Slow dynamics and re-entrant melting in a polydisperse hard-sphere fluid

Extensive molecular dynamics simulations are performed at 6% polydispersity to investigate the phase diagram of a polydisperse hard-sphere fluid and the dynamical behavior in each phase. As the volume fraction phi is increased, the existence of a supercooled liquid is suggested above phi = 0.5524 by the mean-field analysis proposed recently. The first-order phase transition from supercooled liquid to crystal is then shown to occur around phi = 0.5630. The occurrence of re-entrant melting, a first-order phase transition from crystal to supercooled liquid, is also found around phi = 0.5715. The existence of the glass transition is thus suggested, even in the hard-sphere fluid with small polydispersity.     

Communication: crystallite nucleation in supercooled glycerol near the glass transition

Heterogeneity and solid-like structures found near the glass transition provide a key to a better understanding of supercooled liquids and of the glass transition. However, the formation of solid-like structures and its effect on spatial heterogeneity in supercooled liquids is neither well documented nor well understood. In this work, we reveal the crystalline nature of the solid-like structures in supercooled glycerol by means of neutron scattering. The results indicate that inhomogeneous nucleation happens at temperatures near T(g). Nevertheless, the thermal history of the sample is essential for crystallization. This implies such structures in supercooled liquids strongly depend on thermal history. Our work suggests that different thermal histories may lead to different structures and therefore to different length and time scales of heterogeneity near the glass transition.     

The ultimate fate of supercooled liquids

In recent years it has become widely accepted that a dynamical length scale ξ(α) plays an important role in supercooled liquids near the glass transition. We examine the implications of the interplay between the growing ξ(α) and the size of the crystal nucleus, ξ(M), which shrinks on cooling. We argue that at low temperatures where ξ(α) > ξ(M) a new crystallization mechanism emerges, enabling rapid development of a large scale web of sparsely connected crystallinity. Though we predict this web percolates the system at too low a temperature to be easily seen in the laboratory, there are noticeable residual effects near the glass transition that can account for several previously observed unexplained phenomena of deeply supercooled liquids including Fischer clusters and anomalous crystal growth near T(g).     

On the influence of a patterned substrate on crystallization in suspensions of hard spheres

We present a computer simulation study on crystal nucleation and growth in supersaturated suspensions of mono-disperse hard spheres induced by a triangular lattice substrate. The main result is that compressed substrates are wet by the crystalline phase (the crystalline phase directly appears without any induction time), while for stretched substrates we observe heterogeneous nucleation. The shapes of the nucleated crystallites fluctuate strongly. In the case of homogeneous nucleation amorphous precursors have been observed [T. Schilling et al., Phys. Rev. Lett. 105(2), 025701 (2010)]. For heterogeneous nucleation we do not find such precursors. The fluid is directly transformed into highly ordered crystallites.     

Transitions in poly(diethyl siloxane)

An adiabatic heat capacity study of poly(diethylsiloxane) confirms that it has a single glass transition occurring at 130°K, the lowest glass transition reported to date for a high molecular weight polymer. The two previously reported glass transitions are first-order thermodynamic peaks whose location is dependent upon prior thermal history. Combination of these data with low-temperature x-ray diffraction indicates that the transitions in this temperature range are related to a crystal–crystal transformation. A crystal melting transition is observed near 270°K. In addition an anomalous rise in heat capacity near 60°K suggests a sub-glass transition of unknown origin.     

Non-isothermal crystallization kinetics of a Si–Ca–P–Mg bioactive glass

In this work, the crystallization process of a SiO₂–3CaO·P₂O₅–MgO glass was studied by non-isothermal measurements using differential thermal analysis carried out at various heating rates. X-ray diffraction at room and high temperature was used to identify and follow the evolution of crystalline phases with temperature. The activation energy associated with glass transition, (E _g), the activation energy for the crystallization of the primary crystalline phase (E _c), and the Avrami exponent (n) were determined under non-isothermal conditions using different equations, namely from Kissinger, Matusita & Sakka, and Osawa. A complex crystallization process was observed with associated activation energies reflecting the change of behavior during in situ crystal precipitation. It was found that the crystallization process was affected by the fraction of crystallization, (x), giving rise to decreasing activation energy values, E _c(x), with the increase of x. Values ranging from about 580 kJ mol^?1 for the lower crystallized volume fraction to about 480 kJ mol^?1 for volume fractions higher than 80 % were found. The Avrami exponents, calculated for the crystallization process at a constant heating rate of 10 °C min^?1, increased with the crystallized fraction, from 1.6 to 2, indicating that the number of nucleant sites is temperature dependent and that crystals grow as near needle-like structures.     

