平行板间方势阱偶极流体的结构性质研究

在密度泛函理论(DFT)框架下, 应用改进的基本度量理论(MFMT)表达硬球作用对自由能泛函的贡献, 根据统计力学理论结合加权密度近似(WDA)表达偶极作用对自由能泛函的贡献,得到了方势阱偶极流体在平行板间的密度分布表达式, 计算了偶极流体在两平行板间的密度分布, 并探讨了方势阱深度和宽度对体系密度分布的影响. 此外, 通过体系密度分布, 进一步分析了方势阱宽度和深度以及板间尺度与溶剂化力的关系.     

Global strong solutions for a class of compressible non‐Newtonian fluids with vacuum

We study a class of compressible non‐Newtonian fluids in one space dimension. We prove, by using iterative method, the global time existence and uniqueness of strong solutions provided that the initial data satisfy a compatibility condition and the initial density is small in its H¹‐norm. The main difficulty is due to the strong nonlinearity of the system and the initial vacuum. Copyright © 2010 John Wiley & Sons, Ltd.     

Photochromism of dihydroindolizines part X. Photo‐responsive self‐assembling organogelators based on photochromic dihydroindolizines and 11‐aminoundecanoic acid (AUDA)

Multi‐addressable photophysical properties of new synthesized photochromic materials based on photochromic dihydroindolizine system (DHI) covalently linked to N‐acyl‐11 aminoundecanoic acid (AUDA) or to its sodium salt or to its ester, through an amidic or urethane linkage have been studied. The DHI skeleton in these compounds is substituted in both the fluorene part (region A) or in the heterocyclic base (region B) with the gelling moieties. These molecules have been designed to respond to their environment. Interestingly, they are shown to act as efficient gelators for polar organic fluids, water and obviously they exhibit a thermosensitive answer as low molecular mass organogelators. In these fluids, the aggregative properties are totally suppressed upon conversion to neutral carboxylic species. The gels of these carboxylate sodium salts are shown to be markedly affected by light irradiation. Supramolecular gelating assemblies can be disrupted by the photoinduced ring opening of the DHI subunit, so that the macroscopic flowing property is recovered. Upon a further thermal treatment, the system is reversibly converted back to the supramolecular network. Controlled gelation could be achieved using temperature, light, or acidity as external stimuli. These new synthesized photochromic gels with their multi‐addressable properties will find their applications as super photoresponsive materials. Developing and tuning of the photophysical properties of the synthesized compounds by the amide and urethane substituents in the 4‐position of the fluorene and pyridazine regions have been achieved. The absorption maxima (λ_max) and the half‐lives (t_1/2) of the colored betaines were detected in all cases using UV/VIS spectrophotometric measurements. Irradiation of DHI 12‐20 in CH₂Cl₂ or in acetonitrile solutions at ambient temperature with polychromatic light leads to the formation of red to red‐violet colored betaines 12 ′ ‐20 ′. The kinetics of the bleaching process of betaines 12 ′ ‐20 ′ to DHIs 12‐20 were found to take place in the second range (96‐218 s) and fit well the first order thermal back reaction. Some of these DHIs showed a photostability higher than that of the standard one. These interesting photophysical properties will help this family of compounds to find useful applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Finite element and sensitivity analysis of thermally induced flow instabilities

This paper presents a finite element algorithm for the simulation of thermo‐hydrodynamic instabilities causing manufacturing defects in injection molding of plastic and metal powder. Mold‐filling parameters determine the flow pattern during filling, which in turn influences the quality of the final part. Insufficiently, well‐controlled operating conditions may generate inhomogeneities, empty spaces or unusable parts. An understanding of the flow behavior will enable manufacturers to reduce or even eliminate defects and improve their competitiveness. This work presents a rigorous study using numerical simulation and sensitivity analysis. The problem is modeled by the Navier–Stokes equations, the energy equation and a generalized Newtonian viscosity model. The solution algorithm is applied to a simple flow in a symmetrical gate geometry. This problem exhibits both symmetrical and non‐symmetrical solutions depending on the values taken by flow parameters. Under particular combinations of operating conditions, the flow was stable and symmetric, while some other combinations leading to large thermally induced viscosity gradients produce unstable and asymmetric flow. Based on the numerical results, a stability chart of the flow was established, identifying the boundaries between regions of stable and unstable flow in terms of the Graetz number (ratio of thermal conduction time to the convection time scale) and B, a dimensionless ratio indicating the sensitivity of viscosity to temperature changes. Sensitivities with respect to flow parameters are then computed using the continuous sensitivity equations method. We demonstrate that sensitivities are able to detect the transition between the stable and unstable flow regimes and correctly indicate how parameters should change in order to increase the stability of the flow. Copyright © 2009 John Wiley & Sons, Ltd.     

