Modulated phases and slow dynamics in attractive colloids

A system with a short-range attraction and a competing long-range screened repulsion is studied by using the self-consistent Hartree approximation and a replica approach. It is shown that by varying the parameters of the repulsive potential and the temperature yields a phase coexistence, a lamellar and a glassy phase. These results, which are confirmed by molecular dynamic simulations on a system of particles interacting via a DLVO potential, provide novel insights in the role of modulated phases in the slow dynamics of charged colloids in polymeric solutions.     

Screened electrostatic interactions between clay platelets

An effective pair potential for systems of uniformly charged lamellar colloids in the presence of an electrolytic solution of microscopic co- and counterions is derived. The charge distribution on the discs is expressed as a collection of multipole moments, and the tensors which determine the interactions between these multipoles are derived from a screened Coulomb potential. Unlike previous theoretical studies of such systems, the interaction energy may now be expressed for discs at arbitrary mutual orientation. The potential is shown to be exactly equivalent to the use of linearized Poisson–Boltzmann theory.     

Lamellar phase coexistence induced by electrostatic interactions

Membranes containing highly charged biomolecules can have a minimal free-energy state at small separations that originates in the strongly correlated electrostatic interactions mediated by counterions. This phenomenon can lead to a condensed, lamellar phase of charged membranes that coexists in thermodynamic equilibrium with a very dilute membrane phase. Although the dilute phase is mostly water, entropy dictates that this phase must contain some membranes and counterions. Thus, electrostatics alone can give rise to the coexistence of a condensed and an unbound lamellar phase. We use numerical simulations to predict the nature of this coexistence when the charge density of the membrane is large, for the case of multivalent counterions and for a membrane charge that is characteristic of biomolecules. We also investigate the effects of counterion size and salt on the two coexisting phases. With increasing salt concentration, we predict that electrostatic screening by salt can destroy the phase separation.     

Phase behaviour of a dispersion of charge-stabilised colloidal spheres with added non-adsorbing interacting polymer chains

We present a theory for the phase behaviour of mixtures of charge-stabilised colloidal spheres plus interacting polymer chains in good and θ -solvents within the framework of free-volume theory. We use simple but accurate combination rules for the depletion thickness around a colloidal particle and for the osmotic pressure up to the semi-dilute concentration regime. Hence, we obtain expressions for the free energy for mixtures of charged colloidal particles and non-adsorbing interacting polymers. From that, we calculate the phase behaviour, and discuss its topology in dependence on the competition between the charge-induced repulsion and the polymer-induced attraction. The homogeneous mixture of colloids and polymers becomes more stabilised against demixing when increasing the electrostatic repulsion. This charge-induced stabilisation is strongest for small polymer-to-colloid size ratios and is more pronounced for charged colloids mixed with polymers in a good solvent than for polymers in a θ -solvent. For the weakly charged regime we find that the phase diagram becomes salt-concentration-independent in the protein limit for charged colloids plus polymers in a θ -solvent. The liquid window, i.e., the concentration regimes where a colloidal liquid exists, is narrowed down upon increasing the charge-induced repulsion. Also this effect is more pronounced when charged colloids are mixed with polymer chains in a good solvent. In summary, we demonstrate that the solvent quality significantly influences the phase behaviour of mixtures of charged colloids plus non-adsorbing polymers if the range of the screened electrostatic repulsion becomes of the order of the range of the depletion-induced attraction.     

Phase diagram of dipolar hard and soft spheres: manipulation of colloidal crystal structures by an external field

Phase diagrams of hard and soft spheres with a fixed dipole moment are determined by calculating the Helmholtz free energy using simulations. The pair potential is given by a dipole-dipole interaction plus a hard-core and a repulsive Yukawa potential for soft spheres. Our system models colloids in an external electric or magnetic field, with hard spheres corresponding to uncharged and soft spheres to charged colloids. The phase diagram of dipolar hard spheres shows fluid, face-centered-cubic (fcc), hexagonal-close-packed (hcp), and body-centered-tetragonal (bct) phases. The phase diagram of dipolar soft spheres exhibits, in addition to the above mentioned phases, a body-centered-orthorhombic (bco) phase, and it agrees well with the experimental phase diagram [Nature (London) 421, 513 (2003)]. Our results show that bulk hcp, bct, and bco crystals can be realized experimentally by applying an external field.     

