Ab initio molecular-dynamics simulations of short-range order in liquid Al80Mn20 and Al80Ni20 alloys

Atomic structures of liquid Al80Mn20 and Al80Ni20 have been calculated by first-principles molecular-dynamics simulations. For both liquid alloys, the local structure is characterized by a strong Al-TM (transition metal) affinity, which leads to a well-pronounced chemical short-range order. However, we show that the occurrence of magnetic moments localized on Mn atoms plays a key role in determining the short-range arrangement of Mn atoms which is also interpreted on the basis of the local fivefold symmetry.     

钴和铁熔体短程序的分子动力学模拟

通过分子动力学模拟研究了金属钴和铁熔体从普通液态到过冷液态普通微观结构的性质.所计算两体分布函数与可获得的实验结果基本一致,从普通液态到过冷液态的局域结构中的原子配位数为11和12的分布几率随着温度的降低而变小,而原子的配位数大于12的分布几率反而增加,角分布函数位于55.有一个明显的峰,位于110°有一个宽展的峰,位于150°有一个肩膀,表明金属钴和铁熔体的微观局域结构要比规则的二十面体团簇的结构复杂得多.我们的模拟结果表明金属熔体中的二十面体短程序随着温度的降低而增加,并在过冷液态中而占优势.     

非晶合金及合金液体的局域五次对称性

简要回顾了从20世纪30年代至今,有关非晶合金及合金液体的局域结构五次对称性的实验、理论和模拟研究.在简单液体的早期研究中,人们已经意识到五次对称性在简单液体的无序结构、过冷和晶化等起着重要作用,二十面体短程序作为五次对称性的典型代表受到了广泛关注.自从Frank提出简单液体中二十面体短程序的结构单元,大量的理论和实验研究已经明确在简单液体、合金液体和金属玻璃中存在局域五次对称性,并且建立了局域五次对称性与合金液体复杂动力学行为、玻璃转变、液体-液体相变以及非晶合金的形变等统一的定量描述和物理图像,表明了局域五次对称性作为结构参量的简单、普遍和有效性.     

Icosahedral short-range order in amorphous alloys

We have characterized the icosahedral short-range order in amorphous solids using local environment probes. Such topological local order is pronounced even in an amorphous alloy that does not form quasicrystalline phases upon crystallization, as demonstrated by the extended x-ray absorption fine structure and x-ray absorption near-edge structure of a Ni-Ag amorphous alloy analyzed through reverse Monte Carlo simulations.     

The type of atomic distribution in Cd-Al-Sn liquid eutectic alloys

This work presents the results of an x-ray scattering investigation of the short-range order in cadmium-aluminum-tin alloy at the eutectic concentration for a wide interval of temperatures. From the experimental x-ray scattering curves obtained for this sample, a Minsk-22 computer was used to calculate the atomic distribution for different temperatures. According to the analysis of the curves of the scattered x-ray intensity and the atomic distribution curves, it has been established that the eutectic Cd-Al-Sn alloy in the region of complete melting is characterized by a “quasieutectic” distribution of the atoms of the pure components.     

Polyamorphism of liquid silica under compression based on five order-parameters and two-state model: a completed and unified description

The polyamorphism of liquid silica (SiO₂) at 3200?K and in a wide pressure range is investigated by molecular dynamics simulation. Results show that the structure of liquid SiO₂ consists of five order-parameters that do not depend on compression. Three order parameters that relate to the short-range order are SiO_x coordination units (x?=?4, 5, 6) and two order parameters that relate to the intermediate-range order are OSi₂ and OSi₃ linkages. The structure of liquid silica under compression can be described by the two-state model: low-density and high-density states. The low-density state is formed by clustering of OSi₂ linkages (in the low-density state, the short-range order (SRO) is mainly characterized by SiO₄ coordination units), conversely, clustering of OSi₃ linkages will form high-density state (in the high-density state, the SRO is mainly characterized by SiO₅ and SiO₆ coordination units). Under compression, in the liquid silica co-exist two phases: low-density and high-density phases. The size of phase regions significantly depends on compression.     

Using the Ab Initio Molecular Dynamics Method for Simulating the Peculiarities in the Temperature Dependence of Liquid Bismuth Properties

The specific features pertinent to the temperature dependence of the electronic and atomic properties of liquid bismuth that have been observed in experiments are investigated according to the ab initio molecular dynamics method using the SIESTA open software package. The density of electronic states, the radial distribution function of atoms, and the self-diffusion coefficient are calculated for the temperature range from the melting point equal to 545 K to 1500 K. The calculated data are in good agreement with the experimental data. It is found that the position of the first peak in the radial distribution function of atoms and the self-diffusion coefficient are characterized by a nonmonotonic dependence under the conditions of superheating by approximately 150 K above the melting temperature. In the authors’ opinion, this dependence feature is attributed to a change in the liquid short-range order structure.     