Weak correlations between local density and dynamics near the glass transition

We perform experiments on two different dense colloidal suspensions with confocal microscopy to probe the relationship between local structure and dynamics near the glass transition. We calculate the Voronoi volume for our particles and show that this quantity is not a universal probe of glassy structure for all colloidal suspensions. We correlate the Voronoi volume to displacement and find that these quantities are only weakly correlated. We observe qualitatively similar results in a simulation of a polymer melt. These results suggest that the Voronoi volume does not predict dynamical behavior in experimental colloidal suspensions; a purely structural approach based on local single particle volume likely cannot describe the colloidal glass transition.     

Glassy dynamics and kinetic vitrification of isotropic suspensions of hard rods

A nonlinear Langevin equation (NLE) theory for the translational center-of-mass dynamics of hard nonspherical objects has been applied to isotropic fluids of rigid rods. The ideal kinetic glass transition volume fraction is predicted to be a monotonically decreasing function beyond an aspect ratio of two. The functional form of the decrease is weaker than the inverse aspect ratio. Vitrification occurs at lower volume fractions for corrugated tangent bead rods compared to their smooth spherocylinder analogs. The ideal glass transition signals a crossover to activated dynamics, which is estimated to be observable before the nematic phase boundary is encountered if the aspect ratio is less than roughly 25. Calculations of the glassy elastic shear modulus and absolute yield stress reveal a roughly exponential growth with volume fraction. The dependence of entropic barriers and mean barrier hopping times on concentration for rods of variable aspect ratios can be collapsed quite well based on a difference volume fraction variable that quantifies the distance from the ideal glass boundary. Full numerical solution of the NLE theory via stochastic trajectory simulation was performed for tangent bead rods, and the results were compared to their hard sphere analogs. With increasing shape anisotropy the characteristic length scales of the nonequilibrium free energy increase and the magnitude of the localization well and entropic barrier curvatures decreases. These changes result in a significant aspect ratio dependence of dynamical properties and time correlation functions including weaker intermediate time subdiffusive transport, stronger two-step decay of the incoherent dynamic structure factor, longer mean alpha relaxation time, and stronger wavevector-dependent decoupling of relaxation times and the self-diffusion constant. The theoretical results are potentially testable via computer simulation, confocal microscopy, and dynamic light scattering.     

不同结晶度的乙二醇及其水溶液玻璃化转变与焓松弛

为了考察晶体成分对无定形成分玻璃化转变和结构松弛行为的影响,利用差示扫描量热法(DSC),结合低温显微技术,研究了乙二醇(EG)及其50％水溶液在不同结晶度时的玻璃化转变和焓松弛行为.采用等温结晶方法控制骤冷的部分结晶玻璃体中的晶体份额.DSC结果表明,对于部分结晶的EG,只有单一的玻璃化转变过程,而对于50％EG,当结晶度不同时,不同程度地表现出两次玻璃化转变（无定形相Ⅰ和无定形相Ⅱ）.相Ⅰ的玻璃化转变温度和完全无定形态的含水EG的玻璃化转变温度相一致;相Ⅱ的玻璃化转变温度要比此温度约高6 ℃.低温显微观察结果印证了DSC实验结果.DSC等温退火的实验和KWW(Kohlrausch-Williams-Watts)衰变函数分析结果表明,EG无定形和50％EG中的两种无定形有不同的焓松弛行为.     

Polymer induced changes of the crystallization scenario in suspensions of hard sphere like microgel particles

We investigated the crystallization scenario of highly cross linked polystyrene particles dispersed in the good solvent 2-ethylnaphtalene and their mixtures with non-adsorbing low molecular weight polysterene polymer using time resolved static light scattering. The samples were prepared slightly below the melting volume fraction of the polymer free system. For the polymer free samples, we obtained polycrystalline solids via crystallization scenario known from hard sphere suspensions with little competition of wall crystal formation. Addition of non-adsorbing low molecular weight polystyrene polymer leads to a considerably slowing down of the bulk crystallization kinetics. We observed a delay of the precursor to crystal conversion for the bulk crystallization while the induction times for the wall nucleation are reduced. The increased polymer concentration thus shifts the balance between the two competing crystallization pathways giving the possibility to tune the relative amount of wall based crystals.     

