TiF3对氢化燃烧合成Mg95Ni5放氢性能的影响

研究了TiF3的添加对氢化燃烧合成Mg95Ni5放氢性能的影响。添加1%(摩尔分数,下同)TiF3机械球磨10h可使Mg95Ni5的放氢性能达到最佳,在523K时,1800s内的放氢量可达到5.20%(质量分数,下同),并使放氢反应的表观活化能从Mg95Ni5的124kJ/mol降低到86kJ/mol。研究表明,TiF3的催化作用可归因于生成的MgF2和Tix+的氢化物减弱了Mg-H鍵。     

Hydrogen sorption properties of Mg-20wt.%Fe 23 Y8 composite prepared by reactive mechanical alloying

Mg-20wt.% Fe23Y8 composite was successfully prepared by reactive mechanical alloying (RMA). X-ray diffraction (XRD) measurement shows that the main phases of composite are MgH2 and Mg2FeH6. The composite exhibits excellent hydrogen abs/desorption properties and can absorb 4.36wt.% and 5.72wt.% hydrogen at 473 and 573 K in 10 min under 3.0 Mpa hydrogen pressure, respectively. The composite can desorb 5.27wt.% hydrogen at 573 K in 30 min under 0.02 Mpa hydrogen pressure. Compared with the pure MgH2, the hydrogen desorption temperature of Mg-20wt.% Fe23Y8 composite is decreased about 40 ℃. It is supposed that both the catalyst effect of Fe-Y distributed in Mg substrate and the crystal defects play the main role in improving hydrogen sorption properties of Mg-20wt.% Fe23Y8 composite.     

置氢处理对Ti40合金显微组织及相变的影响

先采用感应熔炼法制备SrAl2合金,然后采用机械球磨方法分别添加摩尔分数为x=2％的TiF3、Ti及TiO2催化剂,从而得到不同Ti基催化剂添加的Zintl相合金SrAl2;并将未添加催化剂的SrAl2合金用于对比研究.采用XRD、SEM、EDS、PCT及XPS设备研究了材料的相结构、表面形貌、吸氢性能与催化机理.研究表明:3种Ti基催化剂对Zintl相合金SrAl2的吸氢均能起到催化作用,催化强弱次序如下:TiF3＞ Ti＞ TiO2.对添加Ti基催化剂的SrAl2合金吸氢前后的表面XPS研究分析表明:合金表面Ti 2p电子的结合能发生了改变,说明其化学状态发生了变化.特别是添加了TiF3的合金样品中出现了单质Ti0,这种在反应过程中生成的中间产物Ti0要比刚开始在合金中加入的单质Ti具有更高的催化活性.     

Hydrogen generation via hydrolysis of nanocrystalline MgH2 and MgH2-based composites

Nanocrystalline MgH2 and MgH2-based composites with 25% （mass fraction） of Al, Ca, or CaH2 as an individual additive respectively were prepared by ball milling. The crystallite size and morphology of the as-milled powders were characterized and their hydrolysis behaviours were investigated in comparison with commercial polycrystalline MgH2. The results show that the crystallite size of both MgH2 and MgH2-based composites is reduced to less than 13 nm after milling for 15 h. Due to its enhanced specific surface area and unique nanocrystalline structure, the as-milled MgH2 shows much better hydrolysis kinetics than the commercial polycrystalline MgH2, with the hydrolysed fraction upon hydrolysing for 70 min enhances from 7.5% to about 25%. As compared with the as-milled MgH2, the MgH2-based composites with either Call2 or Ca as an additive present further greatly improved hydrolysis kinetics, with the hydrolysed fraction for 80 min achieving about 76% and 62% respectively. However, the addition of Al doesn＇t show any positive effect on the improvement of the hydrolysis kinetics of Mg H2.     

Improved hydrogenation properties of Mg-x(Ti0.9 Zr0.2 Mn1.5 Cr0.3) composites

Mg-x(Ti_0.9 Zr_0.2 Mn_1.5 Cr_0.3)(x=20%, 30%, 40%) (mass fraction) composite powders were prepared by reactive ball milling with hydrogen and their hydrogen storage properties and microstructure were investigated by XRD, SEM and pressure-composition-temperature measurement. The results show that the composites have 3.83%-5.07% hydrogen capacity at 553 K and good hydrogenation kinetics, even at room temperature. Among them, the milled Mg-30%(Ti_0.9Zr_0.2Mn_1.5Cr_0.3) composite has the highest hydrogenation kinetics as it can quickly absorb 2.1% hydrogen at 373 K, 3.5% in 2 000 s at 473 K, even 3.26% in 60 s at 553 K under 3 MPa hydrogen pressure. The improved hydrogenation properties come from the catalytic effect of Ti_0.9 Zr_0.2 Mn_1.5 Cr_0.3 particles dispersed uniformly on the surface of Mg particles.     