CuAu structure in the restricted primitive model and oppositely charged colloids

We study the phase behavior of oppositely charged equal-size hard spheres both theoretically and experimentally, using Monte Carlo simulations and confocal microscopy. In the simulations, two systems are considered: the restricted primitive model (RPM) and a system of screened Coulomb particles. We construct the phase diagrams of both systems by computer simulations and predict a novel solid phase that has the CuAu structure. In addition, the CuAu structure is observed experimentally in a system of oppositely charged colloids. The qualitative agreement between the RPM, the screened Coulomb system, and the experiments shows that colloids form a suitable model system to study phase behavior in ionic systems.     

Soret motion of a charged spherical colloid

The thermophoretic motion of a charged spherical colloidal particle and its accompanying cloud of counterions and coions in a temperature gradient is studied theoretically. Using the Debye-Hückel approximation, the Soret drift velocity of a weakly charged colloid is calculated analytically. For highly charged colloids, the nonlinear system of electrokinetic equations is solved numerically, and the effects of high surface potential, dielectrophoresis, and convection are examined. Our results are in good agreement with some of the recent experiments on highly charged colloids without using adjustable parameters.     

Semi-analytical method of calculating the electrostatic interaction of colloidal solutions

We present a semi-analytical method of calculating the electrostatic interaction of colloid solutions for confined and unconfined systems. We expand the electrostatic potential of the system in terms of some basis functions such as spherical harmonic function and cylinder function. The expansion coefficients can be obtained by solving the equations of the boundary conditions, combining an analytical translation transform of the coordinates and a numerical multipoint collection method. The precise electrostatic potential and the interaction energy are then obtained automatically. The method is available not only for the uniformly charged colloids but also for nonuniformly charged ones. We have successfully applied it to unconfined diluted colloid system and some confined systems such as the long cylinder wall confinement, the air–water interfacial confinement and porous membrane confinement. The consistence checks of our calculations with some known analytical cases have been made for all our applications. In theory, the method is applicable to any dilute colloid solutions with an arbitrary distribution of the surface charge on the colloidal particle under a regular solid confinement, such as spherical cavity confinement and lamellar confinement.     

Colloids as model systems for metals and alloys: a case study of crystallization

Metallic systems are widely used as materials in daily human life. Their properties depend very much on the production route. In order to improve the production process and even develop novel materials a detailed knowledge of all physical processes involved in crystallization is mandatory. Atomic systems like metals are characterized by very high relaxation rates, which make direct investigations of crystallization very difficult and in some cases impossible. In contrast, phase transitions in colloidal systems are very sluggish and colloidal suspensions are optically transparent. Therefore, colloidal systems are often discussed as model systems for metals. In the present work, we study the crystallization process of charged colloidal systems from the very beginning. Charged colloids offer the advantage that the interaction potential can be systematically tuned by a variation of the particle number density and the salt concentration. We apply light scattering and ultra-small angle x-ray scattering to investigate the formation of short-range order in the liquid state even far from equilibrium, crystal nucleation and crystal growth. The results are compared with equivalent studies on metallic systems.     

Structure factor of charged colloidal suspensions using Brownian-dynamics simulation: Comparison of Yukawa and Sogami pair potentials

Static structure factorsS(Q) are obtained for dilute charged colloidal systems using Brownian dynamics simulation method for the widely used screened Coulomb repulsive Yukawa potential and the recently proposed Sogami pair potential. The latter potential has, in addition to the usual repulsive part, an attractive term which is necessary to understand the reentrant phase transition reported in these colloids. It is shown for the first time thatS(Q) obtained using the Sogami potential for parameters favourable for liquid-like order agrees well with that measured experimentally. Thus it appears that the Sogami potential explains features of a homogeneous liquid as well as phase separated states, whereas Yukawa potential does not.     

