On the Theory of Structural Transformations in Magnetic Fluids

Results of studying a new scenario of condensation phase transition in the ensemble of ferrofluid particles are reported. Phase transition in this ensemble starts with the formation of chain clusters. Chains whose length exceeds a certain critical value dependent on temperature and magnetic field undergo collapse and are transformed into very dense globules. The globule evolution leads to the separation of ferrofluid into two phases with different particle density. Initial (chain collapse) and final (equilibrium) stages of phase transition are investigated. Calculations of the critical length of a chain corresponding to its collapse, as well as the characteristics of dense phase at the final separation stage are in good agreement with the results of known experiments.     

On the Theory of Condensation Phase Transitions in Magnetic and Electrorheological Suspensions

Particle condensation in nonconducting electro- and magnetorheological suspensions under the action of external electric (magnetic) field was theoretically studied. It was shown that the phase separation of the particle system of the gas-liquid type is preceded by the formation of fairly long chain aggregates. Phase transition occurs as a condensation of these chains as a result of their polar electric (magnetic) interaction. This fact denotes the essential difference between the phase separation in the considered suspensions of polarizable particles from the phase transitions in ferro- and Seignette-electric fluids, i.e., colloidal suspensions of monodomain particles with permanent intrinsic moments, as well as from the transitions in molecular systems, where the condensation occurs in the ensemble of individual particles (molecules).     

Solid-liquid phase transition of tin particles observed by UHV high resolution transmission electron microscopy: pseudo-crystalline phase

Solid-liquid transition of fine tin particles having diameter of 2–10 nm is studied in-situ by high-resolution transmission electron microscopy under a ultra-high vacuum condition. Melting temperature is confirmed to decrease with the decrease of particle diameter. The particles less than the critical size, 2r _c?5 nm, are found to have a specific phase between the solid and the liquid phase. The particle in this “pseudo-crystalline” phase contains crystalline embryos in it. Particles larger than the critical size have sharp liquid-solid transition, which completed within the time resolution of our microscope observation, 33 ms upon heating or cooling process. Large solid particles have Wulff's polyhedron, while particles around the critical diameter have rather spherical shape. Structural anomaly at the critical size occurs all over the outer most surface layer slightly below the melting temperature. Origin of the “pseudo-crystalline” phase and surface pre-melting phenomena are discussed.     

Ordering transition and demixing of a binary mixture of thick and thin rodlike molecules in the presence of an external field

The effect of an external field (electric/magnetic) on the phase behavior of the binary mixture of very long thick and thin rodlike particles is studied. Both the thick and thin particles possess positive but different susceptibility anisotropics (Delta alpha). The difference in the extent of interaction between the external field and the two species is varied by means of a coupling parameter (l = Delta alpha(thick)/Delta alpha(thin)). Isotropic-nematic phase transition and demixing phase transitions taking place both in the isotropic and nematic phases are examined as a function of field strength on the level of the second virial theory of Onsager in the range of 0 < l <1. The approximate sixth order Legendre polynomial expansion method is used to represent the excluded volume interaction between the rodlike particles. It is found that the isotropic phase becomes weakly nematic (paranematic) in the presence of external field and the field orients both components in the direction of the field even if the field does not have direct interaction with the thick component (l = 0). Analytical expressions are derived for the external field induced order parameters and birefringence. The increasing field destabilizes both types of demixing transitions (isotropic-isotropic and nematic-nematic) and the paranematic-nematic phase transition. Moreover it induces closed loop immiscibility, and upper and lower critical points terminating the paranematic-nematic phase coexistence may occur for low values of the coupling parameter. It is interesting that while the phase boundaries of the paranematic-paranematic demixing and the paranematic-nematic transitions are very sensitive to the value of the coupling parameter at low pressures, the paranematic-nematic and nematic-nematic phase boundaries are practically independent of the coupling parameter at high pressures.     

On the theory of structural transformations in polar colloids

Structural transformations in the ensemble of particles with permanent intrinsic dipole moment are theoretically studied. In addition to dipole-dipole component, interparticle potential includes central attractive interaction. Such systems belong to ferrocolloids (ferrofluids) whose particle central molecular interaction is not completely screened by the protective surface layers, to polar molecular liquids, and other similar media. Main attention is focused on the analysis of chain-dense globule transitions in particle ensembles. The obtained results demonstrate that even weak central interaction between particles can induce such a transition. The performed studies explain why, in most of the known computer experiments with polar particles, the formation of dense bulk phases is observed only at the presence of central interparticle attraction and only dipole-dipole interaction results in the formation of linear chain structures, but not bulk phases.     