Ordering behaviors of the F.C.C. and B.C.C. phase alloys in the InMg,LiMg and AlZn systems

Expressions of the band-structure energy and the electrostatic energy characterized by the usual long-range and short-range order parameters are given to a binary alloy of simple metals with the f.c.c.-type or b.c.c.-type structure.The ordering energy and the local ordering energy are calculated for the InMg, LiMg and AlZn systems. The numerical results explain successfully the facts that the InMg system has the Ll₀-type and Ll₂-type ordered phases, each of which exists over a wide range of concentration and that the LiMg system has a local order with a negative short-range order parameter, while the AlZn system has that with the positive one. A lattice distortion in the Ll₀-type ordered structure of InMg is also discussed.     

Amorphous carbon

The properties of various types of amorphous carbon and hydrogenated amorphous carbon are reviewed with particular emphasis on the effect of atomic structure on the electronic structure. It is shown how the proportion of sp³ and sp² sites not only defines the short-range order but also a substantial medium-range order. Medium-range order is particularly important in amorphous carbon because it is the source of its optical gap, whereas short-range order is usually sufficient to guarantee a gap in other amorphous semiconductors. The review discusses the following properties: short-range order and the radial distribution function, the infrared and Raman spectra, mechanical strength, the electronic structure, photoemission spectra, optical properties, electron energy-loss spectra, core-level excitation spectra, electrical conductivity, electronic defects and the electronic doping of hydrogenated amorphous carbon.     

Reverse Monte Carlo study on structural order in liquid and glassy AlFe alloys

This paper reports that anomalous local order in liquid and glassy AlFeCe alloy has been detected by x-ray diffraction measurements. The addition of the element Ce has a great effect on this local structural order. The element Ce favours interpenetration of the icosahedra by sharing a common face and edges. It argues that frustration between this short-range order and the long-range crystalline order controls the glass-forming ability of these liquids. The obtained results suggest that a system having a stronger tendency to show local icosahedral order should be a better glass-former. This scenario also naturally explains the close relationship between the local icosahedral order in a liquid, glass-forming ability, and the nucleation barrier. Such topological local order has also been analysed directly using the reverse Monte Carlo method. It also estimated the fraction of local ordered and disordered structural units in a glassy AlFeCe alloy.     

MgCu metallic glass

We generate an amorphous MgCu model using the rapid solidification of the melt through a first-principles molecular dynamics approach within a generalised gradient approximation and reveal, for the first time, its structural features and mechanical properties in details. The liquid and glassy MgCu are found to acquire slightly distinct local structures. Yet in both forms of MgCu, most Cu atoms have a tendency to form the ideal and defective icosahedrons while Mg atoms are arranged in complex configurations. The mean coordination number of Cu and Mg at 300 K is 11.31 and 13.73, respectively. The short-range order of MgCu glass is projected to be different than the known crystalline MgCu and Mg₂Cu phases. The mechanical properties of MgCu glass and the CsCl-type MgCu crystal are computed and compared. On the basis of the enthalpy analyses, a possible pressure-induced crystallisation of the MgCu glass into a CsCl-type structure is proposed to occur at around 11 GPa.     

First x-ray scattering studies on electrostatically levitated metallic liquids: demonstrated influence of local icosahedral order on the nucleation barrier

To explain the unusual stability of undercooled liquids against crystallization, Frank hypothesized that the local structures of undercooled liquids contain a significant degree of icosahedral short-range order, which is incompatible with long-range periodicity. We present here the first direct experimental demonstration of Frank's complete hypothesis, showing a correlation between the nucleation barrier and a growing icosahedral short-range order with decreasing temperature in a Ti39.5Zr39.5Ni21 liquid. A new experimental facility, BESL (Beamline Electrostatic Levitation), was developed to enable the synchrotron x-ray structural studies on deeply undercooled, reactive liquids.     

Synthesis and analysis of silicon nanowire below Si-Au eutectic temperatures using very high frequency plasma enhanced chemical vapor deposition

Silicon nanowires (SiNWs) were synthesized from pure silane precursor gas and Au nanoparticles catalyst at below Au-Si eutectic temperature. The SiNWs were grown onto Si (1 1 1) substrates using very high frequency plasma enhanced chemical vapor deposition via a vapor-solid-solid mechanism at temperatures ranging from 363 to 230 °C. The morphology of the synthesized SiNWs was characterized by means of field emission scanning electron microscope equipped with energy dispersive X-ray, high resolution transmission electron microscopy, X-ray diffraction technique and Raman spectroscope. Results demonstrated that the SiNWs can be grown at the temperature as low as 250 °C. In addition, it was revealed that the grown wires were silicon-crystallized.     

