Second virial coefficient and mechanical moduli of metallic glasses

The relationship between the bulk, shear moduli and second virial coefficient of amorphous materials is derived according to their dependences with the radial distribution function. Lennard-Jones–Gaussian potential is used to investigate the relationship between second virial coefficient and temperature, where Lennard-Jones potential represents interactions with the nearest neighbor atoms, and Gaussian potential is responsible for the multi-atom interactions including the next nearest neighbor atoms and heterogeneous structures for a metallic glass. The results show that deep potential well formed by Gaussian potential causes a large second virial coefficient at low temperatures, which is very obvious for the larger fragility glasses. The quadratic form relationship of shear modulus and compositions is proposed, and confirmed by the experimental results of Pd_xNi_100−x−20P₂₀ alloy.     

Viscosity of strong and fragile glass-forming liquids investigated by means of principal component analysis

The Vogel—Fulcher-Tammann-Hesse (VFTH) equation has been the most widespread tool for describing the temperature dependence with viscosity for strong, moderate and fragile glass-forming liquids. In this work, the VFTH equation was applied over a wide temperature range (between the glass transition temperature, T_g, and the melting point, T_m) for 38 oxide glasses, considering simple, binary and ternary compositions of silicate and borate systems. The Levenberg-Marquart non-linear fitting procedure was used to assess VFTH viscosity parameters B and T₀, maintaining A=−5 fixed (in Pa·s) to reduce the number of adjustable parameters. Regarding this restriction, the VFTH formula has shown to adjust very well to experimental data in a wide temperature range. Previous assertions revealed that there is statistical correlation between B and T₀. Principal component analysis (PCA) was used in the present study to verify the correlation between the B and T₀ parameters [J. F. Mano, E. Pereira, J. Phys. Chem. A 108 (2004) 10824], as well as between T_g and T_m. In brief, PCA is a mathematical method aimed at reorganizing information from data sets. The results have shown that it is possible to map either borate (and almost fragile) or silicate (usually strong up to near fragile) systems. As a statistical tool, PCA justifies the use of B, T₀ and T_g as the main parameters for the fragility indexes m=d(log₁₀η)/d(T_g/T)|_T=Tg and D=B/T₀, where η is the viscosity and T the absolute temperature.     

Segmental Dynamics in net -poly(methyl methacrylate)- co -poly(n-butyl acrylate) Copolymer Networks

Dynamic mechanical spectroscopy and differential scanning calorimetry investigations of segmental dynamics are reported for net-poly(methyl methacrylate)-co-poly(n-butyl acrylate) copolymer networks. Three characteristic temperatures, namely, Vogel (T_∞), glass transition (T _g ), and crossover (T _c ), were used to define cooperativity range and a new reduced temperature parameter (Solidness, S). The results showed that broadness of the α -dispersion (glass transition) and cooperativity length scale at the glass transition temperature decreased with increasing butyl acrylate content and T _g -scaled temperature dependence of the relaxation time (fragility). However, the cooperativity range (T _c –T_∞), decreased with increasing fragility index. Furthermore, the solidness at T _g (S(T _g )) was nearly independent of chemical structure of the samples. Finally, a correlation was found between two measures of cooperativity length scale in the glass transition region, namely, average volume of cooperatively rearranging regions, V _CRR , and the number of basic units in an act of rearrangement in the glass transition region, Z(T _g ), determined from two completely independent experimental techniques.     

The diffraction pattern of pp elastic scattering and the composite structure of the proton

The consequences of the quark-glue structure of hadrons for pp elastic scattering are examined in a simple model where the glue is taken to be the active constituent in normal (low p_T) hadronic collisions. Earlier work based on the study of pp inelastic diffraction led to the conclusion that the glue-glue elastic amplitude t_g is approximately Gaussian in the glue-glue impact parameter b_g, with maximum opacity at b_g = 0. A slight refinement of this approximation, in which t_g is almost maximally opaque over a small b_g interval and is Gaussian at larger b_g, is now shown to account for the remarkable diffraction structure observed in pp elastic scattering at ISR energies. A very simple form is obtained for the form factor describing the impact parameter distribution of the glue inside a proton relative to the proton itself.     

