Polydispersity-induced macrophase separation in diblock copolymer melts

The effect of A-block polydispersity on the phase behavior of AB-diblock copolymer melts is examined using a complete self-consistent field theory treatment that allows for fractionation of the parent molecular-weight distribution. In addition to observing the established shift in phase boundaries, we find the emergence of significant two-phase coexistence regions causing, for instance, the disappearance of the complex phase window. Furthermore, we find evidence that polydispersity relieves packing frustration, which will reduce the tendency for long-range order.     

The hard ellipsoid-of-revolution fluid I. Monte Carlo simulations

We present the results of Monte Carlo simulations on a system of hard ellipsoids of revolution with length-to-breadth ratios a/b = 3, 2.75, 2, 1.25 and b/a = 3, 2.75, 2, 1.25. We identify four distinct phases, viz. isotropic fluid, nematic fluid, ordered solid and plastic solid. The coexistence points of all first order phase transitions are located by performing absolute free energy computations for all coexisting phases. We find nematic phases only for a/b ≥ 2.75 and a/b ≤ 1/2.75. A plastic solid is only observed for 1.25 ≥ a/b ≥ 0.8. It is found that the phase diagram is surprisingly symmetric under interchange of the major and minor axes of the ellipsoids.     

Simulation of fluid-solid coexistence via thermodynamic integration using a modified cell model

Despite recent advances, precise simulation of fluid-solid transitions still remains a challenging task. Thermodynamic integration techniques are the simplest methods to study fluid-solid coexistence. These methods are based on the calculation of the free energies of the fluid and the solid phases, starting from a state of known free energy which is usually an ideal-gas state. Despite their simplicity, the main drawback of thermodynamic integration techniques is the large number of states that must be simulated. In the present work, a thermodynamic integration technique, which reduces the number of simulated states, is proposed and tested on a system of particles interacting via an inverse twelfth-power potential energy function. The simulations are implemented at constant pressure and the solid phase is modeled according to the constrained cell model of Hoover and Ree. The fluid and the solid phases are linked together by performing constant-pressure simulations of a modified cell model. The modified cell model, which was originally proposed by Hoover and Ree, facilitates transitions between the fluid and the solid phase by tuning a homogeneous external field. This model is simulated on a constant-pressure path for a series of progressively increasing values of the field, thus allowing for direct determination of the free energy difference between the fluid and the solid phase via histogram reweighting. The size-dependent results are analyzed using histogram reweighting and finite-size scaling techniques. The scaling analysis is based on studying the size-dependent behavior of the second- and higher-order derivatives of the free energy as well as the dimensionless moment ratios of the order parameter. The results clearly demonstrate the importance of accounting for size effects in simulation studies of fluid-solid transitions.     

Wetting in Multiphase Systems with Complex Geometries

We address the shape and distribution of two-phase systems embedded within a third phase. To motivate this work, we begin by describing transmission electron microscopy observations of the configurations adopted by the solid and vapor phases of lead when these are confined together within a silicon cavity. We then perform analytical calculations of the stability of various possible configurations of two-phase systems confined in a cubic-shaped cavity. The most stable configurations are a function of the volume ratio of the two phases in the cavity, and of a parameter describing the wetting behavior in the three-phase system. The wealth of configurations obtained for embedded solid/fluid or condensed/fluid phases within a solid cavity is presented. Wetting anisotropy on the walls of the cavity, and the faceted or isotropic character of the interface between the two embedded phases, are shown to be physical parameters that determine the number of possible stable configurations.     

Yang-Lee theory for a nonequilibrium phase transition

To analyze phase transitions in a nonequilibrium system, we study its grand canonical partition function as a function of complex fugacity. Real and positive roots of the partition function mark phase transitions. This behavior, first found by Yang and Lee under general conditions for equilibrium systems, can also be applied to nonequilibrium phase transitions. We consider a one-dimensional diffusion model with periodic boundary conditions. Depending on the diffusion rates, we find real and positive roots and can distinguish two regions of analyticity, which can be identified with two different phases. In a region of the parameter space, both of these phases coexist. The condensation point can be computed with high accuracy.     

