Gd_3Al_(2-x)Ga_x系合金磁热效应的研究

对经真空高频磁悬浮炉熔炼、900℃30 h热处理的Gd_3Al_(2-x)Ga_x(x=0,0.1,0.2,0.3)系列合金的组织结构和磁热效应进行了研究。研究发现,Gd_3Al_(2-x)Ga_x系列合金保持了Gd3Al2的简单正方晶体结构,热处理后基相Gd_3Al_2的含量增加,随着Ga含量的增加,Gd_3Al_(2-x)Ga_x合金的居里温度变化在1 K~2 K之间,在1.5 T的外加磁场下,△S_m-T曲线半峰宽几乎不变,Gd_3Al_(1.8)Ga_(0.2)合金的最大磁熵变最大,超过Gd_3Al_2的最大磁熵变30%。少量Ga替代Al可以提高Gd_3Al_2合金的磁热效应。     

铸态La_(2-x)Sm_xMg_(16) Ni(x=0-0.4)合金的气态储氢性能

采用真空感应熔炼技术制备了La_(2-x)Sm_xMg_(16)Ni(x=0,0.1,0.2,0.3,0.4)储氢合金。用X射线衍射(XRD)研究了合金吸放氢前后的相结构,用Sievert测试了合金吸放氢动力学曲线,采用Arrhenius法估算了合金吸放氢的活化能。结果表明,铸态合金的主相是La_2Mg_(17),并存在少量的第二相SmNi和Sm_5Mg_(41)。合金吸氢后形成了氢化物LaH_3和MgH_2。合金的吸氢量、吸放氢动力学随Sm替代量的增加而增加,当Sm替代量从x=0增加到x=0.4时,最大吸氢量从4.458%(质量分数,下同)增加到4.925%。在3 MPa,498 K下,10 min的吸氢量分别为:4.308%,4.342%,4.488%,4.564%,4.787%;在真空、498 K下,20 min的放氢量分别为1.684%,1.521%,1.779%,1.666%,2.131%。Sm替代对合金吸放氢动力学性能的改善主要归因于Sm使合金的活化能降低。随着合金中Sm替代量的增加,合金生成焓ΔH的绝对值及吸氢平台压先减小后增加。制备合金中,La_(1.7_Sm_(0.3)Mg_(16)Ni合金的生成焓ΔH的绝对值最小,为-53.07 k J·mol-1。     

Mn,Al元素替代对A_2B_7型La-Y-Ni储氢合金的影响

采用高频感应熔炼法制备了A_2B_7型LaY_2Ni_(10.5-x)(MnAl)_x, LaY_2Ni_(10.5-0.8x)Mn_(0.5x)Al_(0.3x), LaY_2Ni_(10.5-0.6x)Mn_(0.5x)Al_(0.1x)(x=2.0, 1.5, 1.0)储氢合金,在Ar气氛和925℃下对铸态合金进行退火处理,通过X射线衍射(XRD)和电化学测试等分析方法系统研究了Mn, Al部分替代Ni元素对合金相结构和电化学性能的影响。研究结果表明:合金由Ce_2Ni_7相、 Gd_2Co_7相、 LaNi_5相、 PuNi_3相和Ce_5Co_(19)相组成,随着Mn, Al替代量的降低,合金中的Gd_2Co_7相含量减少至消失, Ce_2Ni_7相含量增加,各相晶胞体积减小。电化学P-C-T曲线显示不同吸氢态造成的双平台现象,随着Mn, Al替代量的降低,合金吸放氢坪台压升高,平台区域变宽。电化学性能测试表明,随着Mn, Al替代量的减少,合金的最大放电容量,倍率性能和循环性能明显提高。合金高倍率性能的提升主要与合金中Gd_2Co_7相含量降低和Ce_2Ni_7相的增加有关。     

