镁合金电子结构与腐蚀特性研究

采用递归法计算了镁合金电子结构.研究发现Mg的态密度在晶内与表面接近,当表面有氧或氢氧时态密度形状改变很大,因此Mg在晶内、表面性质是接近的,但当合金表面渗透氧或氢时,合金性质有明显变化.Al,Y,La三种元素在晶体表面的掺杂原子镶嵌能均低于各自在晶内的掺杂原子镶嵌能,Al, Y, La从晶内向晶体表面扩散、并在合金表面偏聚.Al-O, Y-O, La-O, Mg-O及Mg-O-H间的亲和能均为负数,这些原子间存在亲和力,可以在合金中相互作用形成化合物.由于Mg-O-H间的亲和能远低于Mg-O的亲和能,因此Mg(OH)₂比MgO更稳定.氧化初期氧与Mg, Al, Y, La等生成氧化物,当合金与腐蚀介质接触时,MgO与腐蚀介质中的水发生反应生成Mg(OH)₂.Al₂O₃,（Y,La）₂O₃及Mg(OH)₂能对合金起到保护作用,提高合金的耐腐蚀性能. 关键词： 电子结构 Mg合金 腐蚀特性     

LaNi5-NdNi5,LaNi5-CeNi5赝二元系相图和吸氢性能的研究

本文用X射线衍射和差热分析的方法测定了LaNi₅-NdNi₅,LaNi₅-CeNi₅两个赝二元系相图。用X射线衍射线宽化法测定了活化后LaNi₅-NdNi₅体系的样品晶粒尺寸的各向异性。考查了吸氢性能和第二相存在对LaNi₅吸氢性能的影响。测定和计算了两个体系中样品的点阵常数、单胞体积、原了间距吸氢前后的变化。从结构的观点,解释了LaNi₅-NdNi₅体系中活化后样品晶粒尺寸各向异性的原因。用本实验的结果,解释了RmNi₅(Rm代表混合稀土金属)的吸氢量和平台压力的差异。 关键词：     

掺杂Fe对VH2解氢性能影响的第一性原理研究

采用密度泛函理论(DFT)的第一性原理的平面波超软赝势方法,研究了Fe掺杂对VH₂的电子结构和解氢性能的影响.通过计算Fe掺杂VH₂前后体系的合金形成热、V-H之间的重叠布居数、电子态密度、电子密度,发现Fe掺杂VH₂后,随着Fe含量增加,合金体系的晶胞参数和晶胞体积逐渐减少;体系的负合金形成热逐渐减少,且掺杂后体系的负合金形成热都比VH₂的负合金形成热小,体系的稳定性降低;电子态密度计算也显示Fe掺杂后费米能级处的电子浓度增加,体系稳定性降低;重叠布居数和电子密度计算表明掺杂后V-H之间的重叠布居数由0.1减小为0.08或0.09,V-H之间的电子密度减少,说明V和H原子之间的相互作用减弱,提高了VH₂的解氢性能.计算结果解释了实验现象. 关键词： Fe掺杂 电子结构 解氢性能 第一性原理计算     

Zr基大块非晶中添加元素对非晶形成能力及耐蚀性的影响

运用实空间递归方法研究了添加元素Nb,Ta,Y,La对Zr基非晶合金的非晶形成能力和耐腐蚀性能的影响.用计算机编程构造了Zr基非晶中初始晶化相Zr₂Ni的原子结构模型,用Zr₂Ni中的二十面体原子团簇模拟非晶中的二十面体团簇.计算了替代二十面体中心或顶角位置原子前后Ni,Zr及合金元素的局域态密度、团簇中心Ni与近邻Zr原子及Ni与替代元素Nb,Ta,Y,La间的键级积分,还计算了合金元素替代前后团簇的费米能级.局域态密度计算结果表明：合金元素Cu占据二十面体团 关键词： 电子结构 Zr基大块非晶 非晶形成能力 耐蚀性     