Dielectric study of the slow motional processes in the polymorphic States of anhydrous caffeine

Molecular mobility in crystalline anhydrous caffeine was studied by the dielectric technique of thermally stimulated depolarization currents (TSDC). Two relaxational processes were found, one appearing at approximately -10 degrees C that is ascribed to a reorientational glass transition, and a higher temperature one that probably arises from local molecular motions that are precursors of diffusion and sublimation. The experimental results suggest that both crystalline phases II and I of caffeine, that have distinct crystal structures, are solid rotator phases. Furthermore, this dynamic reorientational disorder shows a reorientational glass transition at the same temperature in phase II and in metastable phase I.     

Polymorph selection in the crystallization of hard-core Yukawa system

Colloid-colloid interactions in charge-stabilized dispersions can to some extent be represented by the hard-core Yukawa model. The crystallization process and polymorph selection of hard-core Yukawa model are studied by means of smart Monte Carlo simulations in the region of face-centered-cubic (fcc) phase. The contact value of hard-core Yukawa potential and the volume fraction of the colloids are fixed, while the Debye screening length can be varied. In the early stage of the crystallization, the precursors with relatively ordered liquid structure have been observed. Although the crystal structure of thermodynamically stable phase is fcc, the system crystallizes into a mixture of fcc and hexagonal close-packed (hcp) structures under small Debye screening length since the colloidal particles act as effective hard spheres. In the intermediate range of Debye screening length, the system crystallizes into a mixture of fcc, hcp, and body-centered-cubic (bcc). The existence of metastable hcp and bcc structures can be interpreted as a manifestation of the Ostwald’s step rule. Until the Debye screening length is large enough, the crystal structure obtained is almost a complete fcc suggesting the system eventually reaches to a thermodynamically stable state.     

Dielectric study of relaxations and polymorphism in poly(diethyl siloxane)

The dielectric behavior of poly(diethyl siloxane) supports the adiabatic calorimetric findings of Beatty and Karasz. In particular, a sub-T_g transition is observed near ?180°C at 100 Hz, the glass transition near ?135°C at 100 Hz, and a first-order transition near ?70°C (crystal–crystal transformation). This glass-transition temperature is the lowest reported polymeric glass transition for polymers.     

The kinetics of homogeneous and two-step nucleation during protein crystal growth from solution

Many experimental reports for the kinetics of crystal nucleation and growth, from an isothermal solution, point to a sigmoidal-like behavior for the process. Here we consider three different nucleation models from the literature and show that all lead to sigmoidal or sigmoidal-like behavior for the kinetics of nucleation. A two-step nucleation process is known to occur within certain supersaturated protein solutions, and it is demonstrated in this report how the sigmoidal law yields kinetic information for the two-step and homogeneous nucleation modes. We propose here that two-step solute-rich associates form in the solution around seed nuclei that are already present at or near the point in time when the solution is prepared. Using this hypothesis, we are able to model the time-dependent volume of the two-step phase per unit volume of solution and show that this compares well with reported experimental data. A kinetic model is given for the proposed process, which leads to a sigmoidal rate law. Additionally, a relation between the initial and final nuclei densities and the induction time is derived. As a result of this study, the conclusion is that two-step activity increases with increasing initial supersaturation or increasing salt concentration.     

Effect of growth conditions on the structure of two-dimensional latex crystals: experiment

The growth kinetics and structure of two-dimensional crystals of fine latex particles on solid substrates have been studied using a variety of microscopic techniques: optical microscopy, surface plasmon resonance microscopy, transmission electron microscopy, scanning electron microscopy and atomic force microscopy. A circular-shaped crystal is grown from a thin layer of a latex suspension by a two-step mechanism: nucleation and crystal growth. Here we report an experimental study of the factors influencing the crystallization process, especially focusing on the water evaporation rate, the liquid meniscus at the crystal boundary, the particle size and concentration, the substrate, etc. Crystals of good quality and structure are grown at a high evaporation rate (low humidity) favoring a convection-dominated influx of particles from the suspension. The particle diffusion plays a role at suppressed evaporation thus causing an increase in the number of crystal defects. The dynamics of the meniscus slope leads to growth instability resulting in a sequence of multilayer rings. A hexagonal lattice prevails in the final crystal whereas a square lattice is observed in the transition regions between two different hexagonal multilayers. These general trends of the crystallization process are the same for different particle diameters (19 nm, 55 nm, 144 nm and 1.696 μm), volume fractions (0.001–0.01) and substrates (bare and metal-coated glass and mica). Received: 8 February 1999 Accepted in revised form: 12 May 1999     