Phase Transitions in Electro- and Magnetorheological Fluids

The model of internal structural phase transformations occurring in electro- and magnetorheological fluids under the action of external electric (magnetic) field is presented. The model describes both types of experimentally observed transformations such as the formation of linear chain clusters and bulk dense phases composed of suspension particles. The main qualitative result of this work is the conclusion that the appearance of chain clusters precedes the suspension separation into bulk phases with different particle densities and considerably affects the phase equilibrium diagrams. This conclusion agrees with the results of known experiments.     

Critical phenomena in particles of mesoscopic size

Anomalous optical properties of small silver particles and some silver halides are discussed as displays of critical phenomena due to particle size decreasing or to their interaction with each other in an ensemble. Special consideration is given to weak localization of conduction electrons in a small metal particle, to plasmon delocalization in ensemble of metal particles, to the effect of zero- dimensional percolation in a small dielectric particle, and to the effect of size on the superionic transition in small AgI particles and thin envelopes.     

Active colloids in liquid crystals

Active colloids in liquid crystals (ACLCs) are an active matter with qualitatively new facets of behavior as compared to active matter that becomes isotropic when relaxed into an equilibrium state. We discuss two classes of ACLCs: (i) “externally driven ACLCs”, in which the motion of colloidal particles is powered by an externally applied electric field, and (ii) “internally driven ACLCs”, formed by self-propelled particles such as bacteria. The liquid crystal (LC) medium is of a thermotropic type in the first case and lyotropic (water based) in the second case. In the absence of external fields and self-propelled particles, the ACLCs are inactive, with the equilibrium LC state exhibiting long-range orientational order. The external electric field causes ACLCs of type (i) to experience translations, rotations, and orbiting, powered by mechanisms such as LC-enabled electrokinetics, Quincke rotations and entrapment at the defects of LC order. A dense system of Quincke rotators, orbiting along circularly shaped smectic defects, undergoes a transition into a collective coherent orbiting when their activity increases. An example of internally driven ACLCs of type (ii) is living liquid crystals, representing swimming bacteria placed in an otherwise passive lyotropic chromonic LC. The LC strongly affects many aspects of bacterial behavior, most notably by shaping their trajectories. As the concentration of bacteria and their activity increase, the orientational order of living liquid crystals experiences two-stage instability: first, the uniform steady equilibrium director is replaced with a periodic bend deformation, then, at higher activity, pairs of positive and negative disclinations nucleate, separate, and annihilate in dynamic patterns of topological turbulence. The ACLCs are contrasted to their isotropic counterparts.     

On the Control of Magnetic Anisotropy through an External Electric Field

The effect of an external electric field on the magnetic anisotropy of a single‐molecule magnet has been investigated, for the first time, with the help of DFT. The application of an electric field can alter the magnetic anisotropy from “easy‐plane” to “easy‐axis” type. Excitation analysis performed through time‐dependent DFT predicts that the external electric field facilitates metal to π‐acceptor ligand charge transfer, leading to uniaxial magnetic anisotropy and concomitant spin Hall effect in a single molecule.     

The phase behavior of two-dimensional symmetrical mixtures in a weak external field of square symmetry

Using Monte Carlo simulation methods in the grand canonical and semigrand canonical ensembles, we study the phase behavior of two-dimensional symmetrical binary mixtures of Lennard-Jones particles subjected to a weakly corrugated external field of a square symmetry. It is shown that the both vapor-liquid condensation and demixing transition in the liquid phase are not appreciably affected by a weakly corrugated external field. On the other hand, even a weakly corrugated external field considerably influences the structure of solid phases and the liquid-solid transition. In particular, the solid phases are found to exhibit uniaxially ordered distorted hexagonal structure. The triple point temperature increases with the corrugation of the external field, while the triple point density becomes lower when the surface corrugation increases. The changes in the location of the triple point are shown to lead to the changes of the phase diagram topology. It is also demonstrated that the solid phase undergoes a demixing transition, which is also very slightly affected by the weakly corrugated external potential. The demixing transition in the solid phase is shown to belong to the universality class of the Ising model.     

