铜金二元系中超结构的形成与点阵间隔的变迁

本文用X射线衍射的方法全面地研究了Cu-Au二元系合金经不同时间(一个月、三个月、六个月、一年)熟炼后缓冷到室温,以及在300℃和600℃淬炼后的物相与相转变过程;精确地测定了点阵间隔,以研究其随成份和热处理的变迁;探讨了长周期超结构的堆垜周期同成份和温度的关系;并用保持不同热处理时间后淬炼的方法来研究等原子成份处的有序化过程。在上述的热处理条件下,整个二元系共出现了六种不同的相:α₁是Au在Cu中的固溶体,α′₁是相当于Cu₃Au的超结构,α₂是Cu在Au中的固溶体,α′₂是相当于CuAu₃的超结构,k是相当于CuAuⅠ的超结构,k′是相当于CuAuⅡ的超结构。值得注意的是,随着热处理时间的加长,有序区逐渐扩大,二相区逐渐缩小,在一年缓冷的合金,二相区几乎完全消失。因此作者认为:Cu-Au系的二相共存是处于介稳状态,以α′₂相而论,最清晰的超结构线并不出现在化学计量成份而在68at.％Au。在等原子成份两边所出现的k′相,当合金经一年熟炼之后,一部分又变成了k相,在等原子成份处,k相和k′相的最高转变温度都并不恰好在等原子成份,而在于或小于49at.％Au。点阵间隔的量度表明:基本单胞平均点阵间隔同成份的关系是正偏离Vegard定律的连续曲线。在α和α′相区内,α值随Au含量而递增。在Au含量小于等原子成份的k′相区内,α值随Au含量而递增,c值则反而递减,同时c/α愈来愈偏离1。而在Au含量大于等原子成份的k′相区内,α值随Au含量的增加而缓慢地下降,c值却随之急速上升,同时c/α愈来愈趋向于1。当k′相转变为k相或k相转变为k′相时,α和c均发生突然的跃变。以热处理时间对点阵间隔的关系而论,在α,α′及k相区内,凡相状态不随熟炼时间而变的部分,点阵间隔在实验条件的范围内是恒定的。在α′₂相区内,从无序相转变到有序相时发生点阵间隔的明显下降,在k′相区内,则凡Au含量小于等原子成份的合金,α值随处理时间而递增,c则递减;而Au含量大于等原子成份的合金,α和c都随处理时间的加长而递减。但在所有k′相区内,同一成份合金的基本单胞体积都随处理时间的增加而减小,作者因此认为:应该把基本单胞的体积作为有序度的普通量度。本文详尽地讨论了k′结构超结构线的指数出现规律和它同k结构超结构线指数的对应关系。从在k到k′的变化中劈裂成双线的线间距离准确地测定了k′结构的堆垜周期,堆垜周期随成份的变化是连续的。凡合金离理想成份愈远,堆垜周期愈大。同一成份的合金,温度愈高则堆垜周期愈大。堆垜周期可以为奇数,也可以为非整数。在介稳二相区内,非但点阵间隔随成份而变,而且k′相的堆垜周期也随成份而变。二相1963年8月曾在长春市举行的第一届全国物质结构学术会议上宣读过。共存实际上是由一种成份的两种结构形式所组成。本文纯粹从热力学的关系证明了Cu-Au二元系的有序、无序变化是二级相交。     

MnGa的晶体结构与有序度

本文叙述了用德拜·谢乐的方法探讨Mn-Ga二元系中γ₃相的晶体结构,并进一步研究了在这个相区内原子排列的有序度随Ga含量的变迁。γ₃相属四方晶系,空间群为D_4h¹—P4/mmm,其理想配比成分为MnGa,每晶胞含1个化合式量,Mn原子和Ga原子分别占据着(0,0,0)和(1/2,1/2,1/2)等效位置。这是一种畸变型的B2结构,如果原晶胞沿c轴转动π/4,则变换后的晶胞就是LI₀型结构,与CuAu-1同型。在室温,原晶胞在42.9at.％Ga成分处的点阵常数为a=2.7475?,c=3.6756?。这个相可看作是γ-Mn的替代式固溶体,由于Ga原子替代了部分Mn原子而在室温稳定存在为四方面心有序结构。在整个相区内,有序度随Ga含量的增加而增加。 关键词：     

