Oxidation of Zr 55 Cu 30 Al 10 Ni 5 bulk metallic glass in the glassy state and the supercooled liquid state

The oxidation behavior of Zr₅₅Cu₃₀Al₁₀Ni₅ bulk metallic glass in air in the glassy state and the supercooled liquid state was studied using a thermogravimetric analyzer, X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. It was found that the isothermal oxidation kinetics of the glass in both states follows a two-step parabolic law. The oxidation process is governed by the inward diffusion of oxygen and the outward diffusion of Cu, with the first being dominant. The faster diffusion of atoms in the supercooled liquid state led to a network precipitation of crystalline Cu, and the crystallization that occurred in this state in the later stage of oxidation caused a reduction in the rate of oxidation. Two types of Zr oxides, i.e. t-ZrO₂ and m-ZrO₂, were formed in the oxidation process in both the glassy and supercooled liquid states. t-ZrO₂ mainly formed in the outer layer of the oxide scale, while m-ZrO₂ tended to form in the inner layer. The formation of m-ZrO₂ is possibly activated by the crystallization of the glass near the interface of the oxide scale and the substrate alloy. In addition, oxidation also has a substantial effect on the formation of crystallized phases. The formation of a Cu-rich phase of Cu₁₀Zr₇ occurred in the oxidizing atmosphere. However, the formation of a Zr-rich phase of Zr₂(Ni, Cu) mainly took place in a vacuum environment. PACS 81.05.Kf; 81.65.Mq; 64.60.-i     

Experimental evidence for a high-pressure isostructural phase transition in osmium

We have measured the isothermal equation of state (EOS) of osmium to 75 GPa under hydrostatic conditions at room temperature using angle-dispersive x-ray diffraction. A least-squares fit of this data using a third-order Birch-Murnaghan EOS yields an isothermal bulk modulus K0=411+/-6 GPa, showing osmium is more compressible than diamond. Most importantly, we have documented an anomaly in the compressibility around 25 GPa associated with a discontinuity in the first pressure derivative of the c/a ratio. This discontinuity plausibly arises from the collapse of the small hole-ellipsoid in the Fermi surface near the L point.     

Crystallization Kinetics of Co48Cr15Mo14C15BaEr2 Bulk Metallic Glass with High Thermal Stability

We investigate the crystallization kinetics of Co48Cr15Mo14C15B6Er2 bulk metallic glass. It is found that Co48Cr15Mo14C15B6Er2 alloy shows extraordinary glass-forming ability, and a fully glassy rod with a diameter of 10mm can be formed, Thermal analysis exhibits that this glassy alloy has a high thermal stability, Johnson-Mehl-Avrami analysis of isothermal differential scanning calorimetry demonstrates that the crystalline phases homogeneously nucleates at a constant rate and grows linearly at a constant rate in three dimensions in the supercooled liquid of the glassy alloy.     

Structural transformations in liquid,crystalline, and glassy B<Subscript>2</Subscript>O<Subscript>3</Subscript> under high pressure

We present in situ (x-ray diffraction) and ex situ (quenching) structural studies of crystalline, liquid, and glassy B₂O₃ up to 9 GPa and 1700 K, drawing equilibrium and nonequilibrium phase diagrams of B₂O₃. Particularly, we have determined the melting curve, the stability regions for crystalline B₂O₃ I and B₂O₃ II modifications, the regions of transformations, such as densification or crystallization, for both the liquid and glassy states, including the region of sharp first-order-like transition in liquid B₂O₃ to a high-density phase near 7 GPa. Quenching experiments also show that the transition to the high-density liquid can occur at much lower pressures in nonstoichiometric melts with an excess of boron. B₂O₃ is the first glassformer whose transformations in the disordered state have been comparatively studied for both liquid and glassy phases.     

Photophysical and photochemical switches based on twisted intramolecular charge transfer (TICT) states

TICT states, accessible in twisted multichromophoric systems, are nonradiative funnels to the ground state in many dyes. By controlling these funnels, faster saturable absorbers for subpicosecond laser pulses can be developed. Oriented assemblies of TICT molecules, as in liquid crystalline polymers, are expected to exhibit light-induced macroscopic charge separation. Chemical approaches to supramolecular bistable species are also shown.     

