Mg含量对氢化燃烧合成MgH_2水解制氢性能的影响

系统研究了Mg的添加量及球磨时间对氢化燃烧合成(Hydriding Combustion Synthesis,HCS)Mg H2在Mg Cl2溶液中水解释氢动力学性能的影响。Mg H2-60%Mg(质量分数,下同)经3 h球磨后在5 min内释氢量为993 m L/g(转化率达80%),经15 min可完全水解,副产物为单一的Mg(OH)2。研究表明:镁的添加在降低制氢成本的同时,一方面可提高释氢动力学性能,另一方面也便于副产物回收再生。     

铟对MgH2脱氢性能的影响

将MgH2和In的混合粉末在行星式球磨机上进行球磨,制备了一种Mg H2-In的复合物。利用XRD分析了复合物的相组成以及吸放氢过程中的相转变;用气相色谱仪和差示扫描量热仪测定了复合物的脱氢性能和相转变温度,并用基于Sievert原理的全自动气体吸附仪测定了复合物的吸放氢热力学和动力学性能。结果表明,脱氢过程中Mg3In和Mg(In)固溶体的形成使Mg H2的脱氢反应焓和激活能显著降低,从而降低了Mg H2的脱氢温度,并显著改善了动力学性能。     

固-气反应球磨制备纳米晶MgH2的研究

采用固.气反应球磨制备纳米晶MgH2粉末,测定纯镁粉在球磨过程中的吸氢动力学曲线.借助X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等分析手段,研究Mg-H2反应球磨过程中的相结构与粉末形貌演变规律.结果表明,在机械球磨驱动作用下,Mg的吸氢过程可分为"缓慢-快速-饱和"3个阶段,其相组成分别对应"Mg(H)-Mg(H)+MgH2-MgH2".在0.5 MPa氢气压条件下,球磨21 h可使Mg完全氢化,获得粉末粒度1～3μm、晶粒尺寸10 nm左右的纳米晶MgH2粉末,其实际氢含量高达7.03%(质量分数,下同).     

Nanocrystalline Mg and Mg alloy powders by hydriding-dehydriding processing

The process of mechanically assisted hydriding and subsequent thermal dehydriding was proposed to produce nanocrystalline Mg and Mg alloy powders using pure Mg and Mg-5.5%Zn-0.6%Zr(mass fraction)(ZK60 Mg) alloy as the starting materal.The hydriding was achieved by room-temperature reaction milling in hydrogen.The dehydriding was carried out by vacuum annealing of the as-milled powders.The microstructure and morphology of both the as-milled and subsequently dehydrided powders were characterized by X-ray diffraction analysis(XRD) ,transmission electron microscopy(TEM) ,and scanning electron microscopy(SEM) ,respectively.The results show that,by reaction milling in hydrogen,both Mg and ZK60 Mg alloy can be fully hydrided to form nanocrystalline MgH2 with an average grain size of 10 nm.After subsequent thermal dehydriding at 300℃,the MgH2 can be turned into Mg again,and the newly formed Mg grains are nanocrystallines,with an average grain size of 25 nm.     

Hydrogen storage behaviors and microstructure of MF3 (M=Ti, Fe)-doped magnesium hydride

MgH2+10%MF3(M=Ti,Fe)(mass fraction) composites were prepared by ball-milling in hydrogen atmosphere,and their hydrogen storage behaviors and microstructure were investigated systematically.The results show that the hydriding and dehydriding kinetics of MgH2 are markedly improved by doping TiF3 and FeF3 fluorides.At 573 K,the two composites can absorb 5.67%-6.07%(mass fraction) hydrogen within 5 min under an initial hydrogen pressure of 3.5 MPa,and desorb 5.34%-6.02% hydrogen within 6 min.Furthermore,the composites can absorb hydrogen rapidly in moderate temperature range of 313-473 K.In comparison,TiF3-doped sample has a better hydriding-dehydriding kinetics than FeF3-doped sample.The microstructure analysis shows that some active particles including MgF2,TiH2 and Fe could be formed in the hydriding-dehydriding processes of the MF3-doped composites.From the Kissinger's plot,the apparent activation energies for the hydrogen desorption of the composites are estimated to be 74.1 kJ/mol for TiF3-doped composite and 77.6 kJ/mol for FeF3-doped composite,indicating MgH2 is significantly activated due to the catalytic effect of the doping of MF3.     

Influence of chloride salts on hydrogen generation via hydrolysis of MgH2 prepared by hydriding combustion synthesis and mechanical milling

The effects of chloride salts (NaCl, MgCl₂ and NH₄Cl) on the hydrolysis kinetics of MgH₂ prepared by hydriding combustion synthesis and mechanical milling (HCS+MM) were discussed. X-ray diffraction (XRD) analyses show that high-purity MgH₂ was successfully prepared by HCS. Hydrolysis performance test results indicate that the chloride salt added during the milling process is favorable to the initial reaction rate and hydrogen generation yield within 60 min. A MgH₂–10% NH₄Cl composite exhibits the best performance with the hydrogen generation yield of 1311 mL/g and a conversion rate of 85.69% in 60 min at room temperature. It is suggested that the chloride salts not only play as grinding aids in the milling process, but also create fresh surface of reactive materials, favoring the hydrolysis reaction.     