Al-Ni-Co三元系中(Ni,Co)_3Al_4的晶体结构——一种由空位控制的新合金相

(Ni,Co)_3Al。是Al-Ni-Co三元系中的一种三元相,其均匀存在范围在室温为,55—58.5A/0Al,26—35A/0Ni和10-15.5A/0Co。这个三元相属立方晶系,空间群为O_k~(10)-Ia3d,每晶胞含112个原子,在室温的点阵常数为α=11.3962。 这个结构是由64个CsCI型基本结构单位堆垛而成的一种超结构。在这64个基本结构单位中,有16个体心位置是有序地空着的,在16(b)的等效位置上构成了16个八面体空位。基本结构单位的角位置16(a)和48(f)都由Al原子占据着,而心位置48(g)则由Ni原子和Co原子无规地占据着。由于空位的存在,原子位置从其原来的CsCl型结构单位位置有所偏离;测定的结果是,x_f=0.010,x_g=0.369。 从合金相的存在范围及原子在结构内的分布情况,这个合金相的理想化合式决定为(Ni,Co)_3Al_4,每单胞含16个化合式量。     

Al-Ni-Co三元系中(Ni,Co)3Al4的晶体结构——一种由空位控制的新合金相

(Ni,Co)₃Al₄。是Al-Ni-Co三元系中的一种三元相,其均匀存在范围在室温为,55—58.5A/0 Al,26—35A/0 Ni和10-15.5A/0 Co。这个三元相属立方晶系,空间群为O_h¹⁰-Ia3d,每晶胞含112个原子,在室温的点阵常数为α=11.3962?。这个结构是由64个CsCI型基本结构单位堆垛而成的一种超结构。在这64个基本结构单位中,有16个体心位置是有序地空着的,在16(b)的等效位置上构成了16个八面体空位。基本结构单位的角位置16(a)和48(f)都由Al原子占据着,而心位置48(g)则由Ni原子和Co原子无规地占据着。由于空位的存在,原子位置从其原来的CsCl型结构单位位置有所偏离;测定的结果是,x_f=0.010,x_g=0.369。从合金相的存在范围及原子在结构内的分布情况,这个合金相的理想化合式决定为(Ni,Co)₃Al₄,每单胞含16个化合式量。 关键词：     

“黑漆古”耐腐蚀机理探讨

“黑漆古”铜镜的表面由非金属层和过渡层组成,价电子结构分析指出,非金属层主要成分Sn_1-xCu_xO₂具有与SnO₂相近的稳定性,而实验数据分析发现,过渡层中,δ相铜锡合金与Sn_1-xCu_xO₂的相界上存在着重合位置点阵(CSL)结构,这种结构降低了相界面上铜原子的能量,使这部分δ相晶粒也十分稳定,从而使整个“黑漆古”表面具有耐腐蚀性能。 关键词：     

标定粉末照相指数的一个新图解法

本文叙述了标定德拜-谢乐照相指数的一个新图解法。利用三条低角度衍射线的sin²θ值和该晶体的密度,在A-C空间画一系列条件直线及等原子曲线。三条条件直线和一条等原子曲线的交点直接决定了晶胞的大小和晶胞内所含的原子数或位形单位数。这个方法可应用于四方晶系和六角晶系。 关键词：     