(La,Ce,Tb)BO3的合成及光谱性质

采用高温固相法合成了(La,Ce,Tb)BO₃绿色发光粉,并对该发光粉进行了XRD和SEM分析。结果表明:(La,Ce,Tb)BO₃的晶体结构和LaBO₃相同,Ce³⁺、Tb³⁺的掺入并没有改变晶体的结构,发光粉颗粒大小均匀,形貌规则,粒度在5 μm左右。研究了(La,Ce,Tb)BO₃的光谱性质,在(La,Ce,Tb)BO₃的发射和激发光谱中除了有Tb³⁺的特征发射和激发峰外,还有Ce³⁺的特征发射和激发峰。比较了(La,Ce)BO₃发射光谱和(La,Tb)BO₃的激发光谱,两者存在重叠,这为Ce³⁺→Tb³⁺的能量传递提供了条件。将(La,Ce,Tb)BO₃的发射光谱与商品粉(La,Ce,Tb)PO₄进行比较,两者的发射主峰都在541 nm处, (La,Ce,Tb)BO₃在489 nm处的峰位稍有红移,通过计算表明,(La,Ce,Tb)BO₃的发光亮度达到商品粉(La,Ce,Tb)PO₄的94.7%。因此,(La,Ce,Tb)BO₃是一种很有应用前景的绿色发光粉。     

富镧混合稀土-镍贮氢材料CO,O2和H2O中毒的表面特征

本文用UPS,XPS研究了贮氢材料MlNi₅(Ml=La,Ce,Pr,Nd)的CO,O₂和H₂O的中毒,在UPS谱中,我们观察到在E_F以下峰α(0.3eV)和峰b(1.2eV)强度随中毒气体暴露量增加有显著变化,并向低动能端位移,逐渐形成肩峰,与此同时,峰c(6eV)和峰d(9.5eV)的强度随暴露量增加而增加,并有能量位移,配合XPS分析,分别确定相应的化学态。氧中毒后的MlNi₅,经300℃加氢还原,从UPS谱可以看到峰α,b强度增加;H₂O和CO中毒后,在超高真空条件下,分别经300℃加热处理,和Ar⁺剥离方法,均获得类似的效果,XPS分析进一步证实了这些结果。实验给出了贮氢材料MlNi₅中过渡金属镍的d电子与气体自由分子轨道间电荷转移的信息,为在实际应用中认识此类贮氢合金的表面催化中毒和再生提供了依据。 关键词：     

新型金属间化合物Sm(TiFe)12的结构与磁性

SmTiFe_x(x的数值为8—11)可形成稳定的金属间化合物,经测定,晶体结构属于ThMn₁₂型四方结构,空间群为14/mmm,本文着重分析了Sm(TiFe)₁₂和Gd(TiFe)₁₂的结构和磁性。Sm(TiFe)₁₂具有很强的单轴磁晶各向异性,易磁化方向为c轴,居里温度610K。通过对Gd(TiFe)₁₂磁性的研究,进一步分析了在Sm(TiFe)₁₂中Sm和Fe次晶格的各向异性,实验结果表明,Sm和Fe次晶格都具有单轴磁晶各向异性,易磁化方向皆沿c轴。这是继Nd₂Fe₁₄B型永磁体以后发现的又一种具有单轴磁晶各向异性的三元稀土-铁金属间化合物。 关键词：     

荧光粉MPO4：Eu3+,Bi3+/Tb3+ (M=La,Gd,Y) 的结构及发光性能研究

采用高温固相法合成了一系列MPO₄：Eu³⁺,Bi³⁺ （M=La,Gd,Y）及 MPO₄：Tb³⁺ （M=La,Gd,Y）荧光粉材料,用X射线衍射（XRD）仪对样品结构进行了表征。所合成的LaPO₄和GdPO₄属单斜晶系,而YPO₄属体心立方晶系。用Diamond软件对结构进行分析并绘出了晶胞结构。对样品发光性质的研究结果表明,虽然MPO₄（M=La,Gd,Y）均属于正磷酸盐,但由于晶格结构不同,其发光性质也不同。立方晶系的YPO₄更有利于掺入其中的稀土离子的发光,Bi³⁺离子的引入能够明显改善样品的发光性能。     

元素替代对MgH2储氢材料释氢影响机理的第一原理研究

用基于密度泛函理论的赝势平面波第一原理方法研究金属元素替代对MgH₂释氢的影响机理.结果表明：带隙的宽窄和带隙中是否存在杂质能级是影响MgH₂储氢材料释氢性能的关键因素,Nb,Fe,Ti,V在能隙近中央引入杂质能级,使得MgH₂的H-Mg键键强减弱,有利于放氢.La在导带底引入杂质能级,降低带隙宽度,晶体中结合最弱的键断裂变得容易,也有利于放氢.Nb,Fe,Ti,V,La与近邻氢原子间形成共价键,形成金属氢化物,对释氢起到催化作用.La与H间的共价作用较弱,其金属氢化物的催化作用相对较弱.掺杂元素使Mg与周围H的静电作用力不对称,与Mg作用力小的H容易释放出来,起到提高MgH₂释氢的作用.比较发现V,Fe明显降低Mg-H间的离子键强度.     