Microscopic theory of gelation and elasticity in polymer-particle suspensions

A simplified mode-coupling theory (MCT) of ergodic-nonergodic transitions, in conjunction with an accurate two-component polymer reference interaction site model (PRISM) theory for equilibrium structural correlations, has been systematically applied to investigate gelation, localization, and elasticity of flexible polymer-hard particle suspensions. The particle volume fraction at the fluid-gel transition is predicted to depend exponentially on reduced polymer concentration and size asymmetry ratio at relatively high colloid concentrations. In contrast, at lower particle volume fractions, a power-law dependence on polymer concentration is found with effective exponents and prefactors that depend systematically on the polymer/particle size ratio. Remarkable power-law and near universal scaling behavior is found for the localization length and elastic shear modulus. Multiple experiments for gel boundaries and shear moduli are in good agreement with the no adjustable parameter theory. The one exception is the absolute magnitude of the shear modulus which is strongly overpredicted, apparently due to nonequilibrium dense cluster formation. The simplified MCT-PRISM theory also captures the qualitative aspects of the weak depletion-driven "glass melting" phenomenon at high particle volume fractions. Calculations based on an effective one-component model of structure within a low particle volume fraction framework yield qualitatively different features than the two-component approach and are apparently all in disagreement with experiments. This suggests that volume fraction and size asymmetry dependent many-body screening of polymer-mediated depletion attractions at finite particle concentrations are important.     

Several routes to the glassy states in the one component soft core system: revisited by molecular dynamics

Molecular dynamics simulations have been performed to study the glass transition for the soft core system with a pair potential φ(n)(r) = ε(σ∕r)(n) of n = 12. Using the compressibility factor, PV/Nk(B)T=P?(ρ*), its phase diagram can be represented as a function of a reduced density, ρ? = ρ(ε∕k(B)T)(3∕n), where ρ = Nσ(3)∕V. In the present work, NVE relaxations to the glassy or crystalline states starting from the unstable states in the phase diagram have been revisited in details and compared with other processes. Relaxation processes can be characterized by the time dependence of the dynamical compressibility factor (PV/Nk(B)T)(t)?(≡g(ρ(t)*)) on the phase diagram. In some cases, g(ρ(t)*) reached a crystal branch in the phase diagram; however, metastable states are found in many cases. With connecting points for the metastable states in the phase diagram, we can define a glass branch where the dynamics of particles are almost frozen. The structures observed there have common properties characterized as glasses. Although overlaps of glass forming process and nanocrystallization process are observed in some cases, these behaviors are distinguishable to each other by the characteristics of structures. There are several routes to the glass branch and we suggest that all of them are the glass transition.     

Superconducting fullerene nanowhiskers

We synthesized superconducting fullerene nanowhiskers (C(60)NWs) by potassium (K) intercalation. They showed large superconducting volume fractions, as high as 80%. The superconducting transition temperature at 17 K was independent of the K content (x) in the range between 1.6 and 6.0 in K-doped C(60) nanowhiskers (K(x)C(60)NWs), while the superconducting volume fractions changed with x. The highest shielding fraction of a full shielding volume was observed in the material of K(3.3)C(60)NW by heating at 200 °C. On the other hand, that of a K-doped fullerene (K-C(60)) crystal was less than 1%. We report the superconducting behaviors of our newly synthesized K(x)C(60)NWs in comparison to those of K(x)C(60) crystals, which show superconductivity at 19 K in K(3)C(60). The lattice structures are also discussed, based on the x-ray diffraction (XRD) analyses.     

Sol-Gel Synthesis and Structure of Borosilicon Oxycarbide Glasses

Existing sol-gel polymerisation/pyrolysis routes employing two separate boron containing metal alkoxide precursors have been applied to form multi-component silicon oxycarbide glasses based on a borosilicon oxycarbide (B–Si–O–C) system. 29Si, and 11B magic angle spinning nuclear magnetic resonance (MAS-NMR) was used to characterize the atomic structure of the gels, glasses and glass ceramics. Structural changes such as glass formation and crystal nucleation were identified by X-ray diffraction (XRD). Transmission electron microscopy (TEM) provided images of crystal nucleation and growth.