LiAlH4/LiNH2+Ti/TiF3复合物的储氢性能

为改善LiAlH4和LiNH2的储氢性能,将两者混合球磨制备LiAlH4/LiNH2复合体系,并添加TiF3和Ti作为复合体系催化剂。采用DSC、TG、XRD和储氢特性测定等手段研究催化剂TiF3和Ti对LiAlH4/LiNH2复合体系储氢性能的影响。结果表明：添加Ti和TiF3可显著改善Li-Al-N-H储氢体系的放氢动力学性能、提高放氢总量和降低体系的放氢温度。添加5%（摩尔分数,下同）TiF3催化剂后,LiAlH4/LiNH2复合体系球磨过程放氢量由1.27%（质量分数,下同）增加到1.69%,总放氢量由5.95%增加到6.85%。起始放氢温度由150 ℃降低到75 ℃。     

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...     

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。     

HCS+MM法制备镁基复合储氢材料结构及储氢性能

采用氢化燃烧合成法制备Mg95Ni5-x%TiFe0.8Mn0.2Zr0.05(x=0, 10, 20, 30)(质量分数)复合物,然后将氢化燃烧合成产物进行机械球磨得到镁基复合储氢材料。采用XRD、SEM、EDS及PCT研究材料的相结构、表面形貌、颗粒化学成分以及吸放氢性能。研究表明,添加30% TiFe0.8Mn0.2Zr0.05合金形成的复合物具有最佳的综合吸放氢性能：在373 K,50 s内基本达到饱和吸氢量4.11% (质量分数);在493和523 K,1800 s内放氢量分别为1.91%和4.3%;其起始放氢温度为420 K,与Mg95Ni5相比降低了20 K,吸放氢性能的改善与复合物的组织结构密切相关。此外,TiFe0.8Mn0.2Zr0.05的加入改善了复合物的放氢动力学性能     

镧对镁吸氢和放氢动力学及热力学性能的影响

研究纳米La2O3对Mg颗粒的助磨作用以及吸氢和放氢的催化作用,对克服Mg吸氢和放氢动力学差的问题有重要意义。Mg粉中添加1.0 mol.%的La2O3于球磨后,XRD分析表明Mg晶粒为49.7 nm,而纯Mg球磨后的晶粒为51.6 nm,La2O3使球磨后Mg晶粒的更小,这有利于提高Mg的吸氢和放氢速率。SEM观测表明,球磨后La2O3纳米晶粒与Mg晶粒紧密接触,呈镶嵌结构,这有利于La2O3对Mg吸氢和放氢发挥催化作用。吸氢和放氢动力学测试表明,添加La2O3使Mg吸氢和放氢速率加快,吸氢反应活化能降低49.8 kJ/mol,放氢反应活化能降低23.1 kJ/mol,即显著地了改善Mg吸氢和放氢的动力学性能。p-c-T等温吸附平衡测试表明,添加La2O3球磨后Mg的吸氢活性更高,平衡氢压较低。DSC放氢分析表明,添加La2O3后MgH2放氢温度有所降低。硬度比Mg大的La2O3纳米颗粒在球磨过程中起助磨作用,不与Mg反应;在加氢和放氢过程中La2O3起催化作用,不与H2反应。     

Ce基催化剂对2LiBH4/MgH2放氢性能的影响

采用球磨方法制备了2LiBH4/MgH2复合储氢材料体系,用XRD、FTIR和储氢性能测试手段等对复合体系结构和储氢性能进行表征,研究了不同Ce基催化剂对复合体系放氢性能的影响,分析了催化剂的催化机理。结果表明:2LiBH4/MgH2复合物加热过程为明显的两步放氢,第1步主要发生MgH2的分解放氢;第2步为第1步生成的Mg与LiBH4发生放氢反应;添加Ce和CeF3都能提高2LiBH4/MgH2体系的放氢性能。Ce主要改善体系第2步放氢特性,CeF3对体系两步放氢反应均产生显著效果。添加5mol%CeF3使2LiBH4/MgH2体系起始放氢温度降低约100℃,体系最大放氢量达到10.6%(质量分数,下同);F-取代部分H-形成LiBH1-xFx,改善了LiBH4的分解特性,从而显著改善了2LiBH4/MgH2体系的放氢性能。     

直流电弧制备的Mg-TiO2复合材料的储氢性能

采用直流电弧等离子体法蒸发Mg＋5%Ti O2的混合物并将其在空气中钝化,制备粉体Mg-Ti O2复合储氢材料。利用电感耦合等离子光谱发生仪（ICP）、X射线衍射仪（XRD）、扫描电子显微镜（SEM）表征粉体复合材料的成分、相组成及形貌。采用压力–成分–温度（PCT）和差示扫描量热仪（DSC）对Mg-Ti O2样品的吸放氢性能进行研究。由PCT测量结果可知,Mg-Ti O2复合粉体中镁的氢化焓和氢化熵分别为-71.5 kJ/mol和-130.1 J/（K·mol）,而粉体的氢化激活能为77.2 k J/mol。结果表明,采用电弧等离子体法在超细镁颗粒中加入Ti O2催化剂可显著增强镁的吸放氢动力学性能。     

