Influence of isotopic substitution on the diffusion and thermal diffusion coefficient of binary liquids

The mutual mass diffusion coefficient (D) and the thermal diffusion coefficient ( D _T) of the liquids acetone, benzene, benzene-d ₁, benzene-d ₃, benzene-d ₅, benzene-d ₆, benzene- ¹³C₆, n-hexane, toluene, 1, 2, 3, 4-tetrahydronaphtalene, isobutylbenzene, and 1, 6-dibromohexane in protonated and perdeuterated cyclohexane have been measured with a transient holographic grating technique at a temperature of 25 ^°C. The mass diffusion coefficient shows a pronounced concentration dependence. Perdeuteration of cyclohexane only leads to marginal changes of the mass diffusion coefficient. The Stokes-Einstein equation describes the limiting tracer diffusion coefficients well if the solute molecule is smaller than the solvent. It is not capable to describe the small isotope effect of a few percent. On the other hand, the isotope effect, which is independent of concentration, is in agreement with the Enskog theory, that does not provide the absolute value of the mass diffusion coefficient of the liquid mixtures. The thermal diffusion coefficient of all the binary mixtures shows a moderate and almost linear concentration dependence. Its isotope effect, which is the change of D _T upon deuteration of cyclohexane, varies with mole fraction. The thermophoretic force acting on any tracer molecule in cyclohexane changes by the same amount when cyclohexane is perdeuterated, irrespective of the magnitude of the thermophoretic force before deuteration. This change of the thermophoretic force is equal but of opposite sign to the difference between the thermophoretic forces acting on cyclohexane and perdeuterated cyclohexane as tracers in any of the above liquids.     

浓悬浮液中渗透性颗粒的扩散特性研究

本文利用浓悬浮液中渗透性颗粒的短时扩散动力学数值模拟的结论,并结合Cohen-de Schepper近似和Percus-Yevick近似,研究了不同粒径渗透性颗粒的有效扩散系数随体积分数和渗透率的变化关系. 结果表明:对于浓悬浮液中一定粒径的渗透性颗粒,其扩散系数随渗透率的增加而增加,随体积分数的增加而减少;具有相同粒径与流体动力学屏蔽深度比值且波数较大的渗透性颗粒,其粒径对扩散的影响可以忽略. 关键词： 渗透性颗粒 有效扩散系数 体积分数 布朗运动短时区域     

Cluster structure of oriented polyethylene terephthalate films

The surface of polyethylene terephthalate films (the degree of crystallinity is 0.12–0.18) subjected to uniaxial drawing near the glass transition temperature of 353 K has been studied by electron microscopy and IR spectroscopy. Formation of a percolation cluster of densely packed particles, which is deformed as a whole entity, has been revealed in the films. The volume fraction of the cluster (Ω ≈ 0.5) and the degree of chain unfolding (β ≈ 0.7) at 343 K are independent of the drawing ratio in the region 1.1 ≤ λ ≤ 3.0. Near λ = 2.5, plane orientation of chains, for which the radius of particles in the amorphous phase is close to the radius of unperturbed coil, has been found. At 363 K, the cluster framework formation (Ω ≈ 0.6 and β ≈ 1) terminates near λ = 2.5. The drawing ratio λ ≥ 4 corresponds to microfibrils of chains with the parameters Ω ≈ 0.15 and β ≈ 1 and the fractal dimensionality D ≈ 1.     

