Testing “microscopic” theories of glass-forming liquids

We assess the validity of “microscopic” approaches of glass-forming liquids based on the sole knowledge of the static pair density correlations. To do so, we apply them to a benchmark provided by two liquid models that share very similar static pair density correlation functions while displaying distinct temperature evolutions of their relaxation times. We find that the approaches are unsuccessful in describing the difference in the dynamical behavior of the two models. Our study is not exhaustive, and we have not tested the effect of adding corrections by including, for instance, three-body density correlations. Yet, our results appear strong enough to challenge the claim that the slowdown of relaxation in glass-forming liquids, for which it is well established that the changes of the static structure factor with temperature are small, can be explained by “microscopic” approaches only requiring the static pair density correlations as nontrivial input.     

The characterisation of atomic structure and glass-forming ability of the Zr–Cu–Co metallic glasses studied by molecular dynamics simulations

In the present work, the glass formation process and structural properties of Zr₅₀Cu_50-xCo_x (0 ≤ x ≤ 50) bulk metallic glasses were investigated by a molecular dynamics simulation with the many body tight-binding potentials. The evolution of structure and glass formation process with temperature were discussed using the coordination number, the radial distribution functions, the volume–temperature curve, icosahedral short-range order, glass transition temperature, Voronoi analysis, Honeycutt–Andersen pair analysis technique and the distribution of bond–angles. Results indicate that adding Co causes similar responses on the nature of the Zr₅₀Cu_50-xCo_x (0 ≤ x ≤ 50) alloys except for higher glass transition temperature and ideal icosahedral type ordered local atomic environment. Also, the differences of the atomic radii play the key role in influencing the atomic structure of these alloys. Both Cu and Co atoms play a significant role in deciding the chemical and topological short-range orders of the Zr₅₀Cu_50-xCo_x ternary liquids and amorphous alloys. The glass-forming ability of these alloys is supported by the experimental observations reported in the literature up to now.     

Effect of Fe on the glass-forming ability,structure and devitrification behavior of Zr–Cu–Al bulk glass-forming alloys

We report on the glass-forming ability and devitrification behavior of Zr₆₀Cu₃₀Al₁₀, Zr₆₀Cu₂₅Al₁₀Fe₅ and Zr_62.5Cu_22.5Al₁₀Fe₅ bulk glass-forming alloys on heating. The effect of Fe addition on the structure of Zr–Al–Cu alloys is also discussed. Crystallization kinetics and structural changes in the glassy alloys were studied using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. The results indicate that good glass-formers, such as Zr_62.5Cu_22.5Al₁₀Fe₅, are located somewhat beyond the equilibrium eutectic point. Possible phase separation in the supercooled liquid on heating and electron beam-induced in situ crystallization are observed and discussed.     

Photon echo experiments on 3–3′ diethylthiacarbocyanine in glass-forming liquids with ultrafast laser pulses

Summary  Photon echo experiments on diethylthiacarbocyanine iodide (DTCI) in dibuthylphthalate (DBP) and glycerol in the glass phase with femtosecond pulses are presented. The PE signal shows nonexponential decays even at low temperatures. This behavior is attributed to the many vibronic resonances of the chromophore/ glass system which can be simultaneously excited by the spectral bandwith of the laser pulses. We are able to extract from the PE decays the contribution of the homogeneous dephasing rate of the 0-0 transition of DTCI up to 20 K in dibutylphthalate and 40 K in glycerol. A beating structure in the echo decay for the system DTCI/DBP is also observed from 8 K up to 180 K (glass transition temperature for DBP). This feature is attributed to an intereference process involving excitation of a vibronic transition of DTCI characterized by a vibrational frequency of 300 cm^-1.     

What do we learn from the local geometry of glass-forming liquids?

We examine the local geometry of a simulated glass-forming polymer melt. Using the Voronoi construction, we find that the distributions of Voronoi volume P(v(V)) and asphericity P(a) appear to be universal properties of dense liquids, supporting the use of packing approaches to understand liquid properties. We also calculate the average free volume along a path of constant density and find that extrapolates to zero at the same temperature T0 that the extrapolated relaxation time diverges. We relate to the Debye-Waller factor, which is measurable by neutron scattering.     

