源于“团簇-共振”模型的理想金属玻璃电子化学势均衡

理想金属玻璃是指完全满足电子结构稳定性的金属玻璃. 在我们前期工作中提出的“团簇加连接原子"及理想金属玻璃的“团簇-共振"结构模型的 基础上, 本文指出理想金属玻璃应该满足电子化学势均衡判据, 可定量给出团簇与连接原子的比例, 最终确定了理想金属玻璃成分式[团簇](连接原子)_x. 运用此判据, 解析了Cu-Zr基和Co-B基块体金属玻璃, 实验确定的最佳形成能力成分满足电子化学势均衡.     

体心立方固溶体合金中的"团簇+连接原子"结构模型

为体现固溶体合金中的溶质原子产生的化学短程序,文章提出了配位数为14的团簇在体心立方(bcc)点阵中的堆垛模式,并建立了基于bcc结构的"团簇+连接原子"结构模型,用团簇成分式[团簇](连接原子)_x表述. 此模型中,与基体组元具有相对大的负混合焓的溶质原子占据团簇心部,其他原子作为连接或者替代团簇壳层基体原子. 1 ∶1结构模型[团簇](连接原子)₁由于最大程度地保证了团簇与连接原子的近邻,构成了连接原子最有效的合金化方式. 在两个实用bcc固溶体合金体系中, 1 ∶1模型指导设计了低V含量的储氢合金 V₁和低弹性模量高强度的 Nb₁合金. 关键词： 体心立方固溶体成分设计 "团簇+连接原子"结构模型 Ti-Cr-V合金 Ti-Zr-Mo-Nb合金     

Co-Al-W基高温合金的团簇成分式

Co-Al-W基高温合金具有类似于Ni基高温合金的γ+γ'相组织结构.根据面心立方固溶体的团簇加连接原子结构模型,Ni基高温合金的成分式即最稳定的化学近程序结构单元可以描述为第一近邻配位多面体团簇加上次近邻的三个连接原子.本文应用类似方法,首次给出了Co-Al-W基高温合金的团簇成分式.利用原子半径和团簇共振模型,可计算出Co-Al-W三元合金的团簇成分通式,为[Al-Co_(12)](Co,Al,W)_3,即以Al为中心原子、Co为壳层原子的[Al-Co_(12)]团簇加上三个连接原子.对于多元合金,需要先将元素进行分类:溶剂元素——类Co元素Co (Co, Cr, Fe, Re, Ni,Ir,Ru)和溶质元素——类Al元素Al (Al,W,Mo, Ta,Ti,Nb,V等);进而根据合金元素的配分行为,将类Co元素分为Co~γ(Cr, Fe, Re)和Co~(γ')(Ni, Ir, Ru);根据混合焓,将类Al元素分为Al, W (W, Mo)和Ta (Ta, Ti, Nb, V等).由此,任何多元Co-Al-W基高温合金均可简化为Co-Al伪二元体系或者Co-Al-(W,Ta)伪三元体系,其团簇加连接原子成分式为[Al-Co_(12)](Co_(1.0)Al_(2.0))(或[Al-Co_(12)] Co_(1.0)Al_(0.5)(W,Ta)_(1.5)=Co_(81.250)Al_(9.375)(W,Ta)_(9.375) at.%).其中,γ与γ'相的团簇成分式分别为[Al-Co_(12)](Co_(1.5)Al_(1.5))(或[Al-Co_(12)] Co_(1.5)Al_(0.5)(W,Ta)_(1.0)=Co_(84.375)Al_(9.375)(W,Ta)_(6.250) at.%)和[Al-Co_(12)](Co_(0.5)Al_(2.5))(或[Al-Co_(12)] Co_(0.5)Al_(0.5)(W, Ta)_(2.0)=Co_(78.125)Al_(9.375)(W,Ta)_(12.500)at.%).例如,Co_(82)Al_9W_9合金的团簇成分式为[Al-Co_(12)]Co_(1.1)Al_(0.4)W_(1.4)(～[Al-Co_(12)]Co_(1.0)Al_(0.5)W_(1.5)),其中γ相的团簇成分式为[Al-Co_(12)]Co_(1.6)Al_(0.4)W_(1.0)(～[Al-Co_(12)]Co_(1.5)Al_(0.5)W_(1.0)),γ'相的团簇成分式为[Al-Co_(12)]Co_(0.3)Al_(0.5)W_(2.2)(～[AlCo_(12)]Co_(0.5)Al_(0.5)W_(2.0)).     

