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Mesoporous films have been shown to exhibit striking behaviors in capillary-driven infiltration experiments. The process has been shown to follow classical Lucas-Washburn dynamics, but the effective pore radius has been calculated from hydrodynamic resistance considerations to be orders of magnitude lower than measured pore dimensions. In addition, the infiltration rate has been observed to decrease with increasing pore diameter, in contrast to the expected trend for capillary-like pores. Here, we present a simple model accounting for the mechanism behind these anomalous effects. We found the infiltration rate to be inversely proportional to the cubed ratio of pore to neck size. This physical scaling correctly modeled both the magnitude of the infiltration rate and its variation with pore diameters, for a wide range of experimental data. The model established a connection between capillary filling dynamics and nanoscale pore structure, which is of practical interest for the design and characterization of mesoporous films.

The fluid-front dynamics resulting from the coexisting infiltration and evaporation phenomena in nanofluidic systems has been investigated. More precisely, water infiltration in both titania and silica mesoporous films was studied through a simple experiment: a sessile drop was deposited over the film and the advancement of the fluid front into the porous structure was optically followed and recorded in time. In the case of titania mesoporous films, capillary infiltration was arrested at a given distance, and a steady annular region of the wetted material was formed. A simple model that combines Lucas-Washburn infiltration and surface evaporation was derived, which appropriately describes the observed filling dynamics and the annulus width in dissimilar mesoporous morphologies. In the case of wormlike mesoporous morphologies, a remarkable phenomenon was found: instead of reaching a steady infiltration-evaporation balance, the fluid front exhibits an oscillating behavior. This complex filling dynamics opens interesting possibilities to study the unusual nanofluidic phenomena and to discover novel applications.

The design of paper-based assays that integrate passive pumping requires a precise programming of the fluid transport, which has to be encoded in the geometrical shape of the substrate. This requirement becomes critical in multiple-step processes, where fluid handling must be accurate and reproducible for each operation. The present work theoretically investigates the capillary imbibition in paper-like substrates to better understand fluid transport in terms of the macroscopic geometry of the flow domain. A fluid dynamic model was derived for homogeneous porous substrates with arbitrary cross-sectional shapes, which allows one to determine the cross-sectional profile required for a prescribed fluid velocity or mass transport rate. An extension of the model to slit microchannels is also demonstrated. Calculations were validated by experiments with prototypes fabricated in our lab. The proposed method constitutes a valuable tool for the rational design of paper-based assays.

The inverse problem of capillary filling, as defined in this work, consists in determining the capillary radius profile from experimental data of the meniscus position l as a function of time t. This problem is central in diverse applications, such as the characterization of nanopore arrays or the design of passive transport in microfluidics; it is mathematically ill posed and has multiple solutions; i.e., capillaries with different geometries may produce the same imbibition kinematics. Here a suitable approach is proposed to solve this problem, which is based on measuring the imbibition kinematics in both tube directions. Capillary filling experiments to validate the calculation were made in a wide range of length scales: glass capillaries with a radius of around 150  μm and anodized alumina membranes with a pores radius of around 30  nm were used. The proposed method was successful in identifying the radius profile in both systems. Fundamental aspects also emerge in this study, notably the fact that the l(t)∝t1/2 kinematics (Lucas-Washburn relation) is not exclusive of uniform cross-sectional capillaries.

The apparent hydrodynamic slip of polymer solutions is a result of polymer depletion at channel walls, and its fluid dynamic effects are well known. This work reviews the evidences of apparent slip in electrokinetics, and discusses practical consequences in the following fields: (i) electrokinetic transport of polymer solutions in microchannels, which is of interest for the design and operation of microfluidic chips, particularly for electrophoresis; (ii) electroosmotic pumping, where it has been observed that the employment of polymer solutions greatly enhances the output pressure; and (iii) electrokinetic energy conversion, where the apparent slip also contributes to improve the conversion efficiency. In all cases, critical discussions are taken from basic physical concepts., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An optofluidic method that accurately identifies the internal geometry of nanochannel arrays is presented. It is based on the dynamics of capillary-driven fluid imbibition, which is followed by laser interferometry. Conical nanochannel arrays in anodized alumina are investigated, which present an asymmetry of the filling times measured from different sides of the membrane. It is demonstrated by theory and experiments that the capillary filling asymmetry only depends on the ratio H of the inlet to outlet pore radii and that the ratio of filling times vary closely as H(7/3). Besides, the capillary filling of conical channels exhibits striking results in comparison to the corresponding cylindrical channels. Apart from these novel results in nanoscale fluid dynamics, the whole method discussed here serves as a characterization technique for nanoporous membranes.

