphous La–Mg–Ni-based LaMg12-type alloys synthesized by mechanical milling

Nanocrystalline and amorphous LaMg₁₁Ni+x% Ni (x=100, 200, mass fraction) alloys were synthesized by mechanical milling. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. The gaseous hydrogen absorption and desorption properties were investigated by Sievert's apparatus and differential scanning calorimeter (DSC) connected with a H₂ detector. The results indicated that increasing Ni content significantly improves the gaseous and electrochemical hydrogen storage performances of the as-milled alloys. The gaseous hydrogen absorption capacities and absorption rates of the as-milled alloys have the maximum values with the variation of the milling time. But the hydrogen desorption kinetics of the alloys always increases with the extending of milling time. In addition, the electrochemical discharge capacity and high rate discharge (HRD) ability of the as-milled alloys both increase first and then decrease with milling time prolonging.     

Structure and Electrochemical Hydrogen Storage Properties of as-Milled Mg-Ce-Ni-Al-Based Alloys

At room temperature,crystalline Mg-based alloys,including Mg_2 Ni,MgNi,REMg_(12) and La_2 Mg_(17),have been proved with weak electrochemical hydrogen storage performances.For improving their electrochemical property,the Mg is partially substituted by Ce in Mg-Ni-based alloys and the surface modification treatment is performed by mechanical coating Ni.Mechanical milling is utilized to synthesize the amorphous and nanocrystalline Mg_(1-x)Ce_xNi_(0.9)Al_(0.1)(x=0,0.02,0.04,0.06,0.08)+50 wt%Ni hydrogen storage alloys.The effects made by Ce substitution and mechanical milling on the electrochemical hydrogen storage property and structure have been analyzed.It shows that the as-milled alloys electrochemically absorb and desorb hydrogen well at room temperature.The as-milled alloys,without any activation,can reach their maximal discharge capacities during first cycling.The maximal value of the 30-h-milled alloy depending on Ce content is 578.4 mAh/g,while that of the x=0.08 alloy always grows when prolonging milling duration.The maximal discharge capacity augments from337.4 to 521.2 mAh/g when milling duration grows from 5 to 30 h.The cycle stability grows with increasing Ce content and milling duration.Concretely,the S_(100) value augments from 55 to 82% for the alloy milled for 30 h with Ce content rising from 0 to 0.08 and from 66 to 82% when milling the x=0.08 alloy mechanically from 5 to 30 h.The alloys' electrochemical dynamics parameters were measured as well which have maximum values depending on Ce content and keep growing up with milling duration extending.     

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.     

纳米晶和非晶Mg20-xLaxNi10(x=0-6)贮氢合金的贮氢行为

用快淬技术制备了Mg2Ni型贮氢合金,合金的名义成分为Mg20-xLaxNi10 (x = 0, 2, 4, 6)。用XRD、SEM、HRTEM分析了合金的微观结构。发现不含La的快淬合金中没有非晶相,但含La快淬合金中显示以非晶相为主。当La含量x≤2时,铸态合金的主相为Mg2Ni相,但随着La含量的进一步增加,铸态合金的主相改变为(La,Mg)Ni3+LaMg3相。应用Sieverts设备研究了铸态及快淬态合金的吸放氢量及动力学,结果表明,x=2的合金吸放氢量及动力学随淬速的增加而增加,但对于x=6的合金,结果是相反的。电化学测试结果表明,x=2合金的放电容量随淬速的增加而增加,而对于x=6合金,结果也是相反的。快淬显著地提高了x=2, 6合金的循环稳定性     

苯溶液中球磨La2Mg16Ni合金的储氢性能

对苯溶液中球磨的La2Mg16Ni合金的储氢性能进行了研究。XRD和SEM分析表明：球磨后合金颗粒粒径减小，且有明显的非晶化趋势；由合金和有机苯溶剂在球磨过程中形成的EDA(electron donor-acceptor)体系极大地提高了合金的活化性能；球磨后的合金即使在低温下也具有良好的吸氢速率；延长球磨时间，可改善合金的吸氢性能。     

添加Nd、Zn、Ti的Mg2Ni基合金微观组织及氢化动力学

为了提高Mg2Ni基合金的储氢动力学性能,通过熔炼方法分别添加金属元素Nd,Zn和Ti来防止镁的氧化和蒸发,将Mg2Ni基合金在有覆盖剂保护的电阻炉中进行熔炼。借助XRD 和 SEM/EDS研究了铸态合金的相组成和微观组织。采用定容法在Sievert’s型PCT测试仪上测试了合金的氢化动力学性能。Nd、Zn和Ti的添加导致了微量相Mg6Ni和Ni3Ti的生成。Nd和Zn溶解在Mg2Ni基合金的α-Mg、Mg2Ni和MgNi2相中。添加Nd元素后,合金的首次吸氢量高于Mg2Ni的,达到2.86%（质量分数）。Mg2Ni基合金的吸氢动力学性能和活化性能均有所提高。在前3次吸放氢循环过程中,添加Zn和Ti的合金吸氢量和吸氢动力学性能均得到提高。采用Hirooka动力学模型分析了合金的氢化动力学性能及反应机制。     

Electrochemical and Hydrogen Absorption/Desorption Properties of Nanocrystalline Mg2Ni-type Alloys Prepared by Melt Spinning

从晶体结构、吸放氢性能和抗粉化性能的角度研究了La1-xYxNi5-yAly (x=0.6,0.7;y=0.1,0.2)金属氢化物合金用于高气压氢压缩机的可行性.XRD分析表明,合金都为CaCu5型六方结构,晶胞体积随着Y含量的增加而减小,随着Al含量的增加而变大.采用恒温体积法在20、30和40℃的实验条件下,对合金的吸放氢PCT曲线和吸氢动力学曲线进行了测定.结果表明,Y和Al能够有效地调节合金的吸放氢平台压,其中Y使合金的平台压升高,Al使合金的平台压降低,两种元素对LaNis基合金的其它储氢性能没有明显的负面影响.分析表明,这些合金能够以“合金对”的形式应用于双级金属氢化物压缩机中,将室温下的2 MPa的低压氢增压为35～40 MPa的高压氢,放氢温度为135～155℃.