Electric-field-induced polarization of the layer of condensed ions on cylindrical colloids

In concentrated suspensions of charged colloids, interactions between colloids can be induced by an external electric field through the polarization of charge distributions (within the diffusive double layer and the layer of condensed ions) and/or electro-osmotic flow. In case of rod-like colloids, these field-induced inter-colloidal interactions have recently been shown to lead to anomalous orientation perpendicular to the external field, and to phase/state transitions and dynamical states, depending on the field amplitude and frequency of the external field. As a first step towards a (semi-) quantitative understanding of these phenomena, we present a linear-response analysis of the frequency-dependent polarization of the layer of condensed ions on a single, long and thin cylindrical colloid. The in-phase and out-phase response functions for the charge distribution and the electric potential are calculated for arbitrary orientation of the cylindrical colloid. The frequency-dependent degree of alignment, which is proportional to the electric-field-induced birefringence, is calculated as well, and compared to experiments on dilute fd virus suspensions.     

Disappearance of the gas-liquid phase transition for highly charged colloids

We calculate the full phase diagram of spherical charged colloidal particles using Monte Carlo free energy calculations. The system is described using the primitive model, consisting of explicit hard-sphere colloids and point counterions in a uniform dielectric continuum. We show that the gas-liquid critical point becomes metastable with respect to a gas-solid phase separation at colloid charges Q > or =20 times the counterion charge. Approximate free energy calculations with only one and four particles in the fluid and solid phases, respectively, are used to determine the critical line for highly charged colloids up to Q=2000. We propose the scaling law T*(c) approximately Q(1/2) for this critical temperature.     

Sedimentation equilibria of ferrofluids: II. Experimental osmotic equations of state of magnetite colloids

The first experimental osmotic equation of state is reported for well-defined magnetic colloids that interact via a dipolar hard-sphere potential. The osmotic pressures are determined from the sedimentation equilibrium concentration profiles in ultrathin capillaries using a low-velocity analytical centrifuge, which is the subject of the accompanying paper I. The pressures of the magnetic colloids, measured accurately to values as low as a few pascals, obey Van 't Hoff's law at low concentrations, whereas at increasing colloid densities non-ideality appears in the form of a negative second virial coefficient. This virial coefficient corresponds to a dipolar coupling constant that agrees with the coupling constant obtained via independent magnetization measurements. The coupling constant manifests an attractive potential of mean force that is significant but yet not quite strong enough to induce dipolar chain formation. Our results disprove van der Waals-like phase behavior of dipolar particles for reasons that are explained.     

Acousto-electric wave instability in ion-implanted semiconductor plasmas

A comprehensive investigation of excitation of acousto-electric modes and novel properties introduced due to presence of negatively charged colloids in magnetized compensated piezoelectric semiconductor plasma is presented analytically. We derive a compact dispersion relation for the acousto-electric waves in colloids laden semiconductor plasma by employing multi-fluid balance equation. It is found that the presence of charged colloids not only modifies the wave spectrum but also alters the amplification characteristics even though colloidal particles, on account of their heavy masses, do not participate in wave propagation. The results of this investigation should be useful in understanding the characteristics of longitudinal acousto-electric wave in ion-implanted piezoelectric semiconductor plasmas whose main constituents are electrons, holes and negatively charged colloids, which are stationary in the background.     

