Colloid fluctuations

Colloidal suspensions are systems of small mesoscopic solid particles suspended in an atomic liquid [1,2]. We will use the term colloid a little loosely, in the sense of colloidal particle. The particles may be irregularly or regularly shaped (Fig. 1). Among the regular shapes are tiny spherical balls, but also cylindrical rods or flat platelets. As the particles are solid, fluctuations of their form do not occur as they do in micellar systems. Not all particles in a suspension will, in general, have the same form. This is an intrinsic effect of the mesoscopic physics. Of course in an atomic system, say silicon, all atoms are precisely similar. One is often interested in the con-... 

Short-time Brownian motion was simulated and compared with experiments [108]. The structural evolution and dynamics [109] and the translational and bond-orientational order [110] were simulated with Brownian dynamics (BD) for dense binary colloidal mixtures. The short-time dynamics was investigated through the velocity autocorrelation function [111] and an algebraic decay of velocity fluctuation in a confined liquid was found [112]. Dissipative particle dynamics [113] is an attempt to bridge the gap between atomistic and mesoscopic simulation. Colloidal adsorption was simulated with BD [114]. The hydrodynamic forces, usually friction forces, are found to be able to enhance the self-diffusion of colloidal particles [115]. A novel MC approach to the dynamics of fluids was proposed in Ref. 116. Spinodal decomposition [117] in binary fluids was simulated. BD simulations for hard spherocylinders in the isotropic [118] and in the nematic phase [119] were done. A two-site Yukawa system [120] was studied with... 

River inputs. The riverine endmember is most often highly variable. Fluctuations of the chemical signature of river water discharging into an estuary are clearly critical to determine the effects of estuarine mixing. The characteristics of U- and Th-series nuclides in rivers are reviewed most recently by Chabaux et al. (2003). Important factors include the major element composition, the characteristics and concentrations of particular constituents that can complex or adsorb U- and Th-series nuclides, such as organic ligands, particles or colloids. River flow rates clearly will also have an effect on the rates and patterns of mixing in the estuary (Ponter et al. 1990 Shiller and Boyle 1991). 

One characteristic of shear banded flow is the presence of fluctuations in the flow field. Such fluctuations also occur in some glassy colloidal materials at colloid volume fractions close to the glass transition. One such system is the soft gel formed by crowded monodisperse multiarm (122) star 1,4-polybutadienes in decane. Using NMR velocimetry Holmes et al. [23] found evidence for fluctuations in the flow behavior across the gap of a wide gap concentric cylindrical Couette device, in association with a degree of apparent slip at the inner wall. The timescale of these fluctuations appeared to be rapid (with respect to the measurement time per shear rate in the flow curve), in the order of tens to hundreds of milliseconds. As a result, the velocity distributions, measured at different points across the cell, exhibited bimodal behavior, as apparent in Figure 2.8.13. These workers interpreted their data... 

Multiparticle collision dynamics describes the interactions in a many-body system in terms of effective collisions that occur at discrete time intervals. Although the dynamics is a simplified representation of real dynamics, it conserves mass, momentum, and energy and preserves phase space volumes. Consequently, it retains many of the basic characteristics of classical Newtonian dynamics. The statistical mechanical basis of multiparticle collision dynamics is well established. Starting with the specification of the dynamics and the collision model, one may verify its dynamical properties, derive macroscopic laws, and, perhaps most importantly, obtain expressions for the transport coefficients. These features distinguish MPC dynamics from a number of other mesoscopic schemes. In order to describe solute motion in solution, MPC dynamics may be combined with molecular dynamics to construct hybrid schemes that can be used to explore a variety of phenomena. The fact that hydrodynamic interactions are properly accounted for in hybrid MPC-MD dynamics makes it a useful tool for the investigation of polymer and colloid dynamics. Since it is a particle-based scheme it incorporates fluctuations so that the reactive and nonreactive dynamics in small systems where such effects are important can be studied. 

