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Dielectric response of concentrated colloidal suspensions

机译:浓缩胶体悬浮液的介电响应

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The determination of the low-frequency (typically 0-1 MHz) dielectric dispersion of colloidal suspensions may become an electrokinetic tool for wider use if the accuracy of experimental data can be improved and if trustable theories, available for a wide range of situations, are made available. In the present work, the focus on the latter aspect: Since the dielectric onstant of the suspensions is in fact a collective property, its determination could be most useful in concentrated suspensions. This is our aim in this paper. Using the classical electrokinetic equations and a cell model accounting for particle-particle interactions, we present calculations of the dielectric spectra of concentrated (volume fractions up to 50%) suspensions of spheres. Most of our results cannot the thought of as any sort of extrapolation of those corresponding to dilute suspensions (the reverse is true), and in fact the notion of a dilute colloidal system is itself not free of uncertainties, as no "critical volume fraction" can be identified separating the dilute and concentrated ranges. According to the calculations described, increasing the particle concentration by a sufficient amount can lead to a decrease of the dielectric constant of the whole system that can be well known below that of the dispersion medium, even for high zeta potentials, delta. The latter quantity affects (and this is also true is PHI -> O) considerably both the dielectric constant epsilon'_r and the relaxation frequency, f_(rel): When delta is increased, both the low-frequency value, epsilon'_r(0), of epsilon'_r, and f_(rel) increase at all particle concentrations. We also analyze the effect of the product kappaa, where a is the particle radius and kappa is the reciprocal Debye length: higher kappaa values correspond to larger epsilon'_r(0) and lower f_(rel). Finally, the model is compared to previously reported experimental data: it is found that the qualitative agreement is excellent both concerning epsilon'_r(0) and f_(rel). Possible improvements of the theory, particularly the inclusion of a dynamic Stern layer, are suggested.
机译:如果可以提高实验数据的准确性,并且在各种情况下都可以使用可信赖的理论,那么确定胶体悬浮液的低频(通常为0-1 MHz)介电色散可能会成为一种电动工具,可以被广泛使用。提供。在当前工作中,重点放在后一个方面:由于悬浮液的介电常数实际上是一种集体性质,因此在浓缩悬浮液中测定其可能是最有用的。这是我们本文的目的。使用经典的电动方程和考虑颗粒-颗粒相互作用的细胞模型,我们提出了球体浓缩(体积分数高达50%)悬浮液的介电谱计算。我们的大多数结果都不能认为是与稀悬液相对应的任何外推法(相反是正确的),实际上,稀胶体系统的概念本身并非没有不确定性,因为没有“临界体积分数”。可以将稀释范围和浓缩范围分开。根据所述的计算,将颗粒浓度增加足够的量可以导致整个系统的介电常数降低,即使对于高的ζ电势δ,该介电常数也可以低于分散介质的介电常数。后者的数量会同时影响介电常数epsilon'_r和弛豫频率f_(rel)(在PHI-> O时也是如此):当增量增加时,低频值epsilon'_r( ε_r的0)和f_(rel)在所有粒子浓度下都增加。我们还分析了乘积kappaa的影响,其中a是粒子半径,kappa是倒数德拜长度:较高的kappaa值对应于较大的epsilon'_r(0)和较低的f_(rel)。最后,将该模型与先前报道的实验数据进行了比较:发现关于epsilon'_r(0)和f_(rel)的定性一致性都很好。建议对该理论进行可能的改进,特别是包含动态Stern层。

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