FeGa3的晶体结构

本文用X射线粉末法测定了FeGa₃的晶体结构,FeGa₃属四方晶系。在20℃的点阵常数是:a=6.2628?,c=6.5559?。每晶胞包含四个化合式量。空间羣为D_4h¹⁴——P4₂/mnm。Fe原子占据在4(f)等效位置上,Ga原子占据在4(c)及8(j)等效位置上;参数为:x_f=0.343,x_j=0.157,z_j=0.264。从结构看来,这是金属互化物的一种新类型。     

V2Ga5的晶体结构

本文利用单晶与粉末衍射方法测定了V₂Ga₅的晶体结构。V₂Ga₅属四方晶系,其单相区约为VGa₂—V₂Ga₅。在18℃的点阵常数是a=8.9540?,c=2.6892?,每个晶胞含有二个化合式量,空间羣为D_4h⁵—P4/mbm。V原子与Ga原子分别占据在4(h)与8(i),2(d)的等效位置上。参数为:x相似文献   

Sn3InSb4合金嵌Li性能的第一性原理研究

采用第一性原理超软赝势平面波方法计算了Sn₃InSb₄的嵌Li性能,得到各种嵌Li相的嵌Li形成能、理论质量比容量、体积膨胀率、能带结构、态密度和差分电荷密度等.从能量角度分析,Li在嵌入时,优先占据晶胞的四面体间隙位置,然后逐步挤出处于节点位置的Sn原子和In原子.在嵌Li过程中,材料表现出较大的体积膨胀率(11.74%-43.40%),这是导致Sn₃InSb₄作为Li离子电极材料循环性能差的重要原因.态密度计算表明,体系的导电性能首先随嵌Li量的增加而增加,当所有的间隙位置被Li填满,发生Sn的替换反应时,富Li态合金相的导电性反而下降.     

Mn3Ga的晶体结构

本文用X射线粉末法,测定了Mn₃Ga的晶体结构。Mn₃Ga属六角晶系。26.8at.%Ga的合金在20℃的点阵常数是:a=5.4065?,c=4.3537?,c/a=0.8053。空间群为D_6h⁴-P6₃/mmc。每个单胞含两个化合式量,其中6个Mn原子占据6(h)的位置,原子参数x_h=0.837,2个Ga原子占据2(c)的位置。这是一个畸变型的DO₁₉有序密堆积超结构。Mn-Ga采内相当于这个结构的均匀范围并不包括理想成分在内,而偏移在富Ga的一边。     

铝、铜、镍三元合金系中τ相的晶体结构变迁

A thorough investigation by means of X-rays has been carried out with the purpose to determine the nature of the ternary phase τ in Al-Cu-Ni alloys. In contrast with the conventional concept of alloy phase which is characterized by a definite type of crystal structure, systematic structure changes are found in the single phase field of τ which occupies quite an extensive area in the isothermal section of the phase diagram at room temperature. There are eight types of structures altogether, all derived from a basic rhombohedron with corners occupied by Al atoms and centres either occupied by the heavy atoms or remaining vacant. The basic rhombohedron is the building stone in the crystal architecture. By transforming the basic rhombohedron into a hexagonal prism in the usual way, all structures may be considered to be built up by stacking together a number of these hexagonal prisms along the triad. The transformation of one structure into another is quite systematic in the way that the number of the stacking stories in the unit cell increases according to the order 10, 11, 12, 13, 14, 15, 16, 17. The atomic arrangements in the different structures are closely related too, in the respect that they are all superstructures due to the presence of ordered vacancies in the rhombohedral centres.The principal factor controlling the formation of these structures has been fully considered. In view of the fact that the change of structure types follows closely with the content of Ni or Cu for alloys of constant Al content, the atomic size factor appears to be unimportant in the formation of these alloys. It has been shown that for alloy phases of the defect lattice type as the r-phase, the most fundamental factor is the average number of valency electrons per structural unit which is the basic rhombohedron in the present case. By assuming Hume-Rothery's valencies, the average number of valency electrons remains remarkably constant throughout the entire phase field, while the electron concentration varies with compositions. It has also been pointed out that for alloy phases where there is no unit cell change, the average number of electrons per structural unit is equivalent to the number of electrons per unit cell, and for alloy phase where there is no defect, this is in effect equivalent to the electron concentration.     