Photon correlation spectroscopy (PCS) has been used extensively for the sizing of submicrometer particles and is now the accepted technique in most sizing determinations. PCS is based on the Brownian motion that colloidal particles undergo, where they are in constant, random motion due to the bombardment of solvent (or gas) molecules surrounding them. The time dependence of the fluctuations in intensity of scattered light from particles undergoing Brownian motion is a function of the size of the particles. Smaller particles move more rapidly than larger ones and the amount of movement is defined by the diffusion coefficient or translational diffusion coefficient, which can be related to size by the Stokes-Einstein equation, as described by... 

As illustrated in Fig. 3, the proton relaxation in super-paramagnetic colloids occurs because of the fluctuations of the dipolar magnetic coupling between the nanocrystal magnetization and the proton spin. The relaxation rate increases with the fluctuation correlation time and with the magnitude of this fluctuation. Different processes cause the fluctuation of the magnetic interaction. 

D. M. Carbeny, J. C. Reid, G. M. Wang, E. M. Sevick, D. J. Searles, and D. J. Evans, Fluctuations and irreversibility an experimental demonstration of a second-law-hke theorem using a colloidal particle held in an optical trap. Phys. Rev. Lett. 92, 140601 (2004). 

Here, the quantities jn ° and ji are, respectively, the chemical potentials of pure solvent and of the solvent at a certain biopolymer concentration V is the molar volume of the solvent and n is the biopolymer number density, defined as n C/M, where C is the biopolymer concentration (% wt/wt) and M is the number-averaged molar weight of the biopolymer. The second virial coefficient has (weight-scale) units of cm mol g. Hence, the more positive the second virial coefficient, the larger is the osmotic pressure in the bulk of the biopolymer solution. This has consequences for the fluctuations in the biopolymer concentration in solution, which affects the solubility of the biopolymer in the solvent, and also the stability of colloidal systems, as will be discussed later on in this chapter. 

Kinetics is concerned with many-particle systems which require movements in space and time of individual particles. The first observations on the kinetic effect of individual molecular movements were reported by R. Brown in 1828. He observed the outward manifestation of molecular motion, now referred to as Brownian motion. The corresponding theory was first proposed in a satisfactory form in 1905 by A. Einstein. At the same time, the Polish physicist and physical chemist M. v. Smolu-chowski worked on problems of diffusion, Brownian motion (and coagulation of colloid particles) [M. v. Smoluchowski (1916)]. He is praised by later leaders in this field [S. Chandrasekhar (1943)] as a scientist whose theory of density fluctuations represents one of the most outstanding achievements in molecular physical chemistry. Further important contributions are due to Fokker, Planck, Burger, Furth, Ornstein, Uhlenbeck, Chandrasekhar, Kramers, among others. An extensive list of references can be found in [G.E. Uhlenbeck, L.S. Ornstein (1930) M.C. Wang, G.E. Uhlenbeck (1945)]. A survey of the field is found in [N. Wax, ed. (1954)]. 

Grimley (G10, Gil) used an ultramicroscope technique to determine the velocities of colloidal particles suspended in a falling film of tap water. It was assumed that the particles moved with the local liquid velocity, so that, by observing the velocities of particles at different distances from the wall, a complete velocity profile could be obtained. These results indicated that the velocity did not follow the semiparabolic pattern predicted by Eq. (11) instead, the maximum velocity occurred a short distance below the free surface, while nearer the wall the experimental results were lower than those given by Eq. (11). It was found, however, that the velocity profile approached the theoretical shape when surface-active material was added and the waves were damped out, and, in the light of later results, it seems probable that the discrepancies in the presence of wavy flow are due to the inclusion of the fluctuating wavy velocities near the free surface. 

Jusufi, A., and Ballauff, M. (2006). Correlations and fluctuations of charged colloids as determined by anomalous small-angle X-ray scattering. Macromol. Theory Simul. 15, 193-197. 

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