An experimental study on the capillary filling of nanoporous silicon with different fluids is presented. Thin nanoporous membranes were obtained by electrochemical anodization, and the filling dynamics was measured by laser interferometry, taking advantage of the optical properties of the system, related with the small pore radius in comparison to light wavelength. This optical technique is relatively simple to implement and yields highly reproducible data. A fluid dynamic model for the filling process is also proposed including the main characteristics of the porous matrix (tortuosity, average hydraulic radius). The model was tested for different ambient pressures, porous layer morphology, and fluid properties. It was found that the model reproduces well the experimental data according to the different conditions. The predicted pore radii quantitatively agree with the image information from scanning electron microscopy. This technique can be readily used as nanofluidic sensor to determine fluid properties such as viscosity and surface tension of a small sample of liquid. Besides, the whole method can be suitable to characterize a porous matrix.

Electrokinetic energy conversion in microfluidic systems is a subject of intense research at present, where the main objective is to improve the thermodynamic efficiency of the process. As a novel strategy to the problem, this work focuses on the fluid dynamic properties of the working fluid. It is shown that polymer solutions with wall depletion can substantially increase the conversion efficiency in comparison to simple electrolytes under the same operating conditions. The effect is given by a reduction of the hydrodynamic conductance, while the streaming current is unaltered. It is also found that the maximum efficiency of electrokinetic power generation differs from that of electroosmotic pumping, in contrast to the case of simple electrolytes. This is due to the non-Newtonian character of polymeric fluids, which leads to nonlinear electrokinetic relations., (Copyright 2010 Elsevier Inc. All rights reserved.)

The EOF of polymer solutions is analysed in the framework of continuum fluid mechanics and the standard electrokinetic model. Two key aspects are taken into consideration: the non-Newtonian character of the fluid and the polymer concentration near the interface, which greatly modify the fluid viscosity in the region where electroosmosis takes place. A satisfactory mathematical model is derived for the electroosmotic mobility of solutions that present polymer depletion at the wall. The case of solutions containing polymers that adsorb onto the wall is briefly reviewed, and a preliminary approach is discussed for the limit of strong polymer adsorption. In order to illustrate the theoretical discussions, experimental data obtained from aqueous solutions of carboxymethyl cellulose in fused-silica capillaries are presented. Relevant results are observed, which are appropriately captured by the modelling proposed. The fundamental phenomena discussed in this work are of interest in microfluidics and electrophoresis.

A theoretical description of the electrokinetic flow of non-Newtonian fluids through slit and cylindrical microchannels is presented. Calculations are based on constitutive models of the fluid viscosity, and take into account wall depletion effects of colloids and polymer solutions. The resulting equations allow one to predict the flow rate and electric current as functions of the simultaneously applied electric potential and pressure gradients. It is found that (i) nonlinear effects induced by the shear-dependent viscosity are limited to the pressure-driven component of the flow, and (ii) the reciprocity between electroosmosis and streaming current is complied. Thus a generalized form of the force-flux relations is proposed, which is of interest in microfluidic applications.

A theoretical relation between the zeta potential of silica capillaries and the composition of the background electrolyte (BGE) is presented in order to be used in capillary zone electrophoresis (CZE). This relation is derived on the basis of the Poisson-Boltzmann equation and considering the equilibrium dissociation of silanol groups at the capillary wall as the mechanism of charge generation. The resulting model involves the relevant physicochemical parameters of the BGE-capillary interface. Special attention is paid to the characterization of the BGE, which can be either salt or/and buffer solutions. The model is successfully applied to electroosmotic flow (EOF) experimental data of different aqueous solutions, covering a wide range of pH and ionic strength. Numerical predictions are also presented showing the capability of the model to quantify the EOF, the control of which is relevant to improve analyte separation performance in CZE.

A theoretical interpretation of simultaneous viscosity measurements and light backscattering experiments is carried out in the framework of the structural model for concentrated dispersions proposed previously by one of the authors. The work is mainly focused on erythrocyte aggregation, hence spherical as well as linear aggregates (rouleaux) were considered in the modeling. A connection between the structural parameters provided by each technique is established, in particular the characteristic shear rates for break up of aggregates. Theoretical predictions were then applied to experimental data of human blood collected from patients with different diseases in a hospital data bank. Finally, we conclude that the structural modeling proposed permits a reasonably good correlation between experimental data of viscometry and light backscattering from blood samples, leading to new perspectives in the analysis of the red blood cell aggregation phenomena.

Heat-induced aggregation of soy proteins in aqueous suspensions was studied through cone and plate rheometry for two different heating conditions. The rheometric data obtained covered the temperature range from 20 degrees C (stable colloidal suspension) to approximately 90 degrees C (onset of network formation). Calorimetric data for the soy protein samples were also obtained to evaluate the degree of protein denaturation in the rheometric cell. Heat-induced transitions in soy globulins, such as dissociation, denaturation, and aggregation, were analyzed in relation to the rheological response of the suspension. The viscosity of the stable colloidal suspension satisfies the Cross model. A viscosity equation for the aggregating suspension was also derived by considering the fractal structure of the particle clusters and the Brownian aggregation mechanism. This equation is suitable to describe the experimental viscosity data.