B改善单晶和多晶Ni3Al合金力学性能的微观机制

通过测量Ｂ含量从０．００至２．２２ａｔ％的单晶和多晶Ｎｉ₃Ａｌ合金的正电子寿命谱，研究了单晶和多晶Ｎｉ₃Ａｌ合金中的微观缺陷和电子结构。结果表明，多晶Ｎｉ₃Ａｌ合金晶界中存在着开空间大于空位的缺陷。晶界缺陷处参与形成Ｎｉ－Ｎｉ和Ｎｉ－Ａｌ键的价电子浓度比基体或位错处的低，晶界是结合力弱化区域。偏聚到Ｎｉ₃Ａｌ合金缺陷上的Ｂ与缺陷处的Ｎｉ或Ａｌ原子形成强的共价键而增强了这些地方的结合力。以间隙方式固溶到Ｎｉ_{3< 关键词：}     

Origin of magnetic interactions and their influence on the structural properties of Ni2MnGa and related compounds

In this work, we perform first-principles DFT calculations to investigate the interplay between magnetic and structural properties in Ni(2)MnGa. We demonstrate that the relative stability of austenite (cubic) and non-modulated martensite (tetragonal) phases depends critically on the magnetic interactions between Mn atoms. While standard approximate DFT functionals stabilize the latter phase, a more accurate treatment of electronic localization and magnetism, obtained with DFT+U, suppresses the non-modulated tetragonal structure for the stoichiometric compound, in better agreement with experiments. We show that the Anderson impurity model, with Mn atoms treated as magnetic impurities, can explain this observation and that the fine balance between super-exchange RKKY type interactions mediated by Ni d and Ga p orbitals determines the equilibrium structure of the crystal. The Anderson model is also demonstrated to capture the effect of the number of valence electrons per unit cell on the structural properties, often used as an empirical parameter to tune the behavior of Ni(2)MnGa based alloys. Finally, we show that off-stoichiometric compositions with excess Mn promote transitions to a non-modulated tetragonal structure, in agreement with experiments.     

Zn,Ni,Mg高掺杂La1.85Sr0.15CuO4的晶体结构比较

对Zn,Ni,Mg高掺杂的La_1.85Sr_0.15CuO₄(LSCO)超导体的X射线衍射谱进行了仔细的分析,从而获得了各掺杂样品的晶格常量、原子结构参量及衍射的峰形参量,比较了不同掺杂所引起的晶体结构的差异,计算了由于掺杂所产生的晶格内部的微应变,结果表明非磁性金属Zn,Mg掺杂比磁性金属Ni掺杂更强烈地抑制了LSCO的超导电性可能与材料中晶格的微应变有关. 关键词： 1.85Sr_0.15CuO₄')" href="#">La_1.85Sr_0.15CuO₄ 磁、非磁掺杂 原子结构参量 晶格微应变     

Os1-xRexB4固溶体系的结构、力学和电子性质的第一性原理研究

利用第一性原理的计算方法,在维也纳从头计算模拟包(VASP)中计算了三种比例Re原子掺杂Os B₄的结构特征及稳定性、电子性质及力学性能.将P42/nmc相Os B₄中的Os元素进行Re元素的替代掺杂,并构建出Os_1-xRe_xB₄(x=0,0.0625,0.125,0.25)固溶体系的结构模型.结果表明:随Re含量的增高Os_1-xRe_xB₄的晶格常数和体积会略微增大,在x高于0.25后发生结构畸变;且P42/nmc-Os_1-xRe_xB₄(x=0,0.0625,0.125)的结构和热力学稳定;态密度主要来源于Os的5d电子和B的2s和2p电子,而Re原子的5d轨道电子对价带和导带态密度也均有贡献,并且随其含量的增高态密度峰值也增大;B-B键和B-Os键具有强共价相互作用是其具有较高的体积和剪切模量的主要原因.随着Re元素的浓度增加,结构的导电性和延展...     