Local order of liquid and supercooled zirconium by ab initio molecular dynamics

It has been suggested that icosahedral short-range order (SRO) occurs in deeply undercooled melts of pure metallic elements. We report results of first-principles molecular dynamics simulations for stable and undercooled zirconium liquids. Our results emphasize the occurrence of a local order more complex than the icosahedral one. For stable liquid, the local order is interpreted on the basis of a competition between a polytetrahedral SRO and a bcc-type SRO. We also demonstrate that a bcc-type SRO increases with the degree of undercooling.     

Ordering behaviors of Cd−Mg and Cd−Zn alloys with the h.c.p.-type structure

The structure dependent energy and the ordering energy for an h.c.p.-type binary alloy composed of simple metals are derived from a basis of the method of pseudopotentials. The expressions of the energies are characterized by the long-range and short-range order parameters.The long-range ordering energy is calculated for alloys in the Cd?Mg system. The numerical results reproduce well the fact that the Cd?Mg system has the B19-type ordered phase around the stoichiometric composition of MgCd and the D0₁₉-type ones around Mg₃Cd and MgCd₃. The calculated local ordering energies explain successfully the existence of a short-range order in the Cd?Mg system and also the insolubility between Cd and Zn.     

Difference in icosahedral short-range order in early and late transition metal liquids

New short-range order data are presented for equilibrium and undercooled liquids of Ti and Ni. These were obtained from in situ synchrotron x-ray diffraction measurements of electrostatically levitated droplets. While the short-range order of liquid Ni is icosahedral, consistent with Frank's hypothesis, significantly distorted icosahedral order is observed in liquid Ti. This is the first experimental observation of distorted icosahedral short-range order in any liquid, although this has been predicted by theoretical studies on atomic clusters.     

Investigation of the particular features of the structure factor of liquid Al-based alloys

We study the structure of liquid binary and ternary alloys of aluminum with transition metals (Al-TM) obtained by Reverse Monte Carlo (RMC) and Molecular Dynamics (MD) simulation methods. Two distinctive features of their structure factor are discussed: the shoulder on the second peak and the prepeak on the left side of the main peak. The quadruples of mutually neighboring atoms (Delaunay simplexes) with a shape close to a regular tetrahedron's (quasi-regular tetrahedra) have been selected in the models and examined. They combine into clusters of different morphology (polytetrahedra) forming a polytetrahedral order (PTO), and there are no compact clusters of these tetrahedra similar to icosahedron in our alloys. It is discussed that the second peak feature of the structure factor is associated with PTO, and does not require for its explanation the presence of icosahedral short-range order (ISRO) in the liquid alloys. The prepeak is caused by the chemical short-range order (CSRO). In our models it is observed mainly on the subsystem of atoms which is complementary to the subsystem of the polytetrahedra. Simulation of the CSRO was performed on a model of monatomic liquid. A new length scale responsible for the prepeak has been obtained in this simulation.     

非晶物质中的临界现象

非晶态材料有着复杂的原子结构(短程有序、长程无序)和特殊的物理性质,其临界现象和相变问题一直受到学术界关注.非晶合金,又称为金属玻璃,是一种新型的非晶态材料,具有很高的强度和优异的弹性.从微观的角度来看,非晶合金可以看作是一个多粒子系统.临界现象的研究对认识和理解多粒子系统之间的相互作用有深刻的意义.本文主要讨论非晶合金中的临界现象,包括非晶合金从制备过程、微观结构到宏观的力学性能以及磁性方面存在的临界现象,并分析这些临界现象之间的内在联系,进而深入理解非晶合金的微观结构对其宏观性质的影响.这为认识非晶合金的形成本质,提高服役可靠性,探索具有实际应用价值的非晶合金提供理论依据.     

Bulk and surface properties of liquid X-Zr (X=Ag, Cu) compound forming alloys

The phase diagrams of the Ag-Zr and Cu-Zr systems exhibit the existence of different intermetallic compounds in the solid state, and since the structure of a liquid alloy is in some respects similar to that of a crystal, the compound formation phenomenon in these liquid alloy systems has been analysed through the study of surface properties (surface tension and surface composition), dynamic properties (chemical diffusion and viscosity) and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the frame of the compound formation model (CFM). Moreover, the associative tendency between unlike constituent elements qualitatively expressed by the microscopic functions indicates the glass-forming ability of both systems at higher Zr-concentrations. These results are in agreement with reported experimental data and confirm the applicability of a statistical mechanical theory in conjunction with the CFM to describe the mixing behaviour of compound forming alloys.     

Microscopic description of an Ising spin glass near the percolation threshold

Monte Carlo results using a microscopic model to describe FexZn(1-x)F2 indicate that its spin-glass phase at x=0.25 and zero magnetic field is characterized by the presence of antiferromagnetic fractal domains, separated by random vacancies and strongly correlated in time. The effective local random-field distribution corroborates this glassy behavior, which emerges irrespective of ab initio competing interactions and is a consequence of the fractal domain structure near the percolation threshold, x(p)=0.24. The aging properties of the system are in agreement with predictions of short-range stochastic spin-glass models and with the droplets model for spin glass close to percolation.