Invar合金的电子化学势均衡判据

用二元团簇作为描述Invar合金的基本结构单元,运用"团簇共振"结构模型,建立起以某一已知二元团簇与连接原子按1:x比例连接,描述Invar合金的电子化学势均衡判据.给出了Invar合金成分的经验分子式,即Invar合金成分=[团簇]1(连接原子)x.运用此判据,解析了部分Invar合金成分.发现典型的Invar合金实验成分与经验分子式相符合,说明基于"团簇共振"模型的Invar合金的电子化学势判据很好地解释了Invar合金成分的形成规律.     

面心立方固溶体合金的团簇加连接原子几何模型及典型工业合金成分解析

工业合金牌号的成分选择体现了固溶体合金的化学短程有序结构,满足由最近邻两层原子组成的"团簇加连接原子"模型,例如对于置换型面心立方固溶体Cu-Zn,其合金牌号成分可以表述为[Zn-Cu_(12)]Zn_(1-6)和[Zn-Cu_(12)](Cu,Zn)_6,其中方括号内为第一近邻配位多面体团簇.基于此,本文赋予团簇式以具体原子结构的含义,对置换型面心立方固溶体结构中团簇的可能存在形式进行了穷尽,得出团簇式所对应的所有"团簇加连接原子"结构单元模型,给出团簇和连接原子之间的比例和空间排列的所有可能,并对Cu-Zn和Cu-Ni合金常用牌号对应的团簇式给出了三维结构模型,进一步验证了前期关于合金团簇式解析的正确性.用这些模型中原子化学序描述合金的成分,赋予团簇式以具体的原子结构意义,为进一步开发新的合金提供了理论依据.     

判定金属玻璃微观结构中的二十面体类团簇

基于Voronoi几何分形法, 分析了理想二十面体团簇和ZrCu二元金属玻璃中各种团簇的结构特点, 提出了一种判定金属玻璃原子结构中二十面体类团簇的方法. 并选取三个ZrCu 非晶成分作为研究对象, 基于Voronoi团簇, 利用该方法提取了各种构型团簇, 证实其中四种构型团簇的基本几何结构与理想二十面体相似, 并具有同样近似于理想二十面体的高致密度、高规则度和高五次对称性, 因此可称之为二十面体类团簇. 此类二十面体类团簇可作为金属玻璃的主要结构单元, 普遍存在于非晶结构中; 二十面体类团簇及其连接能包含几乎所有的原子, 从而形成非晶结构. 研究结果提供了一种新的团簇判定方法, 有助于从微观结构层面分析合金中的非晶形成机理.     

Mg-Al系工业合金牌号的成分式解析

Mg-Al系牌号是应用最广的镁基工业合金,但其牌号背后的成分根源一直未知,构成研发新合金的主要障碍.本文应用描述固溶体短程序结构特征的团簇共振模型,得到了Mg-Al二元固溶体的最理想化学结构单元[Al-Mg_(12)]Mg_1,然后对《the American Society for Testing Materials》手册中所有Mg-Al系工业合金牌号进行成分解析,得到相应团簇成分式,如AZ63A合金解析后的团簇成分式为[Al_(0.78)Zn_(0.16)-Mg_(12)]Mg_(1.04)Mn_(0.02),AZ81A合金解析后的团簇成分式为[Al_(0.97)Zn_(0.03)-Mg_(12)]Mg_(0.98)Mn_(0.02).再根据成分式与化学结构单元之间的误差,对比该牌号合金的力学性能,验证了该化学结构单元在Mg-Al体系中的准确性,揭示出看似复杂的工业合金牌号后面隐藏的简单成分规律,为发展Mg-Al体系合金指出了一个全新的途径.     