Free energy studies of freezing in slit pores: an order-parameter approach using Monte Carlo simulation

We report a molecular simulation study of freezing transitions for simple fluids in narrow slit pores. A major stumbling block in previous studies of freezing in pores has been the lack of any method for calculating the free energy difference between the confined solid and liquid phases. Conventional thermodynamic integration methods often fail for confined systems, due to the difficulty in choosing a suitable path of integration. We use a different approach that involves calculating the Landau free energy as a function of a suitable order parameter, using the grand canonical Monte Carlo simulation method. The grand free energy for each phase can then be obtained by one-dimensional integration of the Landau free energy over the order parameter. These calculations are carried out for two types of wall—fluid interaction, a hard wall and a strongly attractive wall modelled on carbon. The grand free energy results for both cases clearly indicate a first order fluid to solid transition. In the case of the attractive carbon wall, there are three phases. Phase A corresponds to all layers having a liquid-like structure; phase B corresponds to the contact layers (the layers adjacent to the two pore walls) being frozen and the rest of the layers being fluid-like; phase C corresponds to all the layers being frozen. Our results for the angular structure function in the individual molecular layers show strong evidence of a transition from a two-dimensional liquid phase to a hexatic phase. This is followed by a transition from the hexatic to a crystal phase.     

Complex phase behavior induced by repulsive interactions

For a solid in which the interactions have a hard core plus a simple soft repulsive tail we show, using a perturbation theory, that the possible stable crystalline structures give rise to a rich phase behavior. We find two concomitant critical points each corresponding to phase transitions separating bcc and fcc structures, respectively, and the occurrence of a transition between fcc and bcc phases without change in density. This novel phenomenology may be relevant to the behavior of some metallic systems, colloids, and to water.     

New phases of zinc under pressure from first principles

A procedure for finding the many stable phases of an element under hydrostatic pressure p is discussed and applied to zinc. Five new phases are found with several different Bravais symmetries under the constraint of one atom per cell and their stabilities as functions of p calculated. The procedure seems generalizable to find all the phases in all Bravais symmetries in a given range of pressure. In particular fcc Zn, which is unstable at p = 0, is shown to be very stable above 320 kbar to at least 1000 kbar. In agreement with Müller et al. [Phys. Rev. B 60, 16448 (1999)], a rhombohedral (rh) phase is found to be stable at p = 0, and several more rh phases are found at pressures up to 320 kbar. The Gibbs free energies of all phases are evaluated as functions of p, and the pressures of thermodynamically favored phase transitions are found. The behavior of Zn is compared to similar behavior of vanadium, which also shows stable rh phases and cubic phase instability in a range of pressure; the bcc phase instability is also healed by additional pressure.     

Lectures on renormalization and asymptotic safety

A short introduction is given on the functional renormalization group method, putting emphasis on its nonperturbative aspects. The method enables to find nontrivial fixed points in quantum field theoretic models which make them free from divergences and leads to the concept of asymptotic safety. It can be considered as a generalization of the asymptotic freedom which plays a key role in the perturbative renormalization. We summarize and give a short discussion of some important models, which are asymptotically safe such as the Gross–Neveu model, the nonlinear σ$\sigma$ model, the sine–Gordon model, and we consider the model of quantum Einstein gravity which seems to show asymptotic safety, too. We also give a detailed analysis of infrared behavior of such scalar models where a spontaneous symmetry breaking takes place. The deep infrared behavior of the broken phase cannot be treated within the framework of perturbative calculations. We demonstrate that there exists an infrared fixed point in the broken phase which creates a new scaling regime there, however its structure is hidden by the singularity of the renormalization group equations. The theory spaces of these models show several similar properties, namely the models have the same phase and fixed point structure. The quantum Einstein gravity also exhibits similarities when considering the global aspects of its theory space since the appearing two phases there show analogies with the symmetric and the broken phases of the scalar models. These results be nicely uncovered by the functional renormalization group method.     

Finite-temperature Wigner solid and other phases of ripplonic polarons on a helium film

Electrons on liquid helium can form different phases depending on density, and temperature. Also the electron-ripplon coupling strength influences the phase diagram, through the formation of so-called “ripplonic polarons”, that change how electrons are localized, and that shifts the transition between the Wigner solid and the liquid phase. We use an all-coupling, finite-temperature variational method to study the formation of a ripplopolaron Wigner solid on a liquid helium film for different regimes of the electron-ripplon coupling strength. In addition to the three known phases of the ripplopolaron system (electron Wigner solid, polaron Wigner solid, and electron fluid), we define and identify a fourth distinct phase, the ripplopolaron liquid. We analyse the transitions between these four phases and calculate the corresponding phase diagrams. This reveals a reentrant melting of the electron solid as a function of temperature. The calculated regions of existence of the Wigner solid are in agreement with recent experimental data.     