Relation between elastic modulus and glass softening temperature in the delocalized atom model

The ratio of softening temperature (glass transition temperature) to elastic modulus (T _g /E) is mainly determined by the limiting elastic deformation of an interatomic bond, which characterizes the transition of a structural microregion from an elastic into a viscous-flow state. In silicate glasses, this transition is caused by the limiting deformation of directed ionic-covalent Si-O-Si bonds. In the case of amorphous hydrocarbons, it is related to the relatively weak intermolecular bonds between regions in chain macromolecules, and the T _g /E ratio is significantly higher than in inorganic glasses. In glassy systems of one class, this ratio turns out to be constant (T _g /E ?? const), and a linear correlation is detected between softening temperature and elastic modulus, which can be explained in terms of the delocalized atom model. The values of T _g /E can be used to classify glasses similarly to the well-known Angell classification according to so-called fragility.     

Excluded volume effect on entropy and clustering behaviors in supercooled liquids and glasses

We study the significant entropy changes in supercooling and glass transition by developing a two (H and L) state cluster model, where the H-state represents the clusters with the coordination number z being larger than the reference size z_R and the L-state those with z<z_R, respectively. We exploit the excluded volume effect on the clustering behaviors of various glass-formers and the temperature dependence (at fixed pressure of 1 atmosphere) of the entropy difference between the two cluster states on the basis of , where as taken universally for all the glass-formers investigated. The temperature dependence of the average size 〈z_c^∗〉 of clusters with z≥z_R is then determined for some representative glass-formers, such as GeO₂, 1-propanol, glycerol, propylene carbonate, o-terphenyl, and so forth, covering the entire fragility spectrum studied experimentally. As a result, the temperature dependence of 〈z_c^∗〉 is found to highly depend on the fragility index ? associated with the temperature dependence of the excluded volume B^∗(?,T) of which statistical mechanical representation is given by the generic van der Waals equation of state. With decreasing T toward the glass transition temperature T_g, 〈z_c^∗〉 increases to attain universally about 13 at T_g regardless of the fragility and molecular details of the glass-formers. We specifically analyze in depth the theoretical predictions for the cluster sizes and the experimental estimations for the length scales associated with temporary clusters of slow segments in supercooled glycerol as about 1.4±0.5 nm for glycerol at 10 K above T_g. Given the large uncertainties associated with the experiment, the present theory appears to be in good agreement with the experiment.     

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     

Extended Born-Green equation: A new approach for determining pair potentials in disordered systems

The Born-Green equation was tested using molecular dynamics data for liquid rubidium at 319 K. The unsatisfactory results of this equation for the pair potential are caused by the insufficient precision of the Kirkwood approximation for describing the triplet correlation function g₃(r,s,t). A more realistic ansatz for g₃(r,s,t) was employed in the formulation of an extended Born-Green equation. This new approach gives much better results for the potential than the simple Born-Green equation.     

Effect of Alkyl Side Chain Length on Relaxation Behaviors in Poly(n-alkyl Acrylates) and Poly(n-alkyl Methacrylates)

Dynamic mechanical analysis (DMA) is used to investigate the effect of alkyl side chain length on the relaxation behavior of poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) above the glass transition temperature (T_g). Master curves and shift factors (log a_T) were obtained using the time–temperature superposition (TTS) principle. The log a_T curves of PnAA and PnAMA exhibit a dynamic crossover from one Vogel–Fulcher–Tammann–Hesse (VFTH) equation to another above T_g. The corresponding temperature was designated as the dynamic crossover temperature (T_c). It is found that T_c/T_g and the apparent activation energy (E_g) increases, e whereas the fragility index (m) decreases with increasing alkyl side chain length. Further analysis shows that m ∝ T_g, E_g∝ , and E_g∝ m² for both PnAA and PnAMA.     

Resonant Raman scattering from FeS2 (pyrite)

We have observed resonant Raman scattering from the A_g mode of FeS₂ (pyrite) for incident laser energies between 2.41 and 2.73 eV, these energies being well above the fundamental gap at 0.9 eV. In contrast to the behavior of the A_g mode intensity, the E_g and T_g modes do not show resonant behavior. A simple two band model which predicts the Raman cross section proportional to |?χ/?ω|² is found to be inadequate to describe the observed intensity variation with the incident laser energy.     

