Barrande M, Bouchet R, Denoyel R
MADIREL, CNRS-Université de Provence, Centre de St Jérôme, 13397 Marseille cedex 20, France.
Anal Chem. 2007 Dec 1;79(23):9115-21. doi: 10.1021/ac071377r. Epub 2007 Nov 3.
Tortuosity is often used as an adjustable parameter in models of transfer properties through porous media. This parameter, not reducible to classical measured microstructural parameters like specific surface area, porosity, or pore size distribution, reflects the efficiency of percolation paths, which is linked to the topology of the material. The measurement of the effective conductivity of a bed of particles saturated with an electrolyte is a simple way to evaluate tortuosity. Nevertheless, it received only little attention because of the real difficulties in both getting reliable results and interpreting data. Notably, the discrimination between the contribution of interparticle and intraparticle porosities to the tortuosity is not resolved. To our knowledge, there is no model able to fit the experimental data of the tortuosity of a suspension, and a fortiori of a particle bed, in the whole porosity range. Only empirical expressions have been proposed, but they do not allow deriving intratortuosity of a porous particle. For a dilute system, Maxwell's equation predicts the effective conductivity of suspensions of spherical particles as a function of the bulk electrolyte conductivity and of particle conductivity. The intraparticle tortuosity can be derived from the particle conductivity obtained from the Maxwell equation applied to data at infinite dilution of particles. Then, by assuming that the Maxwell equation is a first-order approximation of the conductivity as a function of porosity, we propose an explicit relation of the tortuosity tau of a suspension of porous particles, obtained by conductivity measurement, as tau = tau(epsilon, epsilon(p), tau(p)), where epsilon is the total porosity of the suspension, tau(p) is the intraparticle tortuosity, and epsilon(p) is the particle porosity. This relationship fits the experimental data in the whole porosity range and can be used to determine tau(p) from an experiment at only one porosity. Finally, the obtained values of tau(p) for a set of porous particles used in chromatography are discussed and compared to the data available in the literature.
曲折度通常在通过多孔介质的传输特性模型中用作可调参数。该参数与比表面积、孔隙率或孔径分布等经典测量微观结构参数不同,它反映了渗流路径的效率,而这与材料的拓扑结构相关。测量充满电解质的颗粒床的有效电导率是评估曲折度的一种简单方法。然而,由于在获得可靠结果和解释数据方面都存在实际困难,该方法很少受到关注。值得注意的是,颗粒间孔隙率和颗粒内孔隙率对曲折度的贡献之间的区分尚未得到解决。据我们所知,没有模型能够在整个孔隙率范围内拟合悬浮液(更不用说颗粒床)曲折度的实验数据。仅提出了经验表达式,但它们无法推导多孔颗粒的内部曲折度。对于稀溶液体系,麦克斯韦方程预测球形颗粒悬浮液的有效电导率是本体电解质电导率和颗粒电导率的函数。颗粒内曲折度可以从应用于颗粒无限稀释数据的麦克斯韦方程获得的颗粒电导率推导出来。然后,通过假设麦克斯韦方程是电导率随孔隙率变化的一阶近似,我们提出了通过电导率测量获得的多孔颗粒悬浮液曲折度τ的显式关系,即τ = τ(ε, ε(p), τ(p)),其中ε是悬浮液的总孔隙率,τ(p)是颗粒内曲折度,ε(p)是颗粒孔隙率。这种关系在整个孔隙率范围内都符合实验数据,并且可以用于仅通过一个孔隙率的实验来确定τ(p)。最后,讨论了一组用于色谱分析的多孔颗粒的τ(p)所得值,并与文献中的可用数据进行了比较。