Nd2(Mn1-x,Alx)17化合物的结构性质

对电弧炉熔炼的Nd2 (Mn1 -x,Alx) 1 7(x =1～ 10 )化合物进行了X射线衍射研究。结果表明 ,Nd2 (Mn1 -x,Alx) 1 7(x =1～ 10 )化合物具有Th2 Zn1 7型结构 ,随着Al替代量的增加 ,Nd2 (Mn1 -x,Alx) 1 7(x =1～ 10 )化合物的晶格常数a ,c及单胞体积V都增加。对样品的时效研究表明 ,Nd2 (Mn1 -x,Alx) 1 7(x =1～ 10 )化合物在自然环境中十分稳定 ,这表明Al比C更能使富锰的 2∶17相 (Th2 Zn1 7)稳定。     

Ce替代Y对Y_(1-x)Ce_xFe_2(x=0,0.15,0.25和0.50)合金吸氢性能的影响

利用磁悬浮感应熔炼法制备了Y_(1-x)Ce_xFe_2(x=0,0.15,0.25,和0.50)合金,通过X射线衍射分析(XRD)、扫描电镜(SEM)、电子探针(EPMA)和定容法等测试方法,研究了Ce替代Y对Y_(1-x)Ce_xFe_2合金吸氢性能的影响。研究表明,Y_(1-x)Ce_xFe_2合金为多相结构,主相为MgCu_2型结构的YFe_2相,同时还含有Pu Ni3型结构的YFe_3第二相,且Ce元素有效替代了合金中的Y元素;当x≦0.25时,随着Ce替代量的增加,合金中YFe_3相增多,且合金的吸氢动力学性能和吸放氢循环稳定性得以改善,初始吸氢平衡时间t0.9由48 s降低至12 s,经7次吸放氢循环后,稳定吸氢容量由0.409%升高至0.598%(质量分数),吸氢容量衰减率由79%降低至55%,但合金初始吸氢容量有所下降;这主要归因于YFe_3相较之于YFe_2相结构更加稳定,但其吸氢容量更低;当x=0.50时,合金的吸氢容量及吸放氢循环稳定性均同步下降,此时合金中的YFe2相增多,合金吸氢后歧化反应加剧。因此,在Y_(1-x)Ce_xFe_2中,Ce对Y的替代量以小于0.50为宜。     

P元素的替代对LaFe_(11.4)Si_(1.6)的磁热效应影响

通过电弧炉熔炼法制备了LaFe11.4Si1.6-x P x(x=0.05,0.1,0.2,0.3)系列合金,XRD分析表明少量P元素替代,LaFe11.4Si1.6-x P x(x=0.05,0.1,0.2和0.3)合金仍然保持NaZn13型结构,但晶格常数减小。在居里温度T c附近磁化曲线表明,该系列合金经历由磁场引起巡游电子由顺磁态到铁磁态变磁转变的一级相变。随着P含量的增加,LaFe11.4Si1.6-x P x(x=0.05,0.1和0.2)的居里温度T c减小,等温磁熵变也减小。在外加磁场变化为0~1.5 T时,等温磁熵变最大值分别为19.3 J/(kg·K),15.3 J/(kg·K)和10.3 J/(kg·K)。     

机械合金化制备Mg76-xTi12+xNi9Cr3(x=4,8,12,16)合金贮氢性能的研究

采用机械合金化制备Mg(76-x)Ti(12+x)Ni9Cr3(x=4,8,12,16)合金,通过X射线衍射(XRD)、热分析(DSC)、扫描电子显微镜(SEM)和压强-成分-温度(PCT)分析等方法对合金进行分析和表征.结果表明:Mg(76-x)Ti(12+x)Ni9Cr3(x=4,8,12,16)合金相主要由Mg2...     

Nd（Mn1-x,Alx）17化合物的结构性质

对电弧炉熔炼的Nd2（Mn1-x,Al2)17(x=1-10)化合物进行了X射线衍射研究。结果表明，Nd2（Mn1-x,Al2)17(x=1-10)化合物具有Th2Zn17型结构，随着Al替代量的增加，Nd2（Mn1-x,Al2)17(x=1-10)化合物的晶格常数a，c及单胞体积V都增加。对样品的时效研究表明，Nd2（Mn1-x,Al2)17(x=1-10)化合物在自然环境中十分稳定，这表明Al比C更能使富锰的2：17相(Th2Znl7)稳定。     