First-order transitions from singly peaked distributions

Suppose that, in the thermodynamic limit, a single-component particle system exhibits a standard first-order transition marked by a jump in the density, ρ, at a chemical potential μ_σ(T). In grand canonical simulations of model fluids that realize such a transition when L→∞ (where L is the linear dimension of the simulation volume) the presence of the transition is typically signaled by the appearance of a double-peaked structure in the distribution function, P_N(T,μ_σ;L), of the particle number, N. A simple, explicit counterexample is presented, however, that proves, contrary to popular beliefs, that the converse proposition is false: i.e., a single-peaked distribution, P_N(T,μ_σ;L), may, when L→∞, give rise to a first-order transition. Alternatively, the existence of a first-order transition does not imply a double-peaked distribution. Systems that may exhibit such single-peaked, first-order behavior are discussed and a possible route to constructing explicit models exhibiting the phenomenon is described. Strategies to use in simulating such systems are briefly considered in the light of related studies.     

Surface and interface effects on structural transformation of vapor-deposited ethylbenzene films

We have investigated how the structures of vapor-deposited glassy films change with increasing temperature by using time-of-flight secondary ion mass spectrometry and ion scattering spectroscopy. It is found that intermixing of the topmost layer of an ethylbenzene film occur at temperature (~ 80 K) considerably lower than the glass transition temperature (T_g = 118 K) when the film is deposited at 20 K. This phenomenon can be interpreted as the occurrence of a two-dimensional liquid that diffuses into pores of the film, which is evidenced from comparison with surface diffusivity measurements using a porous silicon layer. For nonporous films deposited at higher temperatures, the molecules intermix gradually prior to the abrupt film morphology change at T_g. This phenomenon can be interpreted as decoupling between translational diffusivity and viscosity in the bulk. The film thickness has no significant effects on the evolution of supercooled liquid at T_g except for the monolayer film, whereas crystallization is quenched for the films thinner than 8 monolayers. The roles of the 2D liquid on the surface and an immobilized layer formed at the interface are discussed in finite-size effects on the glass-liquid transition and crystallization.     

Observation of the strongly anomalous temperature and composition dependence of (δp/δT)s in liquid Li/Pb alloys

(δp/δT)_s which is proportional to the specific heat has been measured between the liquidus temperature and 1250 K for the whole concentration range of liquid Li/Pb alloys. For all concentrations it shows a positive deviation from the values expected for an ideal solution and it exhibits a narrow peak close to the composition Li₄Pb. The variation of T(δp/δT)_s with T is linear only for pure Pb. At 0.2 < x_Li < 0.6 a fall-off after melting is followed by a broad maximum at about 1000 K.     

High frequency and static dielectric constants of zinc blende structured solids

A correlation is presented for the high frequency ε_∞ and static ε_o dielectric constants of A^IIB^{V I} and A^IIIB^V semiconductors with the zinc blende structure. The high frequency ε_∞ and static ε_o dielectric constants can be represented by an empirical linear relation that is a simple function of melting temperature T_m, atomic volume Ω and product of ionic charges (Z₁Z₂). Values of high frequency ε_∞ and static ε_o dielectric constants of A^IIB^{V I} and A^IIIB^V zinc blende semiconductors exhibit a linear relationship when plotted against the k_BT_m/Ω (k_B=Boltzmann’s constant), but fall on two straight lines according to the product of ionic charges of the compounds. The calculated results are compared with available experimental data and previous calculations based on phenomenological models.     

Elastic moduli and theoretical estimations of physical properties of Ge3Se7–As2Te3

The Bulk (100-x)Ge₃Se₇ - (x)As₂Te₃ (0 ≤ x ≤ 30) glassy alloys were prepared using the melt quenching technique. The elastic moduli (Bulk (K), Micro-hardness (H), Young (Y)), and Poisson's ratio (P_r) of the prepared glasses have been determined using the measured values of the ultrasonic velocities and density (ρ). Values of ρ were measured, then the molar volume (V_m) was estimated theoretically. The DSC thermograms are used to determine the glass transition temperature (T_g). The thermal evaporation method was used to prepare the (100-x)Ge₃Se₇- (x)As₂Te₃ (0 ≤ x ≤ 30) thin films under a vacuum of about 10⁻⁴Pa. The absorbance (A) of the films in the spectral range from 0.45 to 0.85 μm has been measured, then the absorption coefficient (α) and energy gap (E_g) were determined. The Chemical Bond Approach (CBA) has been used successfully to estimate theoretically various physical and structural characteristics of the studied system. Theoretical values of E_g and T_g have been obtained using different methods. The results proved a remarkable agreement between the theoretical and experimental values for both the E_g and T_g. The E_g values decreased from 2.1 to 1.73 eV by increasing the As₂Te₃ content from 0 to 30 at. %. Therefore, these compounds can be used as an absorbing layer for electromagnetic radiation in photovoltaic devices and sensors.     