A microfluidic spiral for size-dependent fractionation of magnetic microspheres

Magnetic microspheres (MMS) are useful tools for a variety of medical and pharmaceutical applications. Typically, commercially manufactured MMS exhibit broad size distributions. This polydispersity is problematic for many applications. Since the direct synthesis of monodisperse MMS is often fraught with technical challenges, there is considerable interest in and need associated with the development of techniques for size-dependent fractionation of MMS. In this study we demonstrated continuous size-dependent fractionation of sub-micron scale particles driven by secondary (Dean effect) flows in curved microfluidic channels. Our goal was to demonstrate that such techniques can be applied to MMS containing superparamagnetic nanoparticles. To achieve this goal, we developed and tested a microfluidic chip for continuous MMS fractionation. Our data address two key areas. First, the densities of MMS are typically in the range 1.5–2.5 g/cm³, and thus they tend be non-neutrally buoyant. Our data demonstrate that efficient size-dependent fractionation of MMS entrained in water (density 1 g/cm³) is possible and is not significantly influenced by the density mismatch. In this context we show that a mixture comprising two different monodisperse MMS components can be separated into its constituent parts with 100% and 88% success for the larger and smaller particles, respectively. Similarly, we show that a suspension of polydisperse MMS can be separated into streams containing particles with different mean diameters. Second, our data demonstrate that efficient size-dependent fractionation of MMS is not impeded by magnetic interactions between particles, even under application of homogeneous magnetic fields as large as 35 kA/m. The chip is thus suitable for the separation of different particle fractions in a continuous process and the size fractions can be chosen simply by adjusting the flow velocity of the carrier fluid. These facts open the door to size dependent fractionation of MMS.     

Miscibility phase diagrams of giant vesicles containing sphingomyelin

Saturated sphingomyelin (SM) lipids are implicated in lipid rafts in cell plasma membranes. Here we use fluorescence microscopy to observe coexisting liquid domains in vesicles containing SM, an unsaturated phosphatidylcholine lipid (either DOPC or POPC), and cholesterol. We note similar phase behavior in a model membrane mixture without SM (DOPC/DPPC/Chol), but find no micron-scale liquid domains in membranes of POPC/PSM/Chol. We delineate the onset of solid phases below the miscibility transition temperature, and detail indirect evidence for a three-phase coexistence of one solid and two liquid phases.     

Phase behavior of methane haze

Methane aerosols play a fundamental role in the atmospheres of Neptune, Uranus, and Saturn's moon Titan as borne out by the recent Cassini-Huygens mission. Here we present the first study of the phase behavior of free methane aerosol particles combining collisional cooling with rapid-scan infrared spectroscopy in situ. We find fast (within minutes) phase transitions to crystalline states directly after particle formation and characteristic surface effects for nanometer-sized particles. From our results, we conclude that in atmospheric clouds solid methane particles are crystalline.     

Dielectrowetting driven spreading of droplets

The wetting of solid surfaces can be modified by altering the surface free energy balance between the solid, liquid, and vapor phases. Here we show that liquid dielectrophoresis induced by nonuniform electric fields can be used to enhance and control the wetting of dielectric liquids. In the limit of thick droplets, we show theoretically that the cosine of the contact angle follows a simple voltage squared relationship analogous to that found for electrowetting on dielectric. Experimental observations confirm this predicted dielectrowetting behavior and show that the induced wetting is reversible. Our findings provide a noncontact electrical actuation process for meniscus and droplet control.     

Shape deformation and circle instability in two-dimensional lipid domains by dipolar force: a shape- and size-dependent line tension model

The dipolar energy of a solid monolayer domain surrounded by a fluid phase at an air-water interface is derived approximately as a sum of an additionally negative line tension and a curvature-elastic energy at the boundary. Variation of the domain energy yields an equilibrium domain shape equation. The obvious solutions of the domain shape equation clearly predict a circle, torus, D-form, S-form, and serpentine manner shape found experimentally, depending on the difference in the Gibbs free energy between the solid and fluid phases and the total line tension. Analysis of linear instability for a circle with a fixed area shows that, above a threshold size, the circle can be deformed into an m-sided quasipolygon. The good agreement with the observation and numerical calculation reported by Lee and McConnell [J. Phys. Chem. 91, 9532 (1993)]] shows the quantitative validity of the present theory.     