铝酸盐水泥矿物结构与性能的量子化学计算研究

用量子化学的电荷自洽离散变分Xα(SCC-DV-Xα)计算方法研究了CaO-Al₂O₃系统五种水泥矿物的结构、性能与化学键之间的关系及固溶的杂质离子Na⁺对矿物性能的影响。计算结果表明:Ca-O共价键强度的次序是C₃A < C₁₂A₇ < CA < CA₂ < CA₆,且各矿物的Ca-O键强度都小于它们的Al-O键强度,与相应的水泥矿物水化活性的实验结果一致。Na⁺固溶于C₃A结构后使其Al-O键增强,水化活化能变大,态密度减小,被认为是Na⁺降低C₃A水化活性的主要原因。     

Superconducting transition of amorphous TiFe,ZrFe and HfFe produced by Fe implantation

Amorphous TiFe, ZrFe and HfFe alloys prepared by low temperature implantation of about 10 at% Fe were found to have superconducting transition temperatures, T_c, enhanced above the values of the pure crystalline elements. In addition, T_c = 2.6 K for TiFe is about 1 K higher than T_c of the equivalent amorphous TiCu alloy. A correlation between the recently observed dband behavior of similar binary transition metal alloys and the forming ability is extended to (Ti,Zr,Hf)-Fe alloys to explain their superconducting properties.     

Energy of hydrogen dissolution in FCC hydrides of disordered Ti–V–Cr alloys according to density functional theory data

Ti–V–Cr alloys are hydrogen storage materials, but their characteristics, which are important for practical applications, depend strongly on composition. The search for an optimal composition with given characteristics requires the support of theoretical calculations of the electronic structure of alloys and their hydrides. In this paper, the interstitial energy and energy of hydrogen dissolution in the hydride of a ternary disordered Ti_0.33V_0.27Cr_0.4H_1.75 alloy with a face-centered cubic lattice were calculated within the framework of the density functional theory using the pseudopotential method. The deviation of the dissolution energy distribution from the Gaussian distribution is shown. Based on the data obtained for a particular hydride, the energy distributions of hydrogen dissolution in a number of hydrides of alloys (Ti_0.8Cr)_1–xV_x with x = 0.9, 0.8, 0.7, and 0.6 have been derived. A correlation was found between the theoretically calculated width of the energy distribution of hydrogen dissolution and the experimental slope of the pressure “plateau.”     

Glass formation and microstructure evolution in Al–Ni–RE (RE = La,Ce, Pr,Nd and misch metal) ternary systems

Glass formation has been systematically studied in melt-spun Al-rich Al–Ni–RE (RE?=?La, Ce, Pr, Nd and Mm; Mm?=?misch metal) alloys by navigating the compositions following the observation of microstructure evolution in the resulting ribbons. The optimum glass-forming regions are similarly located around Al₈₅Ni₁₀RE₅ and found in the centre of the composites with primary phase α-Al, Al₁₁RE₃ and Al₃Ni. The similarities in the critical cross-section below which a component is fully amorphous and the optimum compositions in these Al–Ni–RE systems are interpreted in terms of their competing crystalline phases and thermodynamic properties. Interestingly, it is indicated that Ni content is markedly higher than RE content in the best glass-forming alloys, which may be associated with strong interaction between Ni–Al atom pairs and the dense packing due to Ni-centred clusters.     

Magnetic properties of Ho1−xMmxCo2 (x=0, 0.1, 0.2, 0.3 and 0.4) alloys and their hydrides

The influence of Mm (Mm=mischmetal) substitution and hydrogen absorption on the magnetic properties of Ho_1−xMm_xCo₂ (x=0, 0.1, 0.2, 0.3 and 0.4) alloys have been determined through the temperature dependence of ac susceptibility and thermopower measurements. The changes in magnetic-ordering temperature of Ho_1−xMm_xCo₂ alloys have been explained based on the dilution of the magnetic ions and weakening of 4f–3d exchange interactions. The gradual disappearance of the magnetic transition temperature upon increasing hydrogen concentration (y) has been interpreted by the lattice expansion and charge transfer between absorbed hydrogen and 3d-band of Ho_1−xMm_xCo₂.     