Diamagnetic susceptibility effects in NMR measurements of the properties of water in polymeric membranes

The NMR spectra of water adsorbed at various relative humidities on various cellulose ester membranes have been studied. Membranes of cellulose acetate (CA), cellulose triacetate (CTA), and cellulose acetate butyrate (CAB) were investigated. It was found that the resonance peak of a liquid imbibed in or adsorbed on membranes from high relative humidity is very sensitive to the angle between the membrane plane and the direction of the magnetic field, shifting 5–7 ppm to higher fields as the membrane plane is rotated from a perpendicular to a parallel position with respect to the direction of the external magnetic field. This phenomenon was found to be independent of the nature of the polymeric material (namely CA, CTA, or CAB), porosity of the membrane (varying from an “all bulk” dense sheet to an 80% porosity and 0.2 μm average pore size membrane), nature of the magnetic nuclei (H₂O or D₂O), intensity of the external magnetic field (60 Mcps or 100 Mcps), and nature of the liquid in the membrane (water, methanol, or n-hexane). It is therefore concluded that the dependence of the position of the resonance peak on the position of the membrane plane with respect to the external magnetic field, is a geometrical phenomenon due to the magnetic “bulk susceptibility” of the medium. Quantitative estimations of the magnitude of the diamagnetic susceptibility effect in a cylindrically rolled sheet are given. These estimates agree well with the experimentally observed “splittings.”     

Mesoscale constitutive modeling of magnetic dispersions

A constitutive model for dispersions of acicular magnetic particles has been developed by modeling the particles as rigid dumbbells dispersed in a solvent. The effects of Brownian motion, anisotropic hydrodynamic drag, a steric force in the form of the Maier-Saupe potential, and, most importantly, a mean-field magnetic potential are included in the model. The development is similar to previous models for liquid-crystalline polymers. The model predicts multiple orientational states for the dispersion, and this phase behavior is described in terms of an orientational order parameter S and an average alignment parameter J; the latter is introduced because the magnetic particles have distinguishable direction due to polarity. A transition from isotropic to nematic phases at equilibrium is predicted. Multiple nematic phases-both prolate and oblate-are predicted in the presence of steady shear flow and external magnetic field parallel to the flow. The effect of increasing magnetic interparticle interactions and particle concentration is also presented. Comparisons with experimental data for the steady shear viscosity show very good agreement.     

Structure of interparticle space in great noncrystalline packings of Lennard-Jones atoms and its influence on diffusional mobility of admixture particles

Models of 100,000 atoms interacting with Lennard-Jones potential have been constructed using the Monte Carlo method at different densities and temperatures. In these models, the structure of empty space is investigated in which the test particle with a diameter smaller than the diameter of matrix atoms can move. The percolation thresholds, when “infinite” cavities penetrating all model space arise, are found. A change of density and temperature of matrix preparation leads to a non trivial redistribution of volume between cavities of different type. By the method of molecular dynamics it is found that the usual (Einsteinian) law of diffusion is established rather quickly, on average. However, the laws for test particles moving in cavities of different type are more complex and specific to each kind of cavities. It should result in different course of chemical reaction in different local areas of a matrix.     

Phase transitions in liquid-crystalline cyanoethyl cellulose solutions in magnetic field

The cloud-point method and polarization microscopy have been used to investigate the phase transitions and the phase state of cyanoethyl cellulose-dimethylacetamide and cyanoethyl cellulose-dimethylformamide systems in the presence and absence of magnetic field with the help of polarization photoelectric and magnetic setups. The temperature-concentration region of the existence of the liquid-crystalline phase in solutions widens in the magnetic field; the higher the field strength and polymer concentration, the more pronounced this widening. Cyanoethyl cellulose solutions are found to possess “memory”: after the magnetic field is switched-off, the orientation of macromolecules and the increased phase transition temperature are preserved for many hours.     

Theoretical foundation of electroabsorption spectroscopy: Self-contained derivation of the basic equations with the direction cosine method and the Euler angle method

Self-contained derivation of the electroabsorption (E-A, Stark effect) equations of Liptay and Czekalla, which describe the external electric field effects on absorption spectra of a mobile ensemble of light-absorbing molecules at thermal equilibrium, is reported. Two mathematically different ways for obtaining the ensemble averages, the “direction cosine method” and the “Euler angle method”, are compared. Some examples illustrating the application of E-A equations in the analysis of electroabsorption spectra are presented.     

