Polymeric liquids in mesoporous photonic structures: From precursor film spreading to imbibition dynamics at the nanoscale.

Polymers are known to wet nanopores with high surface energy through an atomically thin precursor film followed by slower capillary filling. We present here light interference spectroscopy using a mesoporous membrane-based chip that allows us to observe the dynamics of these phenomena in situ down to the sub-nanometer scale at milli- to microsecond temporal resolution. The device consists of a mesoporous silicon film (average pore size 6 nm) with an integrated photonic crystal, which permits to simultaneously measure the phase shift of thin film interference and the resonance of the photonic crystal upon imbibition. For a styrene dimer, we find a flat fluid front without a precursor film, while the pentamer forms an expanding molecular thin film moving in front of the menisci of the capillary filling. These different behaviors are attributed to a significantly faster pore-surface diffusion compared to the imbibition dynamics for the pentamer and vice versa for the dimer. In addition, both oligomers exhibit anomalously slow imbibition dynamics, which could be explained by apparent viscosities of six and eleven times the bulk value, respectively. However, a more consistent description of the dynamics is achieved by a constriction model that emphasizes the increasing importance of local undulations in the pore radius with the molecular size and includes a sub-nanometer hydrodynamic dead, immobile zone at the pore wall but otherwise uses bulk fluid parameters. Overall, our study illustrates that interferometric, opto-fluidic experiments with mesoporous media allow for a remarkably detailed exploration of the nano-rheology of polymeric liquids.

Synthesis, structure, and characterisation of a ferromagnetically coupled dinuclear complex containing Co(II) ions in a high spin configuration and thiodiacetate and phenanthroline as ligands and of a series of isomorphous heterodinuclear complexes containing different Co : Zn ratios.

We report the synthesis, crystal structure, and characterisation of a dinuclear Co(II) compound with thiodiacetate (tda) and phenanthroline (phen) as ligands (1), and of a series of metal complexes isomorphous to 1 with different Co : Zn ratios (2, 4 : 1; 3, 1 : 1; 4, 1 : 4; 5, 1 : 10). General characterisation methodologies and X-ray data showed that all the synthesised complexes are isomorphous to Zn(II) and Cu(II) analogues (CSD codes: DUHXEL and BEBQII). 1 consists of centrosymmetric Co(II) ion dimers in which the ions are 3.214 Å apart, linked by two µ-O bridges. Each cobalt atom is in a distorted octahedral environment of the N2O3S type. UV-vis spectra of 1 and 5 are in line with high spin (S = 3/2) Co(II) ions in octahedral coordination and indicate that the electronic structure of both Co(II) ions in the dinuclear unit does not significantly change relative to that of the magnetically isolated Co(II) ion. EPR spectra of powder samples of 5 (Co : Zn ratio of 1 : 10) together with spectral simulation indicated high spin Co(II) ions with high rhombic distortion of the zfs [E/D = 0.31(1), D > 0]. DC magnetic susceptibility experiments on 1 and analysis of the data constraining the E/D value obtained by EPR yielded g = 2.595(7), |D| = 61(1) cm-1, and an intradimer ferromagnetic exchange coupling of J = 1.39(4) cm-1. EPR spectra as a function of Co : Zn ratio for both powder and single crystal samples confirmed that they result from two effective S' = 1/2 spins that interact through dipolar and isotropic exchange interactions to yield magnetically isolated S' = 1 centres and that interdimeric exchange interactions, putatively mediated by hydrophobic interactions between phen moieties, are negligible. The latter observation contrasts with that observed in the Cu(II) analogue, where a transition from S = 1 to S' = 1/2 was observed. Computational calculations indicated that the absence of the interdimeric exchange interaction in 1 is due to a lower Co(II) ion spin density delocalisation towards the metal ligands.

A simple method for the assessment of electrophoretic mobility in porous media.