Al2O3/Cu复合材料的导热性能研究

利用高能球磨及粉末冶金法制备了Al2O3/Cu复合材料,采用双试样叠加激光脉冲法测试室温条件下的导热性能.研究发现,随着Al2O3体积分数的增加,热导率逐渐下降,特别是当Al2O3体积分数大于10％以后热导率急剧下降,这说明热导率受Al2O3含量影响很大.要获得良好导热性能的Al2O3/Cu复合材料,应该严格控制Al2O3颗粒的体积分数不高于10％,尽量提高致密度,减少烧结体内的位错、空隙等缺陷.     

常压下催化合成氢化镁放氢动力学研究

研究了常压下催化合成氢化镁在不同温度下的放氢动力学性能，并应用可解析动力学模型分析其放氢动力学机理，从理论上预报了可能得到的实验趋势和结果，预测了催化合成氢化镁的放氢动力学性能，并阐述了它能加速反应的原因。     

Formation and chemical leaching effects of nonequilibrium Al0.6(Fe25Cu75) alloy powder produced by rod milling

The formation and chemical leaching effects of a nonequilibrium Al_0.6(Fe₂₅Cu₇₅)_0.4 powder produced by rod milling is described. X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and vibrating sample magnetometry were used to characterize both the as-milled and leached specimens. After 400 h of milling, only the bcc AlFe phase with an amorphous phase was detected in the XRD patterns. The crystallite size for the bcc AlFe phase (110) after 400 h of milling was about 5.3 nm. The peak temperature and the crystallization temperature of the as-milled powders were 448.7 and 428.0 °C, respectively. Al atoms leaching from the as-milled bcc AlFe powders in the L1 condition did not alter the diffraction pattern significantly, even though Al atoms had been removed. After the L1 specimen was annealed at 500 °C for 1 h, the bcc AlFe phase transformed to the fcc Cu, Fe, and CuFe₂O₄ phases. The peak widths of L1 and L2 specimens were similar, but became broader than that of the as-milled powder. The saturation magnetization decreased with increasing milling time, and a value of 10.4 emu/g was reached after 400 h of milling. After cooling the specimen from 750 °C, the magnetization slowly increased at approximately 491.4 °C, indicating that the bcc AlFe phase had transformed to the fcc Cu and Fe phases.     

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.     

基于BP神经网络的细晶Ti_2AlNb基合金粉末球磨工艺研究

应用BP神经网络算法分析并预测了高能行星式球磨过程中工艺参数和球磨后Ti_2AlNb基合金粉末的形貌特征之间的关系,建立了粉末参数预测模型。BP网络模型的输入参数为球磨转速,球磨时间,球料比;输出参数为球磨后Ti_2AlNb基合金粉末的晶粒尺寸。BP网络模型中间隐含层节点数为9,输入、输出函数分别为tansig、purelin。通过检验样本验证了所建立神经网络模型的准确性。结果表明:该模型在容错性和通用性等方面优点突出,可用于预测球磨法制备细晶Ti_2AlNb基合金粉末的晶粒尺寸,还可以弥补各种球磨过程物理模型应用与表述方面的不足,对于实际的粉末冶金工艺研究具有积极的应用价值和指导意义。     

球磨与烧结对Al2Ti3V2ZrB/2024Al复合材料组织与硬度的影响

利用粉末冶金方法制备了Al2Ti3V2ZrB/2024Al复合材料,研究了球磨工艺和烧结温度对复合材料微观组织和硬度的影响。结果表明,球磨时过高的球磨速度或过长的球磨时间均会造成Al2Ti3V2ZrB颗粒的团聚,影响复合材料的组织均匀性。在球磨速度为150r/min下球磨5h,Al2Ti3V2ZrB颗粒在2024Al基体中的分布最均匀,复合材料的硬度最高。当烧结温度低于510℃时,Al2Ti3V2ZrB颗粒在2024Al基体中分布比较均匀,复合材料密度和硬度随烧结温度升高逐渐增加;超过510℃后Al2Ti3V2ZrB颗粒开始团聚,复合材料密度和硬度下降,在510℃制备的复合材料具有最高的硬度。     

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.     