基于β-FeSi2的(Fe, M)Si2三元合金相形成规律

二元β-FeSi₂相是一种重要的窄带半导体型金属硅化物,研究了基于该二元相的三元合金的形成规律,以丰富其材料范围.首先,利用团簇线判据作为理论依据,选取一个团簇和一个连接原子构成的模型,添加不同的第三组元作为连接原子,设计了Fe₃Si₈M(M=B, Cr, Ni, Cu, Co, Al）系列合金成分,即用添加组元替代二元相中的Fe连接原子.然后,用真空吸铸和真空甩带方法制备合金棒以及薄带,以获得无成分偏析的均匀合 关键词： 2')" href="#">β-FeSi₂ 三元合金 团簇线     

Rh_nAl(n=1～6)团簇结构和磁性的研究

用密度泛函理论中的广义梯度近似方法研究了Rh_nAl(n=1～6)团簇的结构和磁性.结果表明:Rh(_n-1)Al和Rh_n(n=2～7)团簇结构是相似的,结合能随团簇尺寸变化趋势一致,原子间的s,p,d轨道杂化使得Rh_nAl团簇更加稳定.几乎所有Rh原子都是电子受体,Al-Rh键长越小.Rh原子得电子就越多.团簇磁矩主要来自Rh原子的贡献,Rh原子的4d轨道磁矩是Rh原子磁矩的主要部分.Al原子失去的电子越多,则其磁矩就相对越小.     

第一性原理计算LiNBe(N=1～12)团簇的基态结构及其电子性质

从第一性原理出发利用密度泛函理论(DFT)计算了LiNBe(N=1-12)团簇的基态结构及其电子性质.计算结果表明:铍掺杂锂团簇LiNBe(N=1-12)的基态结构相当于Be原子取代LiN 1主团簇基态结构中一个Li原子的位置;当团簇尺寸N≥6时,杂质原子Be被束缚在主团簇笼子内;随着团簇尺寸增大,团簇的离解能和二阶能量差分均出现了奇-偶振荡;从结构稳定性上来看,Li6Be是个幻数团簇.     

Characteristics of cobalt-based alloy coating on tool steel prepared by powder feeding laser cladding

Co-based alloy coating was deposited on tool steel by powder feeding laser cladding. Sections of such coatings were examined to reveal their microstructures and phases using scanning electron microscope (SEM) and X-ray diffractometer (XRD). The results showed that the prime phase (γ-Co dendrite) and other phases, including Cr₂₃C₆, Co₇W₆, and CrNi existed in the coatings. Some different solidification morphologies, such as planar (at the interface), cellular and dendrite formed, varying from the interface to the surface. Fine microstructures of γ-Co dendrite and lamellar eutectic in dendritical regions strengthened the coatings. Besides, the effects of aged treatment on the microstructure and microhardness of the surface coating were studied. Aged treatment led to the precipitations of some carbide particles (Cr₇C₃ and Co₃C) and boride particles (Co₄B) from the cladded coating, causing an increase in microhardness in the laser-cladded coating.     

Microstructure and wear resistance of laser clad cobalt-based alloy multi-layer coatings

Multi-layer Co-based alloy (HMSP 2537) were deposited on Ni-based superalloy plate with a TJ-TL-T5000 type CO₂ laser. Sections of such coatings were examined to reveal their microstructure and phase composition using optical microscope, scanning electron microscope (SEM), and X-ray diffractometer (XRD). The hardness and wear resistance of the coatings were tested. The results showed that the prime phase (γ-Co dendrite) and other phases, such as CrNi, Co₇W₆, and Cr₂₃C₆ existed in the coatings. Dendrite or cellular microstructures were observed perpendicular to the interface, and coarsening microstructures were obtained as more layers deposited. Dendrite paralleling to laser scan speed was also found near the top surface of the last layer. Fine microstructures of γ-Co dendrite and lamellar eutectic in inter-dendritic regions strengthened the coatings. Microhardness and wear resistance of the coatings were much higher than that of substrate but slightly decreased with layers increased.     

