Local structure of supercooled liquid Ga90In10 alloy

The local structure of liquid and supercooled liquid Ga₉₀In₁₀ alloy was studied by the X-ray absorption fine-structure (XAFS), X-ray diffractometer (XRD) and the ab initio molecular dynamics (AIMD) simulation. The ab initio FEFF8 code was applied to simulate the In k-edge X-ray absorption near edge structure (XANES) spectrum of the melt. The local atomic arrangement models have been obtained. The results indicate that the structural evolution from the liquid to supercooled liquid Ga₉₀In₁₀ alloy is mainly caused by the change of the In atom local structure. As the temperature decreases, the nearest neighbor coordination number decreases and the nearest neighbor interatomic distance increases. The nearest neighbor coordination number around In atom decreases from 13 to 12, and there is obvious Ga aggregation under the undercooled condition.     

Comparison of thermal and elastic properties of glassy racemic and enantiomorphic ibuprofen studied by Brillouin light scattering and modulated differential scanning calorimetry

The vitrification process of racemic RS- and enantiomorphic S-ibuprofen was studied by using Brillouin light scattering and modulated differential scanning calorimetry (DSC). The sound velocity and the attenuation coefficient of both compounds were determined for the first time in the glassy, supercooled liquid and liquid states. The sound velocity and the hypersonic damping were similar between the two ibuprofen pharmaceuticals over the whole investigated temperature range including glassy, supercooled liquid and liquid states. The thermal expansion coefficient of the RS-ibuprofen was smaller than that of the S-ibuprofen, which suggests that the intermolecular force of the former is slightly stronger than the latter. The thermal relaxation times derived from the modulated DSC were consistent with the dielectric relaxation times in both RS- and S-ibuprofens. The fragility index of S-ibuprofen just above the glass transition was determined to be 73, which was smaller compared to the value of RS-ibuprofen, 89. This difference in the fragility indicates that the decrease in the fragility of S-ibuprofen compared to the racemic one may improve its stability of the amorphous state below the glass transition temperature against crystallization.     

Ab initio molecular dynamics simulations on structural change of supercooled liquid Si at different temperatures from 1700 to 1100 K

Using ab initio molecular dynamics simulations, the local atomic structure and electronic properties of supercooled liquid Si (l-Si) at different temperatures from 1700 to 1100 K were studied. Our calculated coordination numbers present no obvious change in the temperature range investigated. Our results indicate that the structure of supercooled l-Si may be well described as a combined local atomic configuration of white-tin and diamond type structures. Upon cooling from 1700 to 1100 K, the tetrahedral white-tin type ordering collapses gradually toward the tetrahedral diamond-type structure. No drastic change behavior is observed in our work.     

Correlation of fragility with mechanical moduli in double-well potential for glass-forming liquid

The shoving model and the Vogel-Fulcher relation are employed to derive correlation of the fragility with the mechanical moduli for glass-forming simple liquids. The result shows that a liquid with smaller fragility will have larger ratio of K_∞/G_∞ in dilute liquid system. Based on radial distribution function with the Lennard-Jones potential modified by the Gaussian potential with a second minimum, fragility of the supercooled simple liquid is derived from the correlation between viscosity and shear modulus via configurational entropy. The results demonstrate that the fragility is determined by two parts: thermodynamic components and mechanical moduli. For a weak Gaussian potential liquid, the fragility is proportional to the T_g, while for a strong one, the fragility is inversely proportional to the T_g, and the Gaussian potential will increase fragility.     

A Mössbauer comparison of the recoil-free fraction of a supercooled smectic liquid crystal with its solid state

We have dissolved 0.2% by weight of diacetylferrocene into 4-n-hexoxybenzylidene-4′-n-propylaniline and measured the Fe-57 recoil-free fraction (f) as a function of temperature in the range 100°–300°K in the solid phase and the supercooled smectic H liquid crystalline phase.     

Dynamics of supercooled confined water measured by deep inelastic neutron scattering

In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter ~ 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid–liquid transition of supercooled confined water) on a “wet” sample with hydration h ~ 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually “dry” sample at h ~ 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid–liquid transition hypothesis.     