Developing paper-based electrophoretic methods involve dealing with significant uncertainty levels when compared to their capillary counterparts. Critical information for developing these kinds of methods are the electrophoretic mobility of background electrolytes and samples. This work presents the design and characterization of a device for measuring the electrophoretic mobilities of dyes in porous media. The device was developed with the aim of validating a previously presented model and also proposing a protocol for the straightforward determination of electrophoretic mobilities in porous media when open-channel values are already known. Whatman #1 paper was used as a model substrate as far as it is the most common porous medium substrate for paper-based electrophoresis. The device was designed using a numerical simulation-assisted approach, utilizing OpenFOAM® and specific solvers for capillary transport and electromigration, namely porousMicroTransport and electroMicroTransport, respectively. The electrophoretic mobilities of five dyes were analyzed experimentally with the proposed device. To establish appropriate comparative values at different pHs, experiments in fused silica capillaries were also performed. An effective parameter model for describing the electrophoretic behavior of dyes in porous media, that is, the constriction factor, was found consistent with previous reports for the Whatman #1 paper. This consistency was found after considering (via direct measurements) the chromatographic effect of the medium over each dye. Consequently, the recorded values hold significant worth due to their potential for direct application in designing new experiments or devices in Whatman #1 paper. With the validation of the model through the experiments with the proposed device, those researchers interested on developing electrophoretic methods in porous substrates can make use of the open-channel electrophoretic mobilities reported in the literature, or in the well-known software databases, and correct them for the media of interest just by performing two simple characterization steps.

Precise electroosmotic flow measurements on paper substrates.

A novel method for electroosmotic flow (EOF) measurement on paper substrates is presented; it is based on dynamic mass measurements by simply using an analytical balance. This technique provides a more reliable alternative to other EOF measurement methods on porous media. The proposed method is used to increase the amount and quality of the available information about physical parameters that characterize fluid flow on microfluidic paper-based analytical devices (µPADs). Measurements were performed on some of the most frequently used materials for µPADs, i.e., Whatman #1 , S&S, and Muntktell 00A filter paper. Obtained experimental results are consistent with the few previously reported data, either experimental or numerical, characterizing EOF in paper substrates. Moreover, a thorough analysis is presented for the quantification of the different effects that affect the measurements such as Joule effect and evaporation. Experimental results enabled, for the first time, to establish well-defined electroosmotic characteristics for the three substrates in terms of the magnitude of EOF as funtion of pH, enabling researchers to make a rational choice of the substrate depending on the electrophoretic technique to be implemented. The measurement method can be described as robust, reliable, and affordable enough for being adopted by researchers and companies devoted to electrophoretic µPADs and related technologies.

Precursor Film Spreading during Liquid Imbibition in Nanoporous Photonic Crystals.

When a macroscopic droplet spreads, a thin precursor film of liquid moves ahead of the advancing liquid-solid-vapor contact line. Whereas this phenomenon has been explored extensively for planar solid substrates, its presence in nanostructured geometries has barely been studied so far, despite its importance for many natural and technological fluid transport processes. Here we use porous photonic crystals in silicon to resolve by light interferometry capillarity-driven spreading of liquid fronts in pores of few nanometers in radius. Upon spatiotemporal rescaling the fluid profiles collapse on master curves indicating that all imbibition fronts follow a square-root-of-time broadening dynamics. For the simple liquid (glycerol) a sharp front with a widening typical of Lucas-Washburn capillary-rise dynamics in a medium with pore-size distribution occurs. By contrast, for a polymer (PDMS) a precursor film moving ahead of the main menisci entirely alters the nature of the nanoscale transport, in agreement with predictions of computer simulations.

Spontaneous water adsorption-desorption oscillations in mesoporous thin films.

Understanding fluid transport and phase changes in nanopore structures is of great interest to many application fields, from energy conversion to water harvesting. This work discusses the spontaneous oscillations of the water saturation of mesoporous thin films, in the zone adjacent to a sessile water drop, at ambient conditions. The wetting-front dynamics onto the film is described by considering three coexisting phenomena: infiltration from the water drop, condensation from air vapor, and evaporation to the ambient. It was found that the oscillations follow spontaneous condensation-evaporation imbalances, which are governed by the hysteretic character of the adsorption-desorption behavior of the mesoporous material. The outcomes of this work provide insights on the complex interplay between water and nanopore structures, which has practical implications for the handling of humid microenvironments in lab-on-a-chip technology, as well as for many processes that take part of the cycle of water in nature.

Design keys for paper-based concentration gradient generators.

The generation of concentration gradients is an essential operation for several analytical processes implemented on microfluidic paper-based analytical devices. The dynamic gradient formation is based on the transverse dispersion of chemical species across co-flowing streams. In paper channels, this transverse flux of molecules is dominated by mechanical dispersion, which is substantially different than molecular diffusion, which is the mechanism acting in conventional microchannels. Therefore, the design of gradient generators on paper requires strategies different from those used in traditional microfluidics. This work considers the foundations of transverse dispersion in porous substrates to investigate the optimal design of microfluidic paper-based concentration gradient generators (µPGGs) by computer simulations. A set of novel and versatile µPGGs were designed in the format of numerical prototypes, and virtual experiments were run to explore the ranges of operation and the overall performance of such devices. Then physical prototypes were fabricated and experimentally tested in our lab. Finally, some basic rules for the design of optimized µPGGs are proposed. Apart from improving the efficiency of mixers, diluters and µPGGs, the results of this investigation are relevant to attain highly controlled concentration fields on paper-based devices.