Synchrotron X-ray diffraction study of phenacite at high pressure

We report the results of a natural phenacite from 0 to 30.9 GPa using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at the National Synchrotron Light Source, Brookhaven National Laboratory. Over this pressure range, no phase change or disproportionation has been observed. The isothermal equation of state was determined. The values of V₀, K₀, and K₀′ refined with a third-order Birch-Murnaghan equation of state are V₀=1116.1±1.2 ų, K₀=223±9 GPa, and K₀′=5.5±0.8. Furthermore, we confirm that the linear compressibilities (β) along a and c directions of phenacite are elastically isotropic (β_a=1.50×10^-3 and β_c=1.34×10^-3 GPa^-1). Consequently, it can be concluded that the compressibility of phenacite under high pressures has been accurately constrained.     

Using molecular dynamic simulation data of calcite in a wide pressure range to calculate some of its thermodynamic properties via some universal equations of state

Molecular dynamics, MD, simulation of calcite (CaCO₃) is selected to compare the p-v-T behaviour of some universal equations of state, UEOS, for the temperature range 100 K ≤ T ≤ 800 K, and pressures up to 3000 kbar. The isothermal sets of p-v-T data generated by simulation were each fitted onto some three- and two-parameter EOSs including Parsafar and Mason (PM), Linear Isotherm Regularity (LIR), Birch-Murnaghan (BM), Shanker, Vinet, Baonza and Modified generalized Lennard–Jones (MGLJ) EOSs. It is found that the MD data satisfactorily fit these UEOS with reasonable precision. Some features for a good UEOS criteria such as temperature dependencies of coefficients, pressure deviation, isothermal bulk modulus and its derivative at the zero pressure limit, isobaric thermal expansion, pressure spinodal values and divergence of pseudo critical exponent either near to or far from the spinodal condition, and some regularities for calcite are investigated.     

Grüneisen γ通用函数及完全物态方程

在分析Grüneisen γ近似函数的适用范围和热力学γ高压演化特性的基础上, 根据Grüneisen γ系数的物理性质和变化特点, 利用数学分析的方法建立了Grüneisen γ通用函数γ_n(v). 将γ_n(v)代入热力学函数γ(v, T), γ(v, T)即成为全压力区连续可导的函数, 并由γ(v, T)直接导出了等熵温度函数T_S(v); 再根据等熵温度与Hügoniot 温度的函数关系获得了Hügoniot温度方程的解析函数T_H(v), 从而使Hügoniot方程成为完全物态方程. 对几种金属做了检验, 由等温方程推算Hügoniot方程, 或者由Hügoniot方程推算等温方程, 其结果都与实验符合得很好.     

An interstitialcy theory of structural relaxation and related viscous flow of glasses

A theory of isothermal structural relaxation and creep of glasses below the glass transition temperature is given. According to the interstitialcy theory, the supercooled liquid state does not exist below a Kauzmann "pseudocritical" temperature T(k), which lies above the temperature T(K), commonly called the "Kauzmann temperature." Structural relaxation is simply a reduction with time of the interstitialcy concentration to the crystalline state for TT(k). The predicted viscosity eta is universal, given by eta=eta(0) + eta(T)t, in agreement with experiment. eta is continuous in T, with eta discontinuous at T(k) but linear in 1/T above and below T(k). The dependence of eta on the shear modulus directly connects kinetic and thermodynamic properties of glasses and liquids.     

Correlation between glass transition temperature and thermal expansion coefficients of polymers: Its interpretation and implication

A new approach pertaining to the hole and lattice theories of polymeric systems is developed to interpret the universal inverse relationship between the glass transition temperature (T_g) and the difference in thermal expansion coefficients for liquid and glassy polymers (δ α). The success of this particular theoretical consideration rests upon the familiar hypothesis of the iso-free volume state at T_g and the entropy contribution to the hole-polymer segment interaction energy. Based on the experimental data available, we have established the free volume fraction at T_g, v_g = 0.025, which is identical with the assessment of the empirical Williams-Landel-Ferry (WLF) equation for the temperature-dependence shift factor a_T. However, appreciably higher values of v_g are reported by other contemporary models. The present findings justify an alternative form of the WLF equation with the product T_g, δ α playing the role of δ α. The universality of this novel expression is demonstrated, by means of statistical analysis, to be remarkably more warrantable than its original version.     