Non-monotonic dependence of current upon i-width in silicon p–i–n diodes

Silicon p–i–n diodes with different i-region widths are fabricated and tested. It is found that the current shows the non-monotonic behavior as a function of i-region width at a bias voltage of 1.0 V. In this paper, an analytical model is presented to explain the non-monotonic behavior, which mainly takes into account the diffusion current and recombination current contributing to the total current. The calculation results indicate that the concentration ratio of p-region to n-region plays a crucial role in the non-monotonic behavior, and the carrier lifetime also has a great influence on this abnormal phenomenon.     

Supercooled liquids analogous fractional Stokes–Einstein relation in NaCl solution above room temperature

The Stokes–Einstein relation D～T/η and its two variants D～τ~(-1) and D～T/τ follow a fractional form in supercooled liquids, where D is the diffusion constant, T the temperature, η the shear viscosity, and τ the structural relaxation time.The fractional Stokes–Einstein relation is proposed to result from the dynamic heterogeneity of supercooled liquids.In this work, by performing molecular dynamics simulations, we show that the analogous fractional form also exists in sodium chloride(NaCl) solutions above room temperature.D～τ~(-1) takes a fractional form within 300–800 K; a crossover is observed in both D～T/τ and D～T/η.Both D～T/τ and D～T/η are valid below the crossover temperature T_x,but take a fractional form for T T_x.Our results indicate that the fractional Stokes–Einstein relation not only exists in supercooled liquids but also exists in NaCl solutions at high enough temperatures far away from the glass transition point.We propose that D～T/η and its two variants should be critically evaluated to test the validity of the Stokes–Einstein relation.     

Gas—liquid interfaces of room temperature ionic liquids

The structure of the gas-liquid surface of dimethylimidazolium chloride has been studied using atomistic simulation. We find that there is a region of enhanced density immediately below the interface in which the cations are oriented with their planes perpendicular to the surface and their dipoles in the surface plane. There is negligible segregation of cations and anions. The temperature dependence of the surface tension is predicted to be anomalously low or be reversed in sign. The vapour-liquid interfaces between mixtures of water and dimethylimidazolium chloride show similar regions of enhanced density and preferential orientation of the cations. Water molecules also show preferential orientation in the interface region and are preferentially adsorbed on the vapour side of the interface. The surface tension decreases with increase in the mole fraction of water.     

Effect of water–methanol content on the structure of Nafion in the sandwich model and solvent dynamics in nano-channels; a molecular dynamics study

Continuing an ongoing study, molecular dynamics (MD) simulations were performed to investigate the effects of methanol concentration on Nafion morphology, such as the size of solvent cluster, solvent location, and polymer structure via the sandwich model. Our survey shows that high methanol concentrations resulted in increment of solvent cluster size in Nafion membrane. The sulfonic acid clusters also befall much in order as subsequent layers of such ionic clusters are formed. The number of neighbouring hydronium ions around a sulfur atom is independent of methanol concentration, but the first shell of hydronium and water around sulfonic acid clusters is broader. Although methanol would prefer to interact with water molecules rather than sulfonic acid groups, gathering of methanol molecules via hydrophobic self-aggregation is preferred. Methanol is located closer to the hydrophobic part of the polymer than water, while water is located closer to the hydrophilic part of the polymer. It was found that methanol distributes specifically more than water in nano-channels. Investigation of solvent dynamics in nano-channels shows that diffusion coefficients (D) of water, methanol, and hydronium decrease with increasing methanol concentration and they may be ordered as follows: D _Water?>?D _Methanol?>?D _Hydronium (D _Water?≈?1.6–2.0D _Methanol and D _Methanol?≈?2.1–3.0D _Hydronium).     