Viscosity at small scales in polymer melts

Flows around small colloidal particles of diameter b, or in thin films, capillaries, etc., cannot always be described in terms of the macroscopic polymer viscosity. We discuss these features for entangled polymer melts, where two distinct regimes can be found: (a) the thin regime where b is smaller than the coil radius R₀, but larger than the diameter of the Edwards tube; (b) the ultrathin regime, where . We consider (i) non adsorbing particles, where slippage may occur between the melt and the solid surface; (ii) “hairy” particles, which carry some bound polymer chains. We obtain scaling predictions for mobilities of spheres, of needles, and of clusters of particles. We also discuss translational and rotational diffusion of needles. Received 19 April 1999     

Simulation study of lateral diffusion in lipid-sterol bilayer mixtures

We employ off-lattice Monte Carlo simulations to study lateral diffusion in lipid-sterol bilayers using a two-dimensional model system which has been designed to simulate the experimental phase diagrams of both lipid-cholesterol and lipid-lanosterol systems. We focus on the effects of varying sterol concentration and temperature on the tracer diffusion coefficient, D, which characterizes the lateral motion of single tagged lipids in a bilayer. Generally, we find that increasing the cholesterol concentration suppresses D due to an increased conformational ordering of lipid chains. We argue that this effect competes with an increase in the average free area per lipid, which favours an increase in D. At temperatures close to the main transition temperature, the competition between the two effects leads to intriguing behavior of D. Overall, the model results are in excellent qualitative agreement with available experimental results for lipid-cholesterol mixtures. Additional studies of a model lipid-lanosterol system, for which experimental diffusion results are not available, predict that the presence of lanosterol has a smaller effect than cholesterol on reducing D relative to the pure lipid system. We conclude that the molecular model employed contains the essential features required to describe many of the qualitative features of the lateral diffusion behavior in lipid-sterol systems. Received 24 November 2000 and Received in final form 30 April 2001     

Exact propagator of the Fokker-Planck equation with a space-dependent diffusion coefficient and a time-dependent mean-reverting force

We have investigated the algebraic structure of the Fokker-Planck equation with a variable diffusion coefficient and a time-dependent mean-reverting force. Such a model could be useful to study the general problem of a Brownian walker with a space-dependent diffusion coefficient. We also show that this model is related to the Fokker-Planck equation with a constant diffusion coefficient and a time-dependent anharmonic potential of the form V(x, t) = ?a(t)x ² + b ln x, which has been widely applied to model different physical and biological phenomena, e.g. the study of neuron models and stochastic resonance in monostable nonlinear oscillators. Using the Lie algebraic approach we have derived the exact diffusion propagators for the Fokker-Planck equations associated with different boundary conditions, namely (i) the case of a single absorbing barrier, and (ii) the case of two absorbing barriers. These exact diffusion propagators enable us to study the time evolution of the corresponding stochastic systems. Received 23 October 2001 and Received in final form 24 December 2001     

活性浴中非活性棒的扩散动力学模拟研究：非单调尺寸依赖和反常平动-转动耦合

本文采用Langevin动力学模拟二维刚性棒状示踪粒子在活性浴中的扩散动力学,主要关注示踪粒子平动(转动)扩散系数随其棒长和背景粒子的活性强度如何变化. 本文发现示踪粒子在小时间尺度显示出超扩散行为,并在大时间尺度下恢复到正常扩散,同时平动扩散系数和转动扩散系数均随背景粒子的活性强度增加单调增加,但呈现出与棒长的非单调依赖. 在研究棒的平动-转动耦合时发现这种平衡系统中不存在反直觉现象,即棒在一定参数下会表现出负的平动-转动耦合,表明示踪粒子在平行于棒方向上的扩散比在垂直方向上更慢. 这种异常(扩散)行为随背景粒子的活性强度增加具有重入行为,表明背景粒子的活性导致了两种扩散行为存在竞争关系的效应.     