CoCrFeNiAl_x(x=1,1.5,2)高熵合金的高温氧化行为

通过非自耗真空电弧熔炼制备CoCrFeNiAl_x(x=1,1.5,2)高熵合金,并结合扫描电子显微镜、X射线衍射仪和电子探针研究了900℃下Al含量对CoCrFeNiAl_x合金氧化行为的影响。结果表明,不同Al含量的三种合金均属于抗氧化级,且其氧化动力学曲线均基本符合抛物线规律。随着Al含量的增加,合金的氧化增重逐渐降低。当Al含量x=1时,合金的氧化膜主要由Cr_2O_3为主的尖晶石相外层和Al_2O_3内层组成;当Al含量x=1.5和x=2时,合金氧化膜主要由Al_2O_3外层以及尖晶石相中间层和Al_2O_3内层组成。     

Al元素对ML(NiCoMnAlFe)_(5.5)贮氢合金微结构和电化学性能的影响

用熔体快淬法制备了稀土系AB_5型ML(NiCoMnFe)_(5.5-x)Al_x(x=0.1～0.3)贮氢合金,在氩气气氛中1000℃下对样品进行热处理,通过X射线衍射、PCT和电性能测试等分析了铝元素对AB5型贮氢合金微观组织和电化学性能的影响。结果显示,热处理样品组织主要由CaCu_5型相组成,组织结构中含有少量NiFe杂相,Al=0.30时合金晶胞体积最大88.49?。PCT测试表明,当Al元素部分替代Ni后,合金的吸氢平台压力减小、吸放氢平台变得比较平坦,x=0.10时合金最大吸氢量为0.9146H/M。电化学性能分析,ML(NiCoMnFe)_(5.5-x)Al_x(x=0.1～0.3)合金具有较好的活化性能,x=0.20合金具有较好的综合性能,最高放电容量337.2mAh/g、循环寿命329次。     

LaNi_(5-x)Al_x贮氢合金的研究

本研究用Ａｌ置换ＬａＮｉ５合金中的部分Ｎｉ，得到一系列ＬａＮｉ５－ｘＡｌｘ（ｘ＝０．１，０．３，０．５）贮氢合金。对这些合金的吸放氢热力学和动力学性能的实验研究表明，随着Ａｌ的加入及Ａｌ含量的增加，贮氢合金的平台氢压降低，吸氢量有所减少，而吸放氢速度有所增加。通过对合金及其氢化物晶体结构的ＸＲＤ分析，发现Ａｌ的加入并未使晶体结构类型发生变化，只是晶格常数变大；ＬａＮｉ５－ｘＡｌｘ合金吸氢后原晶体结构也未发生变化，但其晶格常数增加较大。     

Effect of praseodymium substitution for lanthanum on structure and properties of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（X=0.00-0.20） hydrogen storage alloys

In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system (AB3.5-type) hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1(x=0, 0.10, 0.15, 0.2) hydrogen storage alloys were prepared. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) analyses revealed that two alloys (x=0.0 and 0.10) were composed of (La, Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase and (La,Mg)Ni2 phase, while other alloys (x=0.15 and 0.20) consisted of (La,Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase, (La,Mg)Ni2 phase and (La, Mg)(Ni,Al)3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Elec-trochemical studies showed that the discharge capacity decreased from 360 mAh/g (x=0.00) to 335 mAh/g (x=0.20) as x increased. But the high-rate dischargeability (HRD) of alloy electrodes increased from 26% (x=0.00) to 56% (x=0.20) at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.     

Hydriding and dehydriding characteristics of nanocrystalline and amorphous Mg20-xLaxNi10（X=0-6） alloys prepared by melt-spinning