Combinatorial arc plasma deposition search for Ru-based thin film metallic glass

We have discovered a novel Ru-based thin film metallic glass (TFMG) using combinatorial arc plasma deposition (CAPD). To search for Ru-based TFMG, alloy systems of Ru-Zr-Al, Ru-Zr-Fe and Ru-Zr-Mo were investigated by making libraries. Each library consisted of 1089 CAPD samples deposited on a substrate by CAPD. Composition of each sample is different with each other.The composition and phases of the CAPD samples were measured by energy dispersive X-ray fluorescence spectrometry and X-ray diffractometry, respectively. Results showed the amorphous regions depended on the additive elements Al, Fe or Mo. Compared with the addition of Al, the addition of Fe or Mo exhibited high amorphous forming ability.To evaluate the mechanical properties, the glass transition temperature T_g and the crystallization temperature T_x of the amorphous samples in each Ru-Zr-X alloy, larger samples having the same compositions as the typical amorphous CAPD samples were reproduced by sputtering because the CAPD samples were too small to measure the mechanical properties, T_g and T_x.Ru₆₅Zr₃₀Al₅ and Ru₆₇Zr₂₅Al₈ samples were found to exhibit the better fracture stress and elastic limit than conventional TFMGs, while Ru-Zr-Fe and Ru-Zr-Mo samples were found to be brittle. DSC revealed that the Ru₆₅Zr₃₀Al₅ sample was a TFMG, with a T_g of 902 K and T_x of 973 K.     

Spin-Probe ESR Studies on Nanocomposite Polymer Electrolytes

The possibility of using spin-probe electron spin resonance (ESR) as a tool to study glass transition temperature, T _g, of polymer electrolytes is explored in 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL)-doped composite polymer electrolyte (PEG)₄₆LiClO₄ dispersed with nanoparticles of hydrotalcite. The T _g is estimated from the measured values of T _50G, the temperature at which the extrema separation 2A _zz of the broad powder spectrum decreases to 50 G. In another method, the correlation time τ_c for the spin probe dynamics was determined by computer simulation of the ESR spectra and T _g has been identified as the temperature at which τ_c begins to show temperature dependence. While both methods give values of T _g close to those obtained from differential scanning calorimetry, it is concluded that more work is required to establish spin-probe ESR as a reliable technique for the determination of T _g.     

Characterization of solid electrolytes prepared from ionic glass and ionic liquid for all-solid-state lithium batteries

Glassy solid electrolytes were prepared by combining the 50Li₂SO₄·50Li₃BO₃ (mol%) ionic glass and the 1-ethyl-3-methyl-imidazolium tetrafluoroborate ([EMI]BF₄) ionic liquid. High-energy ball milling was carried out for the mixture of the inorganic ionic glass and the organic ionic liquid. The ambient temperature conductivity of the glass electrolyte with 10 mol% [EMI]BF₄ was 10⁻⁴ S cm⁻¹, which was three orders of magnitude higher than that of the 50Li₂SO₄·50Li₃BO₃ glass. The addition of [EMI]BF₄ to the ionic glass decreased glass transition temperature (T_g) of the glass and the decrease of T_g is closely related to the enhancement of conductivity of the glass. Morphology and local structure of the glass electrolyte was characterized. The dissolution of an ionic liquid in an ionic glass with Li⁺ ion conductivity is a novel way to developing glass electrolytes for all-solid-state lithium secondary batteries.     

Theory of spin-resolved photoemission from Fe at finite temperature: The disordered local moment picture

We present first principles calculations of the spin and angle-resolved photoemission spectra for Fe(100) at T = 0 and T = T_c, based on the KKRCPA treatment of the disordered local moment model. At T = 0 the calculations are in generally good agreement with experiment, and are shown to be quite sensitive to the surface potential and magnetisation. The high T calculations are also consistent with existing data, and a strong photon polarisation dependence is predicted as a consequence of the different exchange splitting of the T_2g and E_g states.