Quantum effects on electron-proton bremsstrahlung spectrum in a two-component plasma

The electron-proton low energy bremsstrahlung process is investigated in a two-component plasma. The corrected Kelbg potential taking into account the quantum effects is applied to describe the electron-proton interaction potential in a two-component plasma. The straight-line trajectory method is applied to the motion of the projectile electron in order to investigate the variation of the bremsstrahlung cross-section as a function of the scaled impact parameter, thermal de Broglie wavelength, projectile energy, and photon energy. The results show that the quantum-mechanical effects decrease the bremsstrahlung cross-sections when the de Broglie wavelength (λ) is greater than the Bohr radius (a₀). It is also found that the quantum effects are important only for the region of impact parameters b < 3a ₀. Received 13 March 2001     

Radiation force exerted on nanometer size non-resonant Kerr particle by a tightly focused Gaussian beam

We calculate the radiation force that is exerted by a focused continuous-wave Gaussian beam of wavelength λ on a non-absorbing nonlinear particle of radius a ? 50λ/π. The refractive index of the mechanically-rigid particle is proportional to the incident intensity according to the electro-optic Kerr effect. The force consists of two components representing the contributions of the electromagnetic field gradient and the light scattered by the Kerr particle. The focused intensity distribution is determined using expressions for the six electromagnetic components that are corrected to the fifth order in the numerical aperture (NA) of the focusing objective lens. We found that for particles with a < λ/21.28, the trapping force is dominated by the gradient force and the axial trapping force is symmetric about the geometrical focus. The two contributions are comparable with larger particles and the axial trapping force becomes asymmetric with its zero location displaced away from the focus and towards the beam propagation direction. We study the trapping force behavior versus incident beam power, NA, λ, and relative refractive index between the surrounding liquid and the particle. We also examine the confinement of a Kerr particle that exhibits Brownian motion in a focused beam. Numerical results show that the Kerr effect increases the trapping force strength and significantly improves the confinement of Brownian particles.     

Structure of aluminum alloys irradiated with reactor neutrons

Samples of the CAB-1 alloy in the initial state and irradiated with fast neutrons at an fluence of 2 × 10²¹ neutrons/cm² have been studied by small-angle neutron scattering. It has been demonstrated that the observed large scattering cross sections are associated with the presence of nanosized pores with radii R ∼ 5–50 nm in the alloy, whereas for possible inclusions of the Mg₂Si and Si phases, the contrast factors and limiting volume fractions lead to the estimated cross sections that are two orders of magnitude smaller than those observed in the experiment. As a result of the irradiation, the volume fraction of scattering objects (pores) 40–50 nm in radius decreases by a factor of more than two. This is compensated, to a large extent, by an increase in the total fraction of particles with radii of 5–8 and 20–25 nm as the total surface area of the scattering objects increases by 40%.     

Dynamics of macroparticles in a dusty plasma under microgravity conditions (First experiments on board the ISS)

The results of experimental investigation of macroparticle transport in the dusty plasma of a capacitive high-frequency discharge under microgravity conditions are considered. Experimental data were obtained for monodisperse polymer particles of radius a _p =1.7 mm in a wide range of plasma parameters on the International Space Station. Analysis of macroparticle dynamics for a strongly nonideal dusty plasma, including diffusion and dust vortex formation processes, is carried out.     

Limitations of the permeability-limited compartment model in estimating vascular permeability and interstitial volume fraction in DCE-MRI

Dynamic contrast-enhanced magnetic resonance imaging commonly uses compartment models to estimate tissue parameters in general and perfusion parameters in particular. Compartment models assume a homogeneous distribution of the injected tracer throughout the compartment volume. Since tracer distribution within a compartment cannot be assessed, the parameters obtained by means of a compartment model might differ from the actual physical values.This work systematically examines the widely used permeability-surface-limited one-compartment model to determine the reliability of the parameters obtained by comparing them with their actual values. A computer simulation was used to model spatial tracer distribution within the interstitial volume using diffusion of contrast agent in tissue. Vascular parameters were varied as well as tissue parameters. The vascular parameters used were capillary radius (4 and 12 μm), capillary permeability (from 0.03 to 3.3 μm/s) and intercapillary distances from 30 to 300 μm. The tissue parameters used were tortuosity (λ), porosity (α) and interstitial volume fraction (v_e).Our results suggest that the permeability-surface-limited compartment model generally underestimates capillary permeability for capillaries with a radius of 4 μm by factors from ≈0.03 for α=0.04, to ≈ 0.1 for α=0.2, to ≈ 0.5 for α=1.0. An overestimation of actual capillary permeability for capillaries with a radius of 12 μm by a factor of ≥1.3 was found for α=1.0, while α=0.2 yielded an underestimation by a factor of ≈0.3 and α=0.04 by a factor of ≈ 0.03. The interstitial volume fraction, v_e, obtained by the compartment model differed with increasing intercapillary distances and for low vessel permeability, whereas v_e was found to be estimated approximately accurately for P=0.3 μm/s and P=3.3 μm/s for vessel distances <100 μm.     