In order to improve the hydrogenation and dehydrogenation performances of the Mg2Ni-type alloys, Mg was partially substituted by La in the alloy, and melt spinning technology was used for the preparation of the Mg20-xLaxNi10 (x=0, 2, 4, 6) hydrogen storage alloys. The structures of the alloys were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). It was found that no amorphous phase formed in the as-spun La-free alloy, but the as-spun alloys containing La held a major amorphous phase. When La content x≤2, the major phase in the as-cast alloys was Mg2Ni phase, but with further increase of La content, the major phase of the as-cast alloys changed into LaNi5+LaMg3 phase. Thermal stability of the as-spun alloys was studied by differential scanning calorimetry (DSC), showing that spinning rate was a negligible factor on the crystallization temperature of the amor-phous phase. The hydrogen absorption and desorption kinetics of the as-cast and as-spun alloys were measured using an automatically con-trolled Sieverts apparatus, confirming that the hydrogen absorption and desorption capacities and kinetics of the as-cast alloys clearly in-creased with rising La content. For La content x=2, the as-spun alloy displayed optimal hydrogen desorption kinetics at 200 ℃.     

(La_xNd_y)_(0.90)Mg_(0.10)Ni_(3.09)Mn_(0.12)Co_(0.60)Al_(0.13)贮氢合金自放电性能研究

为了提高La-Mg-Ni基贮氢合金的荷电保持率,本文研究了La/Nd比的变化对La-Mg-Ni基贮氢合金自放电性能的影响。随着Nd替代La量的增加,(LaxNdy)0.9Mg0.10Ni3.09Mn0.12Co0.60Al0.13(x/y=5,4,3,2,1)合金的荷电保持率先增大后减小,当x/y=4时,其荷电保持率达到最大值80.8%(318 K)。合金电极贮存后,FESEM-EDS和XRD分析表明,合金颗粒表面形成了Mg(OH)2和Nd(OH)3。P-C-T曲线和Tafel极化测试表明,随着Nd含量的增加,金属氢化物的稳定性呈现先增加后降低和腐蚀电流先减小后增大的规律。     

La0.8Mg0.2(Ni2.7Co0.6Al0.1Mn0.1)x贮氢合金的电化学性能分析

采用恒电位法、EIS分析及双电极系统对La0.8Mg0.2(Ni2.7Co0.6Al0.1Mn0.1)x(x=0.9～1.10)系列合金进行电化学性能分析。结果表明,x=1.05的合金具有较好的自放电性能(CR=97.3%),而x=1.10的合金有较高的电化学容量(369 mAh.g-1)。合金电极的电化学阻抗谱(EIS)表明,随着化学计量比x的增大,合金电极的电荷迁移电阻先减小后增大,动力学性能先增强后减弱。线性极化测试表明,随着化学计量比x的增大,合金电极表面的电化学反应速率先增大后减小。通过合金电极阳极电流对时间响应的半对数曲线计算的氢扩散系数D随着化学计量比x的增大先增大后降低,说明合金内部的氢扩散能力先增强后降低。     

硼的添加对Mg2Ni储氢合金吸放氢性能的影响

镁系储氢合金有着价格低廉、储氢量大等优点,作为机载储氢材料有着广泛的应用前景,但其过高的氢分解温度,过慢的分解速度等缺点制约着实际应用.采用机械球磨制备出Mg2 Ni-xB(x =0％,1％,5％,10％,15％)系列储氢合金.通过XRD分析了合金的物相结构,采用P-C-T测试仪测定了合金的吸放氢性能,研究了添加不同含量的B对Mg2Ni合金吸放氢性能的影响.研究结果表明,B的添加对合金在200和300℃下吸放氢性能的改善作用不明显,但添加B的合金在400℃下的吸氢量均较Mg2Ni高,B的添加量由1％增至15％的合金吸氢量分别为3.09％,3.00％,2.81％,2.84％,而Mg2Ni的吸氢量则只有2.60％.随着B含量的增加,含B合金吸氢量略有降低;在含B的试样中,含5％B的合金吸氢速率最大,仅需180 s便能完成吸氢.所有含B合金的放氢平台均较Mg2Ni高且较为平坦.本次实验表明,B的添加量对合金性能的提升存在一个最优值,本次实验结果显示,添加5％B相对较好地改善合金的储氢性能,提高合金吸氢量和放氢平台压的同时能保持较快的吸氢速率.     