Rheological Properties of Particle-Stabilized Emulsions

We have studied the rheological properties of fumed silica particle-stabilized emulsions. Two particles of different polarity were considered, the first more hydrophilic “Aerosil R7200,” the second more hydrophobic “Aerosil R972.” These particles flocculate and probably form a network at the investigated concentration. The flow curves of emulsions stabilized by a single type of particles exhibit yield stress, shear-thinning behavior and thixotropy. Moreover they display rheological features typical of gels. These features are attributed to strengthening of the particle network by droplets. Moreover the rheological properties of w/o emulsions stabilized by hydrophobic are similar to the ones of o/w emulsions stabilized by hydrophilic particles. The rheological properties of o/w emulsions stabilized by mixtures of hydrophilic and hydrophobic particles have then been studied by keeping the total particle concentration constant and varying the mass ratio between particles. The results show that when the hydrophobic particle concentration increases, the viscosity and stability of emulsions decrease establishing evidence that the network is weakened due to preferential orientation of hydrophobic particles towards the oil phase.     

Concept of the “stability” of the quantum mechanical state

A new concept of the “stability” of the quantum mechanical state is presented. This concept is closely related to the hydrodynamical theory of quantum mechanics. For charged particles, the “stability” against the application of the external electromagnetic field is examined. Under a nonlinear interaction, a new type of the solitonlike phenomenon is shown as a novel, illustrative example of the “stable” state. An extension for the relativistic treatment is also examined.     

Magnetic nanorods confined in a lamellar lyotropic phase

The dilute lamellar phase of the nonionic surfactant C 12EO 5 was doped with goethite (iron oxide) nanorods up to a fraction of 5 vol %. The interaction between the inclusions and the host phase was studied by polarized optical microscopy (with or without an applied magnetic field) and by small-angle X-ray scattering. We find that, when the orientation of the nanorods is modified using the magnetic field, the texture of the lamellar phase changes accordingly; one can thus induce a homeotropic-planar reorientation transition. On the other hand, the lamellar phase induces an attractive interaction between the nanorods. In more concentrated lamellar phases (under stronger confinement) the particles form aggregates. This behavior is not encountered for a similar system doped with spherical particles, emphasizing the role of particle shape in the interaction between doping particles and the host phase.     

Communication: A simple method for simulation of freezing transitions

Despite recent advances, precise simulation of freezing transitions continues to be a challenging task. In this work, a simulation method for fluid-solid transitions is developed. The method is based on a modification of the constrained cell model which was proposed by Hoover and Ree [J. Chem. Phys. 47, 4873 (1967)]. In the constrained cell model, each particle is confined in a single Wigner-Seitz cell. Hoover and Ree pointed out that the fluid and solid phases can be linked together by adding an external field of variable strength. High values of the external field favor single occupancy configurations and thus stabilize the solid phase. In the present work, the modified cell model is simulated in the constant-pressure ensemble using tempering and histogram reweighting techniques. Simulation results on a system of hard spheres indicate that as the strength of the external field is reduced, the transition from solid to fluid is continuous at low and intermediate pressures and discontinuous at high pressures. Fluid-solid coexistence for the hard-sphere model is established by analyzing the phase transition of the modified model in the limit in which the external field vanishes. The coexistence pressure and densities are in excellent agreement with current state-of-the-art techniques.     

Control of particle assisted wetting by an external magnetic field

It is shown that repulsive particles can assist wetting of a water surface by an organic liquid even at a particle density substantially less than a close packed monolayer. By applying external fields, one can change the interparticle interactions from net attractive to net repulsive and thus induce a transition from nonwetting to wetting conditions. This was achieved by applying superparamagnetic polystyrene particles together with a polymerizable organic liquid (trimethylolpropane trimethacrylate) to a water surface in the middle of a solenoid. Passing a current through the solenoid created a magnetic field perpendicular to the interface that polarized the particles and induced repulsive dipole-dipole forces. Without the field, lenses of the organic liquid that included aggregates of particles floating on the water surface were observed. In the presence of the field, the organic liquid and the particles were evenly distributed across the surface. The interparticle distance increases proportional to the square root of the area per particle and is close to the value expected for hexagonal order.