多体相互作用体系中的弛豫与扩散:一个尚未解决的问题

文章目的在于引起国内研究团体对一系列复杂相互作用体系中的弛豫和扩散的普适性进行关注.研究发现,无论是不同的化学结构(如无机物、有机物、聚合物、生物分子、胶体、金属和离子导电材料),还是不同的物理状态(如晶态、玻璃态、液体、熔体、混合体系和含水系统),以及不同的尺度(如从块体至纳米),这种普适性无处不在[K.L.Ngai.Relaxation and Diffusion in Complex Systems.NewYork:Springer,2011].该现象起源于多体系统的不可逆过程,取决于一些基本物理定律,与非简谐势引发的经典混沌有关.重新认识这种普适性不仅对众多不同领域的发展有利,而且能进一步弄清楚多体系统中的弛豫与扩散问题——一个重要而又未解决的物理问题.作者提出的耦合模型尽管不是一个严格而完整的答案,但却能够预测多体系统的弛豫和扩散特征,而且与实验结果吻合.基于该模型,绝大多数多体系统中的弛豫与扩散行为是相似的.该模型有望为这一难题的彻底解决奠定基石.     

Thermal equation-of-state of osmium: a synchrotron X-ray diffraction study

The pressure-volume-temperature behavior of osmium was studied at pressures and temperatures up to 15 GPa and 1273 K. In situ measurements were conducted using energy-dispersive synchrotron X-ray diffraction in a T-cup 6-8 high pressure apparatus. A fit of room-temperature data by the third-order Birch-Murnaghan equation-of-state yielded isothermal bulk modulus K₀=435(19) GPa and its pressure derivative K′₀=3.5(0.8) GPa. High-temperature data were analyzed using Birch-Murnaghan equation of state and thermal pressure approach. The temperature derivative of bulk modulus was found to be −0.061(9) GPa K⁻¹. Significant anisotropy of osmium compressibility was observed.     

Dynamic properties of Ni, Cu, and Fe in the condensed state: The molecular dynamics method

The distribution function for the density of vibrational states and the velocity distribution function in the crystalline, liquid, and amorphous states of Ni, Cu, and Fe are studied by the molecular dynamics method. In the crystalline and amorphous states, the dynamic properties are qualitatively the same, while in the liquid state, additional low-energy excitations appear. These excitations may be treated as low-frequency resonant modes that arise because of the significant contribution of nonlinearity to the interaction potentials. In all the three states, the velocity distribution functions are found to be Maxwellian; that is, the systems are ergodic, although nonlinearity-related contributions to the interaction potentials are high and the liquid and amorphous states are disordered.     

Volume and structural study of Fe64Mn36 anti-ferromagnetic Invar alloy under high pressure

We have investigated the pressure variation of the volume and structure of an FCC Fe₆₄Mn₃₆ anti-ferromagnetic Invar alloy. The inclination of the pressure-volume (P-V) curve of the FCC structure becomes discontinuous at a pressure of 4 GPa. According to the bulk modulus at zero pressure estimated by the Birch-Murnaghan equation of state, the pressure between 4 and 10 GPa is 33 GPa larger than that at a pressure below 4 GPa. Considering previous experiments on magnetism at high pressure the Neel temperature at 4 GPa almost decreases to room temperature. These results suggest that the increase in the bulk modulus by 33 GPa can be attributed to the pressure-induced magnetic phase transition from anti-ferromagnetism to paramagnetism. Volume at zero pressure was estimated using the Birch-Murnaghan equation of state. The volume of FCC structure in the anti-ferromagnetic state was 1.17% larger than the volume in the paramagnetic state, namely, the spontaneous magnetostriction was 1.17%. Pressure-induced structural transition from FCC to HCP occurs with an increase in the pressure, especially at up to 5 GPa. The value of c/a is 1.62; this value almost corresponds to that of an ideal HCP structure. The bulk modulus of the HCP structure estimated by the Birch-Murnaghan equation of state is larger than that of the FCC structure, and the volume/atom ratio is smaller than that of the FCC structure.     