Fe60CoxZr10Mo5W2B23-x(x=1,3,5,7,9)块状金属玻璃的非晶形成能力

The bulk Fe60CoxZr10Mo5W2B23-x (x= 1, 3, 5, 7, 9) amorphous rods with diameters of1.5 mm were successfully prepared by copper mold casting method with the low purity raw materials.The amorphous and crystalline states, and thermal parameters, such as the glass transition temperature (Tg), the initial crystallization temperature (Tx), the supercooled liquid region (ΔTx = TxTg), the reduced glass transition temperature Trg (Tg/Tm, Tm: the onset temperature of melting of the alloy, and Tg/T1, T1 : the finished temperature of melting of the alloy) were investigated by X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) analysis. Glass forming ability of Fe60CoxZr10Mo5W2B23-x (x=1, 3, 5, 7, 9)bulk metallic glasses has been studied. According to the results, the alloy (x=7) with the highest Trg (Tg/T1 =0. 607, Tg/T1 =0.590) value, has the strongest glass forming ability among these alloys because its composition is near eutectic composition.The wide supercooled liquid region over 72 K indicates the high thermal stability for this alloy system.This bulk metallic glass exhibits quite high strength (Hv 1020). The success of production of the Febased bulk metallic glass with industrial materials is of great significance for the future progress of basic research and practical application.     

添加钕对Mg2Ni储氢合金的结构和电极性能的影响

利用两步法制备了一系列添加Nd的三元Mg2-xNdxNi合金。XRD分析证实，当x=0．05，0．1时，制得的三元Mg2-xNdxNi合金均为Mg2Ni单相合金；三元Mg18Nd0．2Ni(x=0．2，0．3)合金为三相合金，三相分别为Mg2Ni，NdNi，NdMgNi4。模拟电池测试结果表明，同Mg2Ni合金相比，球磨10h的三元Mg1．8Nd0．2Ni合金和Mg17Nd03Ni合金电极的放电容量提高明显，且Mg17Nd03Ni合金电极的循环性能有明显改善。这极有可能与合金中NdMgNi4相的存在以及球磨形成的微结构有关。     

On stress corrosion cracking in aluminum-lithium alloys

The stress corrosion cracking (SCC) susceptibility of two aluminum-lithium alloys, a binary AlLi and a ternary AlLiCu alloy, in 0.5 M NaCl solution was investigated using the constant elongation rate technique (CERT). Susceptibility increased with decreasing strain rate and with aging. The alloys were susceptible under both anodic and cathodic applied potentials. The susceptibility dependence of the alloys as a function of applied potential correlates well with published hydrogen permeability data. The susceptibility increased dramatically when hydrogen was charged into the specimen using a hydrogen re-combination “poison” during CERT testing. These experiments suggest that hydrogen plays a major role in the SCC of these alloys. A brittle hydride having the composition LiAlH₄ forms in the AlLi system under conditions of severe SCC susceptibility. The brittleness of the hydride is explained. The formation of the hydride is a sufficient condition for SCC of AlLi alloys. A process of SCC in AlLi alloys is proposed wherein hydrogen causes damage by the formation of a hydride.     

Enhanced hydrogen storage performance of Mg-Cu-Ni system catalyzed by CeO_2 additive

In this paper,the as-cast Mg_(85)Cu_5Ni_(10) alloy and Mg_(85)Cu_5Ni_(10)-x wt% CeO_2(x=0,4,8) alloys were prepared successfully by vacuum induction smelting and ball milling.The microstructure,hydrogen absorption/desorption kinetics and thermodynamics performances of the alloys were studied in detail.The results show that the Mg_(85)Cu_5Ni_(10) alloys with CeO_2 additive have faster hydrogenation/dehydrogenation kinetics and better thermodynamic properties.The dehydrogenation activation energy is reduced to 81.211 kJ/mol from 119.142 by adding 8 wt% CeO_2.CeO_2 contributes to producing structural defects,nanocrystallines,grain boundaries,partial amorphous,lattice dislocations and cracks which are favorable to provide more hydrogen diffusion channels during hydriding/dehydriding process.Meanwhile,CeO_2 additive weakens the bond energy of Mg-H.These micro structural changes caused by CeO_2 additive improve the hydrogen storage performance of Mg_(85)Cu_5Ni_(10) markedly.