机械合金化过程中Fe50Als50二元系的结构演变

利用高能球磨和后续热处理技术制备纳米晶Fe5A150（摩尔分数，％）合金粉体。采用X射线衍射、透射电镜和扫描电镜对元素混合粉在机械合金化过程中的结构演变及热处理对合金化粉体结构的影响等进行分析，讨论其机械合金化合成机制。结果表明：球磨过程中Al向Fe中扩散，形成Fe（A1）固溶体。机械合金化合成Fe（Al）遵循连续扩散混合机制；球磨30h后，粉体主要由纳米晶Fe（A1）构成，晶粒尺寸5．65nm；热处理导致Fe（A1）纳米晶粉体有序度提高，转变为有序的B2型FeAl金属间化合物，粉体的晶粒尺寸增大，但仍在纳米尺度范围。     

基于镍基固溶体催化的氢化镁储氢性能

采用高能球磨制备Ni?25％X(X=Fe,Co,Cu,摩尔分数)固溶体,然后将其掺杂于MgH2体系中.与球磨纯MgH2相比,MgH2/Ni?25％X复合体系初始放氢温度降低近90℃,其中,Ni?25％Co固溶体呈最佳催化效果.球磨MgH2/Ni?25％Co复合体系在300℃、10 min内可释放5.19％(质量分数)氢...     

离心成型法制备无宏观界面的Al2O3/Ni功能梯度材料

采用一种新颖的离心成型法制备了无宏观界面的Al2O3/Ni功能梯度材料, 并研究了料浆调制工艺、离心成型制备机理和梯度材料的力学性能。结果表明, 配制料浆时,粘结剂(聚乙二醇)含量为2 mass%、固相含量为63vol.%、球磨时间为36h,可得到流动性良好的料浆,经离心成型（40min,转速3000 r/min）得到无宏观界面的坯体,在1400 C真空烧结2 h,最终得到致密、组元宏观连续过渡的Al2O3/Ni梯度材料。通过调整固相含量和粘结剂含量,可调控Al2O3/Ni复合材料的成分梯度。     

球磨条件下Fe合金化改善MgH2体系性能的机理

基于密度泛函理论的第一原理方法,通过计算清洁、空位缺陷Mg(0001)表面吸附氢分子(H2)前后以及Fe合金化镁氢化合物(MgH2)体系的能量与电子结构,对球磨条件下Fe合金化改善MgH2体系性能的原因进行初步探讨。结果表明:与清洁Mg表面相比,由于球磨改变了Mg颗粒的表面结构,使Mg表面产生较多缺陷,而缺陷的存在增强了H2的物理吸附能力,并且Mg表面向H2转移的电荷数增多,因而体系球磨后具有较好的吸氢性能;而在Fe合金化MgH2体系中,Fe固溶于MgH2中形成(MgFe)H2固溶体和合金化形成少量Mg2FeH6相,MgH2系结构稳定性均降低,对应体系解氢性能增强。分析电子结构发现:空位缺陷有助H2吸附于Mg表面,与Mg(0001)表面最上层与H2直接产生吸附作用的金属原子在费米能级(EF)附近s轨道的成键电子数密切相关;在Fe合金化MgH2体系中,与合金化元素Fe近邻的H原子形成空位的难度增加,H原子较难释放;与Mg近邻的H原子形成空位的难度减少,H原子容易释放;Fe合金化导致Mg-H之间存在较弱的成键作用,因此,MgH2体系的解氢性能得到提高。     

Interactions of particles with solidifying front in Al_2O_(3P) /Al Si composites

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Mg70Al20Ca10合金机械合金化过程中的结构变化

以纯金属Mg、Al和Ca为原料,采用机械合金化的方法制备了Mg70Al20Ca10非晶态合金,分析了球磨过程中粉末试样的晶粒尺寸变化和相结构变化情况.结果表明,球磨过程中形成纳米晶和两种非晶相.Mg-Al-Ca合金在化学驱动力较小的条件下,可以通过机械驱动力的作用提高Ca、Al在Mg中的固溶度,导致非晶转变的发生.     

Mechanical and microstructural characterization of dispersion strengthened Al–C system nanocomposites

Al and different amounts of C and C–Cu mixtures were used to produce Al–C and Al–C–Cu powder samples by mechanical milling. Microhardness tests were carried out to evaluate the mechanical properties of the nanocomposites in the as-milled condition. In general, the measured values were considerably higher than pure Al. In order to determine the causes of this hardening, the crystallite size and dislocation density were measured by means of X-ray analyses coupled with a convolutional multiple whole profile (CMWP) fitting program and a comparison with atomic force microscopy (AFM) observations. In Al–C samples, the hardening is mainly due to the decrease of the crystallite size, however for the Al–C–Cu, an additional strengthening mechanism appears and it seems that it is due by a dispersion of graphite nanoparticles in the Al matrix. The strengthening contributions of dislocation density, crystallite size and particle dispersion were modeled by superposing of every single contribution to strengthening (via hardness analyses). We found a direct relationship between the mechanical properties and the nominal amount of C–Cu, where Cu apparently acts as C nanoparticles integration and dispersion agent.