Pressure-driven flow of a rate-type fluid with stress threshold in an infinite channel

In this paper we extend some of our previous works on continua with stress threshold. In particular here we propose a mathematical model for a continuum which behaves as a non-linear upper convected Maxwell fluid if the stress is above a certain threshold and as a Oldroyd-B type fluid if the stress is below such a threshold. We derive the constitutive equations for each phase exploiting the theory of natural configurations (introduced by Rajagopal and co-workers) and the criterion of the maximization of the rate of dissipation. We state the mathematical problem for a one-dimensional flow driven by a constant pressure gradient and study two peculiar cases in which the velocity of the inner part of the fluid is spatially homogeneous.     

A parametrisation of the direct correlation function for the square-shoulder fluid

We introduce a parametrisation of the direct correlation function for the square-shoulder fluid and demonstrate that this parametrisation is in quantitative agreement with the numerical solution of the Ornstein–Zernike equation within the Percus–Yevick approximation. Moreover, the radial distribution function obtained from the parametrisation reproduces quantitatively Monte Carlo simulation data. Our results show that the parametrisation is accurate over a large regime of densities for different interaction ranges and potential strengths.     

Monte Carlo simulations of star-branched polyelectrolyte micelles

The concentration profiles of monomers and counterions in star-branched polyelectrolyte micelles are calculated through Monte Carlo simulations, using the freely jointed chain model. We have investigated the onset of different regimes corresponding to the spherical and Manning condensation of counterions as a function of the strength of the Coulomb coupling. The Monte Carlo results are in fair agreement with the predictions of Self-Consistent-Field analytical models. We have simulated a real system of diblock copolymer micelles of (sodium-polystyrene-sulfonate)(NaPSS)-(polyethylene-propylene)(PEP) with f = 54 hydrophilic branches of N = 251 monomers at room temperature in salt-free solution. The calculated form factor compares nicely with our neutron scattering data. Received 18 July 2002 and Received in final form 11 October 2002 RID="a" ID="a"e-mail: roger@drecam.saclay.cea.fr     

Towards finite-dimensional gelation

We consider the gelation of particles which are permanently connected by random crosslinks, drawn from an ensemble of finite-dimensional continuum percolation. To average over the randomness, we apply the replica trick, and interpret the replicated and crosslink-averaged model as an effective molecular fluid. A Mayer-cluster expansion for moments of the local static density fluctuations is set up. The simplest non-trivial contribution to this series leads back to mean-field theory. The central quantity of mean-field theory is the distribution of localization lengths, which we compute for all connectivities. The highly crosslinked gel is characterized by a one-to-one correspondence of connectivity and localization length. Taking into account higher contributions in the Mayer-cluster expansion, systematic corrections to mean-field can be included. The sol-gel transition shifts to a higher number of crosslinks per particle, as more compact structures are favored. The critical behavior of the model remains unchanged as long as finite truncations of the cluster expansion are considered. To complete the picture, we also discuss various geometrical properties of the crosslink network, e.g. connectivity correlations, and relate the studied crosslink ensemble to a wider class of ensembles, including the Deam-Edwards distribution. Received on 24 April 2002 Published online 14 October 2002 RID="a" ID="a"deceased RID="b" ID="b"e-mail: weigt@theorie.physik.uni-goettingen.de     

A superdense star model as charged analogue of Schwarzschild’s interior solution

A charged analogue of Schwarzschilds interior solution has been derived by considering the non-gravitational energy density to be constant along with a special choice of electric intensity. The charged fluid sphere so obtained is seen to be more general than that of P.S. Florides and joins smoothly with the Reissner-Nordström metric at the pressure-free interface. Also the new charged fluid sphere is capable of representing a superdense star with surface density of 2×10¹⁴ g cm^–3 which can occupy maximum mass 1.502408 times the solar mass. In the process of deriving the solution, the authors have also come across A. L. Mehras gaseous charged fluid model which is found to be unphysical as it has negative pressure at least at the center of the model.This revised version was published online in April 2005. The publishing date was inserted.     

Heck coupling reaction of iodobenzene and styrene using supercritical water in the absence of a catalyst

Heck coupling reaction of iodobenzene and styrene proceeds rapidly and selectively in supercritical water even without any catalyst in the presence of base. Both the choice of base and the reaction conditions had a significant effect on the conversion and the selectivity of the coupling products. The addition of a relatively mild base such as potassium acetate facilitated the cross-coupling reaction, while the hydrolysis of phenyl halide was favored in the presence of a strong base. The conversion and the yields of coupling products increased with increasing temperature, reaching a maximum at 650 K near the critical temperature of water, and then decreased as the temperature was further increased. Water density had a significant influence on the reaction rate, showing nearly 30% augmentation with a slight increase in density from 0.45 to 0.56 g cm(-3), but had less effect on the product selectivity. Two possibilities of the role of water responsible for the noncatalytic Heck coupling reaction in supercritical water, that is, ion and water-catalyzed mechanisms have been considered.