Analysis of the valence electronic structures and calculation of the physical properties of Fe,Co, and Ni

The valence electronic structures of Fe, Co and Ni have been investigated with Empirical Electron Theory of Solids and Molecules. The magnetic moments, Curie temperature, cohesive energy and melting point have been calculated according to the valence electronic structure. These calculations fit the experimental data very well. Based on the calculations, the magnetic moments are proportional to the number of 3d magnetic electrons. Curie temperatures are related to the magnetic electrons and the bond lengths between magnetic atoms. Cohesive energies increase with the increase of the number of covalent electrons, and the decrease of the number of magnetic and dumb pair electrons. The melting point is mainly related to the number of covalent electron pairs distributed in the strongest bond. The contribution from the lattice electrons is very small, the dumb pair electrons weaken the melting point; however, the contribution to melting point of the magnetic electrons can be neglected. It reveals that the magnetic and thermal properties are closely related to the valence electronic structures, and the changes or transitions between the electrons obviously affect the physical properties. Supported by the National High Technology Development Program of China (Grant No. 2007AA03Z458)     

On the magnetic properties of mechanosynthesized Co-Fe-Ni ternary alloys

X-ray diffraction, Mössbauer spectroscopy and magnetization measurements were used as complementary methods to obtain structural data and to determine magnetic properties of the mechanically synthesized and subsequently thermally treated Co-Fe-Ni alloys. New, however approximate, phase diagrams were established on the basis of X-ray diffraction investigations. Mössbauer spectroscopy and magnetization measurements allowed to reveal practically linear correlation between the average values of the hyperfine magnetic field induction, 〈B_hf〉, and the effective magnetic moments, μ_eff, of the alloys. The decrease in 〈B_hf〉 with the number of electrons per atom, e/a, was observed. Moreover, the dependence of μ_eff on the valence 3d and 4s electrons per atom follows the Slater-Pauling curve. Thermal treatment of mechanosynthesized Co-Fe-Ni alloys led to some changes in the phase diagrams, increase in the grain size and decrease of the level of internal strains in alloys. Dependencies of lattice constants, average hyperfine magnetic fields, effective magnetic moments and Curie temperatures on the number of electrons per atom have the same trends for mechanically synthesized as well as for thermally treated alloys.     

Correlation between electronic structure and energy band in Eu-doped CuInTe_2 semiconductor compound with chalcopyrite structure

The Eu-doped Cu(In, Eu)Te_2 semiconductors with chalcopyrite structures are promising materials for their applications in the absorption layer for thin-film solar cells due to their wider band-gaps and better optical properties than those of CuInTe_2. In this paper, the Eu-doped CuInTe_2(CuIn_(1-x)Eu_xTe_2, x = 0, 0.1, 0.2, 0.3) are studied systemically based on the empirical electron theory(EET). The studies cover crystal structures, bonding regularities, cohesive energies, energy levels,and valence electron structures. The theoretical values fit the experimental results very well. The physical mechanism of a broadened band-gap induced by Eu doping into CuInTe_2 is the transitions between different hybridization energy levels induced by electron hopping between s and d orbitals and the transformations from the lattice electrons to valence electrons for Cu and In ions. The research results reveal that the photovoltaic effect induces the increase of lattice electrons of In and causes the electric resistivity to decrease. The Eu doping into CuInTe_2 mainly influences the transition between different hybridization energy levels for Cu atoms, which shows that the 3d electron numbers of Cu atoms change before and after Eu doping. In single phase CuIn_(1-x)Eu_xTe_2, the number of valence electrons changes regularly with increasing Eu content,and the calculated band gap E_g also increases, which implies that the optical properties of Eu-doped CuIn_(1-x)Eu_xTe_2 are improved.