Transverse solute dispersion in microfluidic paper-based analytical devices (µPADs).

The transport of molecules and particles across adjacent flow streams is a key process in several operations implemented in microfluidic paper-based analytical devices (µPADs). Here, the transverse dispersion of analytes was quantitatively evaluated by theory and experiments. Different tests were carried out to independently measure the coefficients of both Brownian diffusion and mechanical dispersion under capillary-driven flow. The dispersion width was found to be independent of fluid velocity and analyte properties, and fully determined by the dispersivity coefficient, which is a characteristic of the paper microstructure. This information introduces a change of paradigm for the design of mixers, diluters, and concentration gradient generators on µPADs; therefore, efforts were made to rationalize these operations on paper. The research reveals that mixers and concentration gradient generators can be much more efficient than their counterparts made on conventional microchannels; in contrast, separators such as the H-filter need to be appropriately engineered on paper, because the working principle can be hindered by mechanical dispersion. The knowledge gained throughout this work would contribute to the design of µPADs with a new level of precision and control over the formation of localized concentration profiles.

Rational design of capillary-driven flows for paper-based microfluidics.

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.

Inverse problem of capillary filling.

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.

Real-time study of protein adsorption kinetics in porous silicon.

This paper presents an optical method for real-time monitoring of protein adsorption using porous silicon self-supported microcavities as a label-free detection platform. The study combines an experimental approach with a physical model for the adsorption process. The proposed model agrees well with experimental observations, and provides information about the kinetics of diffusion and adsorption of proteins within the pores, which will be useful for future experimental designs.

Optofluidic characterization of nanoporous membranes.

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.

Current-voltage characteristics in macroporous silicon/SiOx/SnO2:F heterojunctions.

We study the electrical characteristics of macroporous silicon/transparent conductor oxide junctions obtained by the deposition of fluorine doped-SnO2 onto macroporous silicon thin films using the spray pyrolysis technique. Macroporous silicon was prepared by the electrochemical anodization of a silicon wafer to produce pore sizes ranging between 0.9 to 1.2 µm in diameter. Scanning electronic microscopy was performed to confirm the pore filling and surface coverage. The transport of charge carriers through the interface was studied by measuring the current-voltage curves in the dark and under illumination. In the best configuration, we obtain a modest open-circuit voltage of about 70 mV and a short-circuit current of 3.5 mA/cm2 at an illumination of 110 mW/cm2. In order to analyze the effects of the illumination on the electrical properties of the junction, we proposed a model of two opposing diodes, each one associated with an independent current source. We obtain a good accordance between the experimental data and the model. The current-voltage curves in illuminated conditions are well fitted with the same parameters obtained in the dark where only the photocurrent intensities in the diodes are free parameters.

Capillary filling in nanostructured porous silicon.

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.

Analytical study of the acoustic field in a spherical resonator for single bubble sonoluminescence.

The acoustic field in the liquid within a spherical solid shell is calculated. The proposed model takes into account Stoke's wave equation in the viscous fluid, the membrane theory to describe the solid shell motion and the energy loss through the external couplings of the system. A point source at the resonator center is included to reproduce the acoustic emission of a sonoluminescence bubble. Particular calculations of the resulting acoustic field are performed for viscous liquids of interest in single bubble sonoluminescence. The model reveals that in case of radially symmetric modes of low frequency, the quality factor is mainly determined by the acoustic energy flowing through the mechanical coupling of the resonator. Alternatively, for high frequency modes the quality factor is mainly determined by the viscous dissipation in the liquid. Furthermore, the interaction between the bubble acoustic emission and the resonator modes is analyzed. It was found that the bubble acoustic emission produces local maxima in the resonator response. The calculated amplitudes and relative phases of the harmonics constituting the bubble acoustic environment can be used to improve multi-frequency driving in sonoluminescence.

Dynamics of sonoluminescing bubbles within a liquid hammer device.