Dynamics in dense suspensions of charge-stabilized colloidal particles

The dynamic behavior of charge-stabilized colloidal particles in suspension was studied by photon correlation spectroscopy with coherent X-rays (XPCS). The short-time diffusion coefficient, D(Q) , was measured for volume concentrations φ ⩽ 0.18 and compared to the free particle diffusion constant D₀ and the static structure factor S(Q) . The data show that indirect, hydrodynamic interactions are relevant for the system and hydrodynamic functions were derived. The results are in striking contrast to the predictions of the PA (pairwise-additive approximation) model, but show features typical for a hard-sphere system. The observed mobility is however considerably smaller than the one of a respective hard-sphere system. The hydrodynamic functions can be modelled quantitatively if one allows for an increased effective viscosity relative to the hard-sphere case.     

Escape of Brownian particles in an asymmetric bistable sawtooth potential driven by cross-correlated noises

The relative escape rate (RER) for Brownian particles in an asymmetric bistable sawtooth potential driven by cross correlations between multiplicative white noise and additive white noise is studied. A new expression of the mean first-passage time is derived under the condition of piecewise linear potentials and discontinuous diffusion function. Based on the results of RER numerically calculated, it is found that (i) under positively correlated noises action (i.e. λ > 0, and λ is the correlation strength), the escape rate exhibits the suppression platform as the intensity of multiplicative noise varies. The effect of suppression becomes more pronounced with the growth of height of the deterministic potential barrier for transition, and with the increase of λ. However, for the case of uncorrelated noises (λ = 0) and of negatively correlated noises (λ < 0), the suppression platform disappears. (ii) The positive correlation between noises amplifies the change of the escape rate with the height of barrier for transition, while the negative correlation between noises suppresses this change. Received 20 November 2002 / Received in final form 19 October 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: kmdcmei@public.km.yn.cn     

Theoretical analysis of acoustic-optic frequency shifter by dual mode fiber

The frequency shifting between two modes in an optical fiber resulting from acoustic wave propagation has been studied theoretically. Our theoretical results confirm the earlier experimental work. The polarization effect introduced by acoustic waves has been examined as well. The analysis shows that the polarization characteristic and symmetry property of the modes are not preserved in the coupling process of acoustic-optic frequency shifting for arbitrary ratio of the fiber cladding radius to the acoustic wavelengthd/ _a, in contrast to stable mechanical microbending, and that for the givend/ _a = 0.397, the polarized light signal at frequency ₂, shifted from that at frequency ₁, is quasi-linearly polarized for any acoustic-optic interaction length. However, the polarization effect can be neglected when the fiber cladding radius is much smaller than the acoustic wavelength.     