Inter-lamellar interactions modulated by addition of guest components

We have investigated the effects of a guest component (polymer or spherical colloidal particle) confined between flexible lamellar slits on the inter-lamellar interaction by means of a small-angle X-ray scattering technique and a neutron spin echo technique. The dominant interaction between flexible lamellar membranes without guest components is the Helfrich mechanism. The addition of a neutral polymer into the lamellar phase induces an attractive inter-lamellar interaction and finally destabilizes the lamellar phase. On the other hand, spherical colloidal particles confined between flexible lamellar membranes reduce the undulational fluctuations of lamellae and bring a repulsive inter-lamellar interaction. The behavior of the layer compression modulus of the lamellar membrane containing colloidal particles is well described by the entropical repulsive inter-lamellar interaction driven by steric hindrance.Received: 26 March 2004, Published online: 4 May 2004PACS: 82.70.Uv Surfactants, micellar solutions, vesicles, lamellae, amphiphilic systems, (hydrophilic and hydrophobic interactions) - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 83.80.Hj Suspensions, dispersions, pastes, slurries, colloids - 89.75.Fb Structures and organization in complex systems     

Band formation in mixtures of oppositely charged colloids driven by an ac electric field

We present experiments on pattern formation in a Brownian system of oppositely charged colloids driven by an ac electric field. Using confocal laser scanning microscopy we observe complete segregation of the two particle species into bands perpendicular to a field of sufficient strength when the frequency is in a well-defined range. Because of its Brownian nature the system spontaneously returns to the equilibrium mixture after the field is turned off. We show that band formation is linked to the time scale associated with collisions between particles moving in opposite directions.     

软凝聚态物质物理学

软物质是指其某种物理性质在小的外力作用下能产生很大变化的凝聚态物,典型的例子包括液晶、高分子体系、胶体、微乳液等。软物质的结构和性质主要不是由内能,而是由熵来决定,较通俗地介绍了软物质的概念,仔细分析了熵在软物质中所起的作用,同时详细介绍了聚合物体系、胶体及生物膜等几种典型的软物质,通过硫化橡胶和无管虹吸等十分有趣的例子。说明了聚合物对流变性质的影响;通过分析硬球胶体的相变及相分离等行为说明了熵力的概念;仔细分仔了电稳定胶体的相互作用,并介绍了DLVO理论以及近年来发现的对这一理论的偏离,特别是约束条件下同号带电胶球的长程吸引相互作用及其对此现象的一些解释;对生物膜也作了初步介绍。人们对软物质的研究和理解目前还处于一个非常原始的阶段,深入研究和理解软物质的各种性质必将促进人类对自然和人类自身的认识。     

结晶紫在混合正、负电性银胶上的表面增强拉曼散射

利用化学还原的方法分别制备了具有正、负电性的纳米银胶 ,通过测定结晶紫分子在正、负电性银胶以及混合银胶体系的表面增强拉曼光谱的变化 ,探讨了不同电性银胶基底对结晶紫分子表面增强拉曼活性的影响。结果表明 ,混合银胶体系能有效的改进单银胶体系的表面增强拉曼活性。     

Longitudinal electro-kinetic waves in ion-implanted semiconductor plasmas

A comprehensive investigation of propagation of new longitudinal electro-kinetic modes and novel properties introduced due to presence of negatively charged colloids in semiconductor plasma is presented. By employing the multi-fluid balance equations, a compact dispersion relation for the cases in which wave phase velocity is either larger or smaller than electron thermal velocity is derived. This dispersion relation is used to study wave phenomena and electro-kinetic mode instability numerically. We find important modifications in electro-kinetic branch as well as the existence of new modes of propagation in colloids laden semiconductor plasma. The results of this investigation should be useful in understanding the characteristics of longitudinal electro-kinetic wave in colloids laden semiconductor plasmas whose main constituents are electrons, holes and negatively charged colloids.Received: 15 June 2004, Published online: 7 September 2004PACS: 52.35.Fp Electrostatic waves and oscillations (e.g., ion-acoustic waves) - 72.30. + q High-frequency effects; plasma effects - 61.72.Ww Doping and impurity implantation in other materials - 82.70.Dd Colloids