Hydrogen-induced dynamic slowdown of metallic glass-forming liquids

Dynamics of hydrogen doped Cu_(50) Zr_(50) glass-forming liquids are investigated by using the newly developed modified embedded atomic method(MEAM) potential based on molecular dynamics simulations. We find that the doping of hydrogen atoms slows down the relaxation dynamics, reduces the fragility of supercooled melts, and promotes the occurrence of glass transitions. The dynamic slowdown is suggested to be closely related to the effect of hydrogen atoms on locally ordered structure of melts. With increasing concentration of hydrogen, the five-fold symmetry associated with Cu-and Zr-centered polyhedrons is lowered, on the other hand, the local order featuring metal hydrides is enhanced. The latter dominates the dynamic behaviors of glass-forming liquids, especially for Zr atoms, and results in the dynamic slowdown.     

块体非晶合金的黏度与玻璃形成能力的关系

基于经典结晶理论讨论了非晶合金的晶化动力学因素和晶化热力学因素对玻璃形成能力（GFA）的影响.分析表明,合金的等温转变（TTT）曲线“鼻尖”温度T_n对应的黏度与晶化阻力因子成正比;重新加热时晶化开始温度T_x对应的黏度与晶化驱动力因子成反比.由此得到了新的GFA参数ω₀=（T_g-T₀）/（T_x-T₀）-（T_g-T₀）/（T_n-T₀）,其中T_g为玻璃转变温度,T₀为理想玻璃转变温度.统计结果显示,ω₀与临界冷却速率具有较高的相关性,R²高达09626.进一步分析表明：新提出的ω₀参数可以合理地解释过冷熔体的黏度、脆性、液相稳定性、热稳定性以及T_rg、ΔT_x、γ、γ_m、ΔT_rg、α、β、δ和φ等参数与GFA的关系. 关键词： 块体非晶合金 黏度 脆性 玻璃形成能力     

基于Weiss分子场理论对极性液体中静态介电常数随温度变化及其相应取向关联的研究

迄今为止,并没有被普遍接受的液体静态介电常数的微观理论模型, 主要原因是对属于强关联系统的液体中分子之间的取向关联特征仍不十分清楚. 本文基于Weiss分子场理论(WMFT), 对水(water, H₂O)、甲醇(methanol, CH₄O)、乙醇(ethanol, C₂H₆O)和正丙醇(1-propanol, C₃H₈O)等4种极性液体中静态介电常数, 具体为Curie-Weiss常数、Curie温度和Weiss分子场因子随温度变化规律进行分析研究, 得出上述液体中: 1)铁电关联(ferroelectric correlation, FC)和反铁电关联(anti-ferroelectric correlation, AFC)共存, 且FC比AFC强得多, 以及随温度降低FC减弱和/或AFC增强; 2)结构均匀的WMFT不能定量描述上述液体中足够低的温度下反常大的静态介电常数. 可以想象FC和较弱AFC的共存必然导致极性液体中关联序的空间不均匀, 由此作者提出了空间不均匀关联序的粗粒近似的Weiss分子场理论, 并用此理论对上述液体中静态介电常数随温度快速变化的行为进行了解释. 上述结果对深入认知液体物理学, 包括玻璃化转变机制的探索, 无疑是有价值的.     

二十面体团簇的遗传:一个与快凝Cu56Zr44合金玻璃形成能力有关的动力学参数

采用分子动力学方法模拟研究了液态Cu₅₆Zr₄₄合金在不同冷速γ与压力P下的快速凝固过程, 并通过基于Honeycutt-Andersen键型指数的扩展团簇类型指数法对其微结构演变特性进行了分析. 结果表明: 快凝玻璃合金的局域原子组态主要是(12 12/1551)规则二十面体、以及 (12 8/1551 2/1541 2/1431)与(12 2/1441 8/1551 2/1661) 缺陷二十面体. 通过原子轨迹的逆向跟踪分析发现: 从过冷液体中遗传下来的二十面体对快凝合金的玻璃形成能力(GFA)具有重要影响, 不仅其可遗传分数F_i =N_{300 K←Tg}ⁱ/N_Tg 与GFA密切相关, 而且其遗传起始温度(T_onset)与合金约化玻璃转变温度T_rg = T_g/T_m也存在很好的对应关系.     