Metallic glassy fibers

A review on the formation and unique physical and mechanical properties of metallic glassy fibers (MGFs) with the diameter ranging from micro to nano scales fabricated by a supercooled liquid extraction method (SLEM) is given. The SLEM method, through driving metallic glass rods in their supercooled liquid region via superplasticity, can fabricate MGFs with precisely designed and controlled size and properties, high structural uniformity and surface smoothness and extreme flexibility. The SLEM method is efficient and the MGFs can be continuously prepared by this method. A parameter f based on the thermal and rheological properties of MG-forming alloys is proposed to control the preparation and size of the fibers. We show that the novel MGFs with superior properties may attract intensive scientific interests and propel more engineering and functional applications.     

On the problem of the existence of a supercooled liquid phase of cryovacuum ethanol condensates

Our previous IR-spectrometry and thermodesorption studies of thin films of cryovacuum ethanol condensates and comparison of these data with the results obtained in works of some groups have allowed us to make several conclusions relative to temperature ranges of existence of low-temperature states of ethanol. Newly acquired experimental data indicate that the cryovacuum condensates of ethanol formed at temperatures considerably below the glass transition temperature T _g ≈ 98 K pass through the state that can be characterized as a supercooled liquid phase in the course of subsequent thermally stimulated transformations. The temperature range of the solid-liquid transformation (97–100 K) agrees well with the data of researchers who studied the ethanol samples obtained by the vitrification from the liquid phase.     

Increasing Superplasticity and Strong Dynamic Behaviour of Zr--Cu--Ni--Al Bulk Metallic Glass

The plasticity and the dynamic fragility of bulk metallic glass of a Zr62 CuxsNiloAllo alloy are studied by three- point beam bending methods. We find that the alloy behaves super plastic not only at room temperature, but also at high temperatures. More importantly, it is found that the superplasticity increases with increasing temperature. In addition, the dynamic fragility parameter m for the supercooled liquid of this alloy is measured to be 34.87 and the supercooled liquid of Zr62 CuxsNixoAlxo alloy behaves as a strong liquid.     

Tracer diffusion in glassforming liquids

In the last decades, a wide collection of experimental evidence has been found in the study of supercooled glassformers on the existence of a crossover between two dynamical regimes at a temperature T_c. We discuss the validity of the Vogel-Fulcher-Tammann in both regions. The breakdown of the Stokes-Einstein relation below T_c is presented, indicating that the diffusion coefficient of a tracer becomes decoupled from the viscosity through an exponent ξ, and the diffusion process is intensified. We verify that a temperature shift on the diffusion coefficient introduces the same effect as the Stokes-Einstein breakdown equation. We present the dependence of this exponent on the ratio between the radii of the tracer and the host liquid molecule.     

Crystallization behaviour in a new multicomponent Ti16.6Zr16.6Hf16.6Ni20Cu20Al10 metallic glass developed by the equiatomic substitution technique

A new amorphous Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ alloy has been developed using the novel equiatomic substitution technique. Melt spinning Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ forms an amorphous phase with a large supercooled liquid region, ΔT=70°C. After isothermal annealing within the supercooled liquid region for 3 h at 470°C, the amorphous alloy crystallizes to form a fine-scale distribution of 2–5 nm nanocrystals, and the supercooled liquid region increases to ΔT=108°C. Atomic-scale compositional analysis of this partially crystalline material using a three-dimensional atom probe (3DAP) is unable to detect any compositional difference between the nanocrystals and the remaining amorphous phase. After annealing for 1 hr at 620°C, the amorphous alloy crystallizes to form 20–50nm equiaxed grains of a hexagonal-type C14 Laves phase with lattice parameters a = 5.2Å and c = 9.0 Å. 3DAP analysis shows that this Laves phase has a composition very close to that of the initial amorphous phase, suggesting that the alloy crystallizes via a polymorphic rather than a primary crystallization mechanism, despite the complexity of the alloy composition.     

Glass-forming liquids

When liquids are cooled below their melting temperature T_m, sometimes they do not solidify immediately but remain in supercooled state up to temperatures far below the melting point. Under certain conditions, they can solidify into the form of amorphous solids without crystallizing. A supercooled liquid and a amorphous solid are metastable phases, which are not completely understood in terms of structural arrangement and thermodynamic behaviour. But by far the most interesting feature is the glass transition which is the manifestation of a true thermodynamic transition and a dynamic event since a dramatic dynamic arrest intervenes. A unified theory of supercooled liquids and glass transition does not yet exist and, more specifically, the link between the sharp increase of the relaxation time and the correlation length is a question still largely open. This article presents in the most elementary manner a brief overview of this delicate issue.     