Cluster formulae for metallic glasses derived from devitrification phases

Bulk metallic glasses are known to have a composition formula [cluster](glue atom)_1,3 within the framework of the cluster-plus-glue-atom model. The key issue in applying the cluster formula is the determination of the right clusters and glue atoms. As examples, alloy phases in the glass-forming systems Al–Ni–Zr and B–Co–Si are analysed from the viewpoint of nearest coordination polyhedral clusters. These alloy phases are described by [effective cluster](glue atom) _x , where the effective cluster refers to true cluster composition after taking account of cluster-sharing in the phase structure. For each alloy phase, a principal cluster can be identified that features the local short-range order of that phase. It is pointed out that the principal clusters can express compositions with high glass-forming abilities, as verified by our experiments in Al–Ni–Zr and B–Co–Si–Ta.     

过渡金属硼碳化物TM_3B_3C和TM_4B_3C_2稳定性和性能的理论计算

在过渡金属轻元素化合物中,寻找新的硬质或者超硬材料是当前的一个研究热点.目前寻找范围多集中在过渡金属硼化物、碳化物和氮化物等二元体系,三元相的研究则相对较少.本文以已知Nb_3B_3C和Nb_4B_3C_2结构为模板,采用元素替代法构建了29种TM_3B_3C (TM为过渡金属元素)结构和29种TM_4B_3C_2结构,采用基于密度泛函理论的第一性原理计算方法,成功找到了热力学、动力学以及力学都稳定的Ta_3B_3C和Ta4B_3C2两种新相.结构搜索计算确认了这两相为全局能量最优结构.能带结构和态密度的计算显示这两相均为导体,导电性主要源于Ta原子的d电子.这两种新相的硬度大约为26 GPa,说明Ta_3B_3C和Ta_4B_3C_2属于高硬度材料,但不是超硬材料.     

GEOMETRIC AND ELECTRONIC STRUCTURES OF Ti8C12 CLUSTER

The electronic structure of Ti₈C₁₂ clusters with three possible geometric structures suggested in the literature is studied using the discrete-variational local-density-functional method. The results show that the ground states of the clusters are all degenerate, which means further Jahn-Teller distortions for the geometric structures of clusters. The results also indicate that the distorted dodecahedral Ti₈C₁₂ cluster, which is proposed by Guo et al. and optimized by the first principle calculations, is the most stable one among the clusters we considered and its electronic structure can explain the experimental observations. In this cluster, there is a strong pd bonding between Ti and C atoms, and the density of states at the Fermi energy is high.     

Microstructural analysis of carbonitrided austenitic steels

An austenitic heat resisting steel containing 25% Cr and 19% Ni was internally carbonitrided in an atmosphere of 0.5% C₃H₆, 9.5% H₂ and 90% N₂. Immediately below the alloy surface, globular precipitates were observed. At greater depth, two zones of lamellar morphology precipitates were observed to form. M₇C₃ was found directly beneath the surface and M₂₃C₆ was found closer to the reaction front. The lamellar carbide morphology is more typically characteristic of the precipitates formed during nitriding rather than carburising, suggesting that nitrogen plays some role in the precipitation process. A focused ion beam (FIB) miller was used to create thin, electron transparent locations at specific regions in the precipitation zone in order to characterise, via transmission electron microscopy, the crystallography and composition of the phases present. In this study, thin areas were produced in the lamellar region at the transition between the M₂₃C₆ and M₇C₃ regions. The composition, crystal structure, and orientation relationships are reported and compared to those found previously at both the internal precipitation front and the sample surface.     

Metallic Rb4C60 and Rb5C60 on the top layer of C60 single crystal

Photoemission studies reveal the existences of metallic Rb₄C₆₀ and Rb₅C₆₀ surface phases on the top layer of C₆₀ single crystal. After Rb₃C₆₀ thin film with thickness of nanometers has formed on the (1 1 1) surface layers of the C₆₀ single crystal, the excess deposition of Rb atoms do not induce the bulk-like face-centered cubic to body-centered tetragonal or body-centered cubic structure transitions at room temperature. The large size of C₆₀ molecule offers the surface vacancies for the formation of Rb₄C₆₀ and Rb₅C₆₀ monolayer that is further verified by Rb 3d core-level photoemission measurements. Valence band photoemission results exhibit the surface phases are metallic.