Thermal conductivity of the diamond-paraffin wax composite

The thermal conductivity of diamond-paraffin wax composites prepared by infiltration of a hydrocarbon binder with the thermal conductivity λ _m = 0.2 W m⁻¹ K⁻¹ into a dense bed of diamond particles (λ _f ∼ 1500 W m⁻¹ K⁻¹) with sizes of 400 and 180 μm has been investigated. The calculations using universally accepted models considering isolated inclusions in a matrix have demonstrated that the best agreement with the measured values of the thermal conductivity of the composite λ = 10–12 W m⁻¹ K⁻¹ is achieved with the use of the differential effective medium model, the Maxwell mean field scheme gives a very underestimated calculated value of λ, and the effective medium theory leads to a very overestimated value. An agreement between the calculation and the experiment can be provided by constructing thermal conductivity functions. The calculation of the thermal conductivity at the percolation threshold has shown that the experimental thermal conductivity of the composites is higher than this critical value. It has been established that, for the composites with closely packed diamond particles (the volume fraction is ∼0.63 for a monodisperse binder), the use of the isolated particle model (Hasselman-Johnson and differential effective medium models) for calculating the thermal conductivity is not quite correct, because the model does not take into account the percolation component of the thermal conductivity. In particular, this holds true for the calculation of the heat conductance of diamond-matrix interfaces in diamond-metal composites with a high thermal conductivity.     

NMR velocimetry studies of the steady-shear rheology of a concentrated hard-sphere colloidal system

NMR velocimetry has been used to observe the steady-shear rheological behaviour of a concentrated suspension of hard-sphere like 370 nm diameter PMMA core-shell latex particles at the volume fraction Φ = 0.46, the liquid core of the spheres rendering possible NMR observation of the particles themselves. Rheological measurements in a cone-and-plate geometry indicate that when aged (i.e. left at rest for two weeks), the material exhibits yield stress behaviour at very low shear rates. For shear rates greater than 1 s ^{- 1} a transition to liquid-like behaviour was observed, leading to a rejuvenated fluid state which exhibits shear-thinning behaviour over a wide range of shear rates. A similar yield stress behaviour was reflected in NMR velocimetry measurements in a Couette geometry, where the solid-to liquid transition could be clearly observed. Under steady-state flow, the fluid state inside the radius at which yield stress was observed, exhibited shear-thinning behaviour with a power law exponent n slowly approaching unity with increasing shear rate. This behaviour has some similarities with a model of Derec et al. in which aging and rejuvenation effects compete. Substantial wall slip was observed both at the inner and at the outer wall, an effect which disappeared as the shear rate was increased. No radial particle migration from the high-shear region at the inner wall was observed.     

Flory radius of polymers in a periodic field: An exact analytic theory

We found an exact expression for the Flory radius R _F of Gaussian polymers placed in an external periodic field. This solution is expressed in terms of the two parameters η and a that describe the reduced strength of an external field and the period of the field to the polymer gyration radius ratio, respectively. R _F is found to be a decaying function of η for any values of a . Provided that the gyration radius is of the order of the period of an external field or less, the ground-state (GS) approximation of the exact result for R _F is shown to give qualitatively incorrect results. In addition to the “ground-state” contribution, the exact solution for R _F contains an additional term that is overlooked by the GS approximation. This term gives rise to the fact that R _F as a function of η exhibits power law behavior (rather than exponential decay obtained from the GS result) once η exceeds the threshold value η_con .     

Anomalous transport in heterogeneous media

The diffusion dynamics of particles in heterogeneous media is studied using particle-based simulation techniques. A special focus is placed on systems where the transport of particles at long times exhibits anomalies such as subdiffusive or superdiffusive behavior. First, a two-dimensional model system is considered containing gas particles (tracers) that diffuse through a random arrangement of pinned, disk-shaped particles. This system is similar to a classical Lorentz gas. However, different from the original Lorentz model, soft instead of hard interactions are considered and we also discuss the case where the tracer particles interact with each other. We show that the modification from hard to soft interactions strongly affects anomalous-diffusive transport at high obstacle densities. Second, non-linear active micro-rheology in a glass-forming binary Yukawa mixture is investigated, pulling single particles through a deeply supercooled state by applying a constant force. Here, we observe superdiffusion in force direction and analyze its origin. Finally, we consider the Brownian dynamics of a particle which is pulled through a two-dimensional random force field. We discuss the similarities of this model with the Lorentz gas as well as active micro-rheology in glass-forming systems.