On the applicability of mode coupling theory to a ϕ 4-model with first order phase transition

A ? ⁴-model with symmetric double-well-like on-site potential and anharmonic, infinite range interactions is investigated. This model exhibits a first order phase transition at a temperature T _c. The time-dependent displacement correlation function is studied in the framework of the mode coupling theory (MCT). Depending on the choice of slow modes, MCT makes qualitatively different predictions which are compared with MD-results. These numerical results suggest that only the order parameter mode {ie1-1} should be considered as slow. In that case it is shown that MCT yields a dynamical transition in the supercooled high-temperature phase {ie1-2} at a temperature T* which coincides with the spinodal temperature T _s (T _s = 0 for our model) where the metastable supercooled phase becomes instable.     

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     

Nuclear spin relaxation of Xe in liquid Te

By the method of time differential perturbed angular distribution following a nuclear reaction, the relaxation rateT _r ^?1 of the 8 msI ^π=10⁺ isomer of¹³²Xe has been measured in liquid Te. Between 670 °K (supercooled liquid) and 1,000 °K the rate decreases from about 720/s by about a factor of two. From existing experimental material it is concluded thatT _r ^?1 is mainly due to quadrupolar interaction (T _r ^?1 ≈T _Q ^?1 ). Its magnitude is discussed considering the metallic and the noble gas limit as models for the Xe-Te-interactions. The temperature dependenceT _Q(T) apparently does not correlate with the diffusion constant of Te in contrast to a simplified theoretical treatment. — The nuclearg value of the isomer has been determined to be g=(?)0.195(5) thus confirming the configuration (vh_11/2)².     

Compressed-exponential relaxations in supercooled liquid trehalose

We investigated the α-relaxations in supercooled liquid trehalose by using photon correlation spectroscopy (PCS) and found an interesting compressed-exponential relaxation at temperatures above 140 °C. The q^?1 dependence of its relaxation time corresponds to an ultraslow ballistic motion due to the local structure rearrangements. In the same temperature range, we found the glycosidic bond structure changes in trehalose molecule from the Raman scattering and the X-ray direction measurements. We concluded that the compressed-exponential relaxation in supercooled liquid trehalose might originate from the intra-molecular (glycosidic bond) structure change.     

Glass transition kinetics of the binary Si12.5Te87.5 alloy

Binary Si_12.5Te_87.5 glass was prepared using the melt-quench technique. Differential scanning calorimetry measurements of the obtained glass measured at different heating rates (10 ≤ α ≤ 70 K/min) have shown three, one endo- and two exothermic, peaks. The glass transition kinetics have been analyzed using the isoconversional (model-free) methods in addition to the model-fitting method. The analysis of the present data shows that the glass transition kinetics are not constant values but vary with the transformed extent (x) and hence with temperature of the specimen. Non-linear decrease of E with increase in the transformed extent could be attributed to a complicated mechanism. Based on the peak shape of n(α) relation, one concludes that two competing mechanisms are working together during transformation of the solid glass to supercooled liquid state. A good agreement between the experimental and the reconstructed (x–T) curves confirms the validity of the applied models.     

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.     

A statistical model of a metallic inclusion in semiconducting media

The atomic dynamics of the binary Al_100–xCu_x system is simulated at a temperature T = 973 K, a pressure p = 1.0 bar, and various copper concentrations x. These conditions (temperature, pressure) make it possible to cover the equilibrium liquid Al_100–xCu_x phase at copper concentrations 0 ≤ x ≤ 40% and the supercooled melt in the concentration range 40% ≤ x ≤ 100%. The calculated spectral densities of the time correlation functions of the longitudinal \({\tilde C_L}\)(k, ω) and transverse \({\tilde C_T}\)(k, ω) currents in the Al_100–xCu_x melt at a temperature T = 973 K reveal propagating collective excitations of longitudinal and transverse polarizations in a wide wavenumber range. It is shown that the maximum sound velocity in the v_L(x) concentration dependence takes place for the equilibrium melt at an atomic copper concentration x = 10 ± 5%, whereas the supercooled Al_100–xCu_x melt saturated with copper atoms (x ≥ 40%) is characterized by the minimum sound velocity. In the case of the supercooled melt, the concentration dependence of the kinematic viscosity ν(x) is found to be interpolated by a linear dependence, and a deviation from the linear dependence is observed in the case of equilibrium melt at x < 40%. An insignificant shoulder in the ν(x) dependence is observed at low copper concentrations (x < 20%), and it is supported by the experimental data. This shoulder is caused by the specific features in the concentration dependence of the density ρ(x).