熔体初始温度对液态金属Ni凝固过程中微观结构演变影响的模拟研究

采用量子 Sutton-Chen多体势, 对熔体初始温度热历史条件对液态金属Ni快速凝固过程中微观结构演变的影响进行了分子动力学模拟研究. 采用双体分布函数g(r)曲线、键型指数法、原子团类型指数法和三维可视化等分析方法对凝固过程中微观结构的演变进行了分析. 结果表明: 熔体初始温度对凝固微结构有显著影响, 但在液态和过冷态时的影响并不明显, 只有在结晶转变温度T_c附近才开始充分显现出来. 体系在1×10¹² K/s的冷速下, 最终均形成以1421和1422键型或面心立方(12 0 0 0 12 0)与六角密集(12 0 0 0 6 6) 基本原子团为主的晶态结构. 末态时, 不同初始温度体系中的主要键型和团簇的数目有很大的变化范围, 且与熔体初始温度的高低呈非线性变化关系. 然而, 体系能量随初始温度呈线性变化关系, 初始温度越高, 末态能量越低, 其晶化程度越高. 通过三维可视化分析进一步发现, 在初始温度较高的体系中, 同类团簇结构的原子出现明显的分层聚集现象, 随着初始温度的下降, 这种分层现象将被弥散开去. 可视化分析将更有助于对凝固过程中微观结构演变进行更为深入的研究. 关键词： 液态金属Ni 熔体初始温度 微观结构 分子动力学模拟     

Spatial correlation of irreversible displacement in oscillatory-sheared metallic glasses

We report computer simulations on the oscillatory of CuZr metallic glasses at zero temperature with different shear amplitudes. In small system a homogenous shear deformation is found, while in large system an inhomogeneous shear deformation is found with a shear band formed. Concomitantly, spatial correlation of irreversible displacement exhibits an isotropic and exponential decay in the case of homogeneous deformation, whereas a mixed power-law and exponential decay in the case of anisotropic and inhomogeneous deformation. By projecting the azimuthal-dependent correlation function onto the spherical harmonics, we found a strong polar symmetry that accounts for the emerged shear band, and a weaker quadrupolar symmetry that accounts for the elastic filed generated by Eshelby inclusions. By this, we conclude that the anisotropy and decaying formula of the plastic correlation are dominated by the homogeneity or inhomogeneity for the deformation in the metallic glasses.     

Effects of Mo additions on the glass-forming ability and magnetic properties of bulk amorphous Fe-C-Si-B-P-Mo alloys

Glass formation, mechanical and magnetic properties of the Fe76-xC7.0Si3.3B5.0P8.7Mox (x=0, 1 at.%, 3 at.% and 5 at.%) alloys prepared using an industrial Fe-P master alloy have been studied. With the substitution of Mo for Fe, glass-forming ability (GFA) was significantly enhanced and fully amorphous rods with a diameter of up to 5 mm were produced in the alloy with 3% Mo. The Mo-containing amorphous alloys also exhibited high fracture strength of 3635–3881 MPa and excellent magnetic properties including a high saturation magnetization of 1.10–1.41 T, a high Curie temperature and a low coercive force. The unique combination of high GFA, high fracture strength and excellent magnetic properties make the newly developed bulk metallic glasses viable for practical engineering applications.     

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.     

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.     

金属液体结构与性能研究的新进展

金属液体的结构演化与其性能的关联一直都是凝聚态物理和材料科学领域的研究热点。文章介绍了金属液体结构的研究方法,以及液—液相变、物性参数和易碎性指数与其结构之间的内在关联性等基础科学问题的最新研究进展。随着金属液体结构和性能研究的不断深入,特别是大量先进实验方法的引入,加深了人们对金属液体的认识,同时促进了新材料的开发和性能改善等。