The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

The subject of this paper is inspired by microphase-separated copolymer melts in which a small-scale structure is present inside one of the phases of a large-scale structure. Such a situation can arise in a diblock copolymer melt, if one of the blocks of the diblock is in itself a multiblock copolymer or a comb copolymer. Due to the presence of the large-scale structure, the chains are stretched. The aim of this paper is to investigate the influence of this chain stretching on the formation of the small-scale structure. To gain insight we study infinite melts of infinitely long copolymer chains that are subjected to a stretching force. For melts of monodisperse multiblock copolymers we find that the stretching destabilizes the homogeneous phase. If the stretching is strong, the lamellar structure is the only stable structure. The periodicity increases with the degree of stretching. For melts of monodisperse comb copolymers the chain stretching has no influence on the stability of the homogeneous phase. If the stretching is strong, the lamellar structure and the hexagonal structure are the only stable structures. The periodicity is independent of the degree of stretching. For the multiblock copolymer we investigated the influence of block length polydispersity. For small polydispersity the period of the structure increases monotonically with the degree of stretching. For intermediate polydispersity, the period initially decreases before it starts to increase. For large polydispersity, the mean-field period at the spinodal is infinite, becoming finite once the stretching force exceeds some critical value. For very large polydispersity the mean-field period at the spinodal remains infinite for any value of the stretching force. Received: 14 February 2002 / Accepted: 24 March 2003 / Published online: 29 April 2003 RID="a" ID="a"e-mail: hindrik.angerman@abp.nl     

Magnetic and structural properties of as-milled and heat-treated bcc-Fe70Cu30 alloy

A ferromagnetic solid solution with a nominal atomic composition Fe₇₀Cu₃₀ and a body-centered structure has been obtained by high-energy ball milling. The decomposition of the system is monitored by X-ray diffraction (XRD), magnetic measurements and Mössbauer spectroscopy. According to XRD, for healing temperatures below 723 K there is only a bcc phase in the material, while for heating temperatures above 723 K a new phase, with a fcc structure, appears, suggesting that the solid solution has decomposed into bcc-Fe and fcc-Cu. However, the magnetic behavior observed during the decomposition process indicates that this evolution is more complex than the simple decomposition into the equilibrium phases. This behavior can be summarized in two points: (1) a decrease in the magnetization at 5 K, and (2) drastic changes in the coercive field with the thermal treatment, soft magnetic behavior for the material in the as-milled state, superparamagnetism for low heating temperatures and a hardening of the material heated to above 723 K, for which the values of the coercive field at room temperature are several times higher than those for the as-milled sample. The Mössbauer spectroscopy performed at room temperature shows that for the heat-treated samples the Fe atoms are in two different phases: a ferromagnetic phase, which evolves to bcc-Fe, and a paramagnetic phase.     

The onset of convection in a couple stress fluid saturated porous layer using a thermal non-equilibrium model

The stability of a couple stress fluid saturated horizontal porous layer heated from below and cooled from above when the fluid and solid phases are not in local thermal equilibrium is investigated. The Darcy model is used for the momentum equation and a two-field model is used for energy equation each representing the solid and fluid phases separately. The linear stability theory is employed to obtain the condition for the onset of convection. The effect of thermal non-equilibrium on the onset of convection is discussed. It is shown that the results of the thermal non-equilibrium Darcy model for the Newtonian fluid case can be recovered in the limit as couple stress parameter C→0. We also present asymptotic analysis for both small and large values of the inter phase heat transfer coefficient H. We found an excellent agreement between the exact solutions and asymptotic solutions when H is very small.     

Bonding in the superionic phase of water

The predicted superionic phase of water is investigated via ab initio molecular dynamics at densities of 2.0--3.0 g/cc (34-115 GPa) along the 2000 K isotherm. We find that extremely rapid (superionic) diffusion of protons occurs in a fluid phase at pressures between 34 and 58 GPa. A transition to a stable body-centered cubic O lattice with superionic proton conductivity is observed between 70 and 75 GPa, a much higher pressure than suggested in prior work. We find that all molecular species at pressures greater than 75 GPa are too short lived to be classified as bound states. Up to 95 GPa, we find a solid superionic phase characterized by covalent O-H bonding. Above 95 GPa, a transient network phase is found characterized by symmetric O-H hydrogen bonding with nearly 50% covalent character. In addition, we describe a metastable superionic phase with quenched O disorder.     

Elusiveness of fluid-fluid demixing in additive hard-core mixtures

The conjecture that when an additive hard-core mixture phase separates when one of the phases is spatially ordered, well supported by considerable evidence, is in contradiction with some simulations of a binary mixture of hard cubes on cubic lattices. By extending Rosenfeld's fundamental measure theory to lattice models we show that the phase behavior of this mixture is far more complex than simulations show, exhibiting regions of stability of several smectic, columnar, and solid phases, but no fluid-fluid demixing. A comparison with the simulations show that they are, in fact, compatible with a fluid-columnar demixing transition, thus bringing this model into the same demixing scheme as the rest of additive hard-core mixtures.