钒基固溶体储氢材料弹性性质第一性原理研究

采用基于密度泛函理论的第一性原理赝势平面波方法,计算了（59Cr-41Ti）_100－xV_x（x=5,15,30,60,80,100）六种钒基储氢合金的晶格常数、弹性性质和电子态密度,计算结果与实验值符合较好.发现当x=60时的钒基合金具有较好弹性性质,杨氏模量为14930 GPa,切变模量为5442 GPa及体弹模量为19396 GPa.结合实验循环性能分析认为在吸放氢过程中合金已经发生塑性变形,弹性 关键词： 钒基固溶体 储氢合金材料 密度泛函理论 弹性性质     

Effect of multielement doping on low-field magnetotransport in La0.7−xMmxCa0.3MnO3 (0.0?x?0.45) manganite

We report the synthesis, structure and low-field magnetotransport properties of Mischmetal (Mm)-doped La_0.7−xMm_xCa_0.3MnO₃ (0?x?0.45) manganite. Mischmetal—Mm—is a natural mixture of rare earth elements La, Ce, Pr and Nd with ∼28%, 50%, 6% and 16% composition, respectively. All the samples crystallize in orthorhombic structure. Increasing x (Mm), corresponding to decreasing the La-site average ionic radii (〈r_A〉) hence increasing the size mismatch (i.e. variance σ²), results in strong suppression of ferromagnetism (T_C) and the associated metallicity (T_IM). It may be pointed out that Mm (La, Ce, Pr and Nd) substitution has been done to create two effects. First, creation of multivalence of Mn (2+, 3+ and 4+) via Ce substitution and second to create higher degree of disorder due to size difference brought in not only by Ce but also by Pr and Nd. Evidences and arguments based on XPS analysis suggest that multivalent ions La, Mm and Ca, and the resulting presence of Mn²⁺, Mn³⁺ and Mn⁴⁺, causes the simultaneous operation of ferromagnetism-double exchange (Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺) and antiferromagnetic-superexchange (Mn³⁺/Mn³⁺ and Mn²⁺/Mn²⁺) interaction. In addition, Mm doping also creates inhomogenities at La—as well as Mn—site due to size and valency difference. A curiously huge magnetoresistance as high as ∼63% for x=0.35, under a moderate magnetic field of ∼10 kOe has been observed and even at low magnetic field of ∼3 kOe MR is ∼30%. The competing double exchange and superexchange coupled with inhomogenities are the most likely cause for the occurrence of large ∼63% CMR in the Mm-doped LCMO.     

Study of the Characteristics of Elementary Processes in a Chain Hydrogen Burning Reaction in Oxygen

The characteristics of possible chain explosive hydrogen burning reactions in an oxidizing medium are calculated on the potential energy surface. Specifically, reactions H₂ + O₂ → H₂O + O, H₂ + O₂ → HO₂ + H, and H₂ + O₂ → OH + OH are considered. Special attention is devoted to the production of a pair of fast highly reactive OH radicals. Because of the high activation threshold, this reaction is often excluded from the known kinetic scheme of hydrogen burning. However, a spread in estimates of kinetic characteristics and a disagreement between theoretical predictions with experimental results suggest that the kinetic scheme should be refined.     

氢对几种非晶态合金磁性的影响

本文研究了电解充氢对3种不同成分的非晶态合金磁性的影响。实验结果表明,充氢后试样变得很脆,软磁特性显著变劣,但饱和磁化强度σ₃和平均超精细场H_f显著提高。将试样在室温下放置,随着氢气的外逸,磁性、韧性以及H_f可得到逐步恢复。 关键词：     

The synthesis and properties of nanocrystalline electrode materials by mechanical alloying

In this work, we have experimentally studied the structure and electrochemical properties of nanocrystalline TiFe- and LaNi₅-type alloys. These materials were prepared by mechanical alloying (MA) followed by annealing. The properties of hydrogen host materials can be modified substantially by alloying to obtain the desired storage characteristics. It was found that the respective replacement of Fe in TiFe by Ni and/or by Cr, Co, Mo, Zr improved not only the discharge capacity but also the cycle life of these electrodes. In the nanocrystalline TiFe_0.25Ni_0.75, powder discharge capacity up to 155 mA h g⁻¹ was measured (at 40 mA g⁻¹ discharge current). On the other hand, a partial substitution of Ni by Al or Mn in LaNi_5−xM_x alloy leads to an increase in discharge capacity. The alloying elements such as Al, Mn and Co greatly improved the cycle life of LaNi₅ material. For example, in the nanocrystalline LaNi_3.75Mn_0.75Al_0.25Co_0.25 powder, discharge capacity up to 258 mA h g⁻¹ was measured (at 40 mA g⁻¹ discharge current). The studies show, that electrochemical properties of Ni–MH batteries are the function of the microstructure and the chemical composition of used electrode materials.