SiO2包覆对含微量CO氢环境中LaNi4.25Al0.75吸氢动力学性能的影响

采用气相二氧化硅法制备了LaNi4.25Al0.75/SiO2复合材料,研究了该复合材料表面形貌以及氢中微量CO对LaNi4.25Al0.75合金及LaNi4.25Al0.75/SiO2复合材料吸氢动力学性能的影响。结果表明：合金被毒化后,在表面生成含NiO、La(OH)3、La2O3、Al(OH)3的氧化层,并且吸附大量CO,导致合金的吸氢量减少,动力学变慢。表面包覆SiO2可显著改善合金抗毒化性能     

Phase-structure and Hydrogen Storage Behaviors of Mg+10% Ni2P Composite Prepared by Reactive Ball-Milling

采用反应球磨法制备了Mg+10%Ni2P(质量分数,下同)新型复合物,对比研究了球磨复合物和球磨纯镁的相结构与储氢性能。研究表明:在纯Mg中添加10%的Ni2P进行复合球磨,可以明显提高其吸/放氢性能。此外,添加Ni2P球磨明显地改善了镁的循环放氢性能。复合物的晶粒尺寸随着球磨时间的增加而减小;添加Ni2P能有效地抑制Mg/MgH2在吸/放氢过程中产生团聚;在Mg中添加Ni2P球磨能降低体系的放氢反应温度。     

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.     

(TiB_2 TiAl_3)/AlSi_6Cu_4复合材料的研究

利用K2 TiF6 KBF4混合盐和AlSi6 Cu4熔体反应可以制备TiB2 TiAl3颗粒增强AlSi6 Cu4基复合材料。通过XRD和SEM等仪器对复合材料的凝固组织和力学性能进行了研究 ,随K2 TiF6 和KBF4混合盐加入量的增加 ,原位反应生成的颗粒尺寸减小 ,分布更均匀 ;所得到的AlSi6 Cu4复合材料的强度比AlSi6 Cu4基体明显提高。     

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。     

Desorption behaviour and microstructure change of nanostructured hydrided AZ31 Mg alloy powders

In order to optimize the dehydriding process for producing nanocrystalline Mg alloy powders by hydriding-dehydriding treatment,nano-structured as-hydrided Mg-3%Al-1%Zn(AZ31 Mg)(mass fraction)alloy powders were thermally dehydrided at various temperatures from 275 to 375℃.The kinetics of hydrogen desorption was examined by hydrogen discharge measurement during dehydriding.The microstructure of the as-hydrided and the subsequently fully dehydrided alloy powders was investigated by X-ray diffraction analysis(XRD)and transmission electron microscopy(TEM),respectively.Both the desorption kinetics and the grain size of the alloy after complete dehydriding were found to be strongly dependent on the processing temperature.The higher the temperature,the faster the desorption,and the more significant the grain growth.When the desorption temperature was raised from 300 to 375℃,the time to achieve complete dehydriding was shortened from 190 to 20 min,and the average grain size increased correspondingly from 20 to 58 nm.     

Preparation and hydrogen sorption properties of Mg-Cu-Y-H systems

Mg-xwt.%CuY (x=15, 20, 25) composites were successfully prepared by reactive mechanical alloying (RMA).X-ray diffraction (XRD) measurement shows that main phases of the as milled composites are MgH2 and Mg2Cu, and they converted into Mg and MgCu2 after dehydrogenation, respectively.Pressure-Composition-Isotherm (PCI) test shows that the composites exhibit double pressure plateau at each isothermal desorption process.The hydrogen absorption and desorption kinetics of the composites become worse with increasing x content, indicating that Mg-Cu phase has a negative effect on the hydrogen sorption properties of the composites.It is supposed that the good hydrogen sorption properties of the composites attribute to the catalyst effect of yttrium hydride distributed in Mg substrate and the particles size reduction and crystal defects formed by RMA.     

Effect of SiC volume fraction on the age-hardening behavior in SiC particulate-reinforced 6061 aluminum alloy composites

The age-hardening behavior in the SiC particulate-reinforced 6061 aluminum alloy composites (SiCp/6061 Al alloy composites) was investigated using hardness measurement, calorimetric technique and transmission electron microscopy. The aging time for the peak hardness in 10%SiCp/6061 Al and 20%SiCp/6061 Al alloy composites was shorter than that of the unreinforced 6061 Al alloy, and the age-hardening was most accelerated in the 20%SiCp/6061 Al alloy composite. It is induced from the high density of dislocations in SiCp/6061 Al alloy composites which act as heterogeneous nucleation sites of precipitates and as a high diffusivity path of alloy elements. The precipitation sequence and the aspect of precipitates in the 6061 Al alloy cannot be affected considerably by the presence of SiC particulate and the volume fraction of SiC particulate. The activation energies for the formation of the intermediate β' phase in the unreinforced 6061 Al alloy, 10%SiCp/6061 Al and 20%SiCp/6061 Al alloy composite were 142.6 kJ/mol, 127.3 kJ/mol, 106.1 kJ/mol, respectively.