Stable dynamic states at the nematic liquid crystals in weak shear flow

We study stable equilibria of liquid crystals in the flow being at rest and the stable dynamic states for nematic liquid crystals under weak shear flow for the Doi model [M. Doi, S.F. Edwards, The Theory of Polymer Dynamics, Oxford University Press, 1986]. It is first theoretically proven that there is a hysteresis phenomenon in the flow being at rest when the non-dimensional potential intensity among particles changes. Furthermore, in the weak shear flow, we show that there exist many stable dynamic states: flow aligning, tumbing, log-rolling and kayaking, which depend on the initial concentrated orientation of liquid crystal particles. The results are consistent with those of numerical simulation [M.G. Forest, Q. Wang, R. Zhou, The weak shear kinetic phase diagram for nematic polymers, Rheol. Acta 43 (2004) 17-37; M.G. Forest, R. Zhou, Q.Wang, Full-tensor alignment criteria for sheared nematic polymers, J. Rheol. 47 (2003) 105-127] and experimental discoveries [W.R. Burghardt, Molecular orientation and rheology in sheared lyotropic liquid crystalline polymers, Macromol. Chem. Phys. 199 (1998) 471-488; Ch. Gähwiller, Temperature dependence of flow alignment in nematic liquid crystals, Phys. Rev. Lett. 28 (1972) 1554-1556]. Theoretical analysis is reported the first time that the Kayaking state does not circulate around a fixed direction but the asymmetric axis will periodically change.     

A phenomenological theory of metastable states in disordered Ising magnets

A mechanism of the formation of an exponentially large number of metastable states in magnetic phases of disordered Ising magnets as a result of condensation of fractal delocalized modes near the localization threshold is suggested. The thermodynamic properties of metastable states are studied in the effective-field approximation in the vicinity of transitions in magnets with zero uniform magnetization in the ground state such as dilute antiferromagnets, spin glasses, and dilute ferromagnets with dipole interaction. These properties are shown to determine the parameters of nonequilibrium processes in the glassy phase, namely, the shape of the hysteresis loop, the thermodynamic values in field-cooled and zero-field-cooled regimes, and the thermoremanent and isothermal remanent magnetization values.     

An in situ high-pressure X-ray diffraction experiment of hydroxyapophyllite

The compression behavior of a natural hydroxyapophyllite is investigated up to about 10.01 GPa at 300 K using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at High Pressure Experiment Station, Beijing Synchrotron Radiation Facility (BSRF). Over this pressure range, no phase change or disproportionation is observed. The isothermal equation of state is determined for the first time. The values of zero-pressure volume V₀, isothermal bulk modulus K₀, and K₀' refined with a third-order Birch-Murnaghan equation of state are V₀=1276.3±0.9 ų, K₀=71±3 GPa, and K₀'=8±1. Furthermore, we confirm that the values of linear compressibility β along a and c directions of hydroxyapophyllite are elastically anisotropic.     

Athermal character of the solid state amorphization of lactose induced by ball milling

In this paper, we report the possibility to reach pure glassy amorphous lactose by ball milling of crystalline α lactose under a dry nitrogen atmosphere. This route to the glassy state is found to be free of mutarotation towards the anomer β while this mutarotation is unavoidable using the usual thermal route, i.e. the quench of the liquid. This result definitely makes the ‘local quench melting’ hypothesis unsuitable to account for amorphization by ball milling.     

Corresponding states of nematic birefringence: an order parameter universality

In this work, experimental birefringence data of several nematic liquid crystals, which share the presence of a nematic–isotropic and a nematic–crystalline phase transition, are used to show that the birefringence presents a universal behaviour which encompasses the entire range of the nematic phase. The meaning and consequences of such behaviour are discussed; as the order parameter is proportional to the birefringence, this result implies that the order parameter has an extended universal profile, similar to a corresponding state law, which is independent of the liquid crystal compound and becomes determined once the temperature interval of the existence of the nematic compounds is obtained.     

Isothermal compressibility and bulk modulus for methanol under the effect of pressure and temperatures

It has been demonstrated that the spinodal model produces very well the isothermal compressibility of liquid methanol for a wide range of pressures and temperatures. We have used the pseudospinodal model further to determine pressure derivatives, first-order as well as second-order of isothermal compressibility and bulk modulus for liquid methanol in the range of pressures (0–100 MPa) and temperatures (208.17 K–298.16 K). The results have been found to present close agreement with the available experimental data. We have also calculated the values of densities as a function of pressure and temperature for methanol using the Stacey equation of state.