We studied the dynamics of a single sonoluminescing bubble (SBSL) in a liquid hammer device. In particular, we investigated the phosphoric acid-xenon system, in which pulses up to four orders of magnitude brighter than SBSL in water systems (about 10;{12} photons per pulse) have been previously reported [Chakravarty, Phys. Rev. E 69, 066317 (2004)]. We used stroboscopic photography and a Mie scattering technique in order to measure the radius evolution of the bubbles. Under adequate conditions we may position a bubble at the bottom of the tube (cavity) and a second bubble trapped at the middle of the tube (upper bubble). During its collapse, the cavity produces the compression of the liquid column. This compression drives impulsively the dynamics of the upper bubble. Our measurements reveal that the observed light emissions produced by the upper bubble are generated at its second collapse. We employed a simple numerical model to investigate the conditions that occur during the upper bubble collapse. We found good agreement between numerical and experimental values for the light intensity (fluence) and light pulse widths. Results from the model show that the light emission is increased mainly due to an increase in noble gas ambient radius and not because the maximum temperature increases. Even for the brightest pulses obtained ( 2x10;{13} photons, about 20W of peak power) the maximum temperatures computed for the upper bubble are always lower than 20000K .

Experimental study of transient paths to the extinction in sonoluminescence.

An experimental study of the extinction threshold of single bubble sonoluminescence in an air-water system is presented. Different runs from 5% to 100% of air concentrations were performed at room pressure and temperature. The intensity of sonoluminescence (SL) and time of collapse (t(c)) with respect to the driving were measured while the acoustic pressure was linearly increased from the onset of SL until the bubble extinction. The experimental data were compared with theoretical predictions for shape and position instability thresholds. It was found that the extinction of the bubble is determined by different mechanisms depending on the air concentration. For concentrations greater than approximately 30%-40% with respect to the saturation, the parametric instability limits the maximum value of R(0) that can be reached. On the other hand, for lower concentrations, the extinction appears as a limitation in the time of collapse. Two different mechanisms emerge in this range, i.e., the Bjerknes force and the Rayleigh-Taylor instability. The bubble acoustic emission produces backreaction on the bubble itself. This effect occurs in both mechanisms and is essential for the correct prediction of the extinction threshold in the case of low air dissolved concentration.

Trapping an intensely bright, stable sonoluminescing bubble.

Previous works on single bubble sonoluminescence in sulfuric acid solutions have stressed the fact that the sonoluminescence (SL) emissions are the highest ever found, but at the same time the bubble moves in orbits. We have fixed the SL bubble spatially and at the same time we have reached higher SL emissions using another harmonic acoustic signal to produce the acoustic excitation. Multiple harmonic excitation produces up to a fourfold increase in SL emissions, reaching the peak value of about 40 microW for a moving bubble and 15 microW for a nonmoving bubble. The ability to have a bright stationary bubble also opens new research opportunities. In particular, we develop a new method to measure the absolute radius evolution of the bubble that exploits this stability.

Positional stability as the light emission limit in sonoluminescence with sulfuric acid.

We studied a single bubble sonoluminescence system consisting of an argon bubble in a sulfuric acid aq. solution. We experimentally determined the relevant variables of the system. We also measured the bubble position, extent of the bubble orbits, and light intensity as a function of acoustic pressure for different argon concentrations. We find that the Bjerknes force is responsible for the bubble mean position and this imposes a limitation in the maximum acoustic pressure that can be applied to the bubble. The Rayleigh-Taylor instability does not play a role in this system and, at a given gas concentration, the SL intensity depends more on the bubble time of collapse than any other investigated parameter.

Numerical and experimental study of dissociation in an air-water single-bubble sonoluminescence system.

We performed a comprehensive numerical and experimental analysis of dissociation effects in an air bubble in water acoustically levitated in a spherical resonator. Our numerical approach is based on suitable models for the different effects considered. We compared model predictions with experimental results obtained in our laboratory in the whole phase parameter space, for acoustic pressures from the bubble dissolution limit up to bubble extinction. The effects were taken into account simultaneously to consider the transition from nonsonoluminescence to sonoluminescence bubbles. The model includes (1) inside the bubble, transient and spatially nonuniform heat transfer using a collocation points method, dissociation of O2 and N2, and mass diffusion of vapor in the noncondensable gases; (2) at the bubble interface, nonequilibrium evaporation and condensation of water and a temperature jump due to the accommodation coefficient; (3) in the liquid, transient and spatially nonuniform heat transfer using a collocation points method, and mass diffusion of the gas in the liquid. The model is completed with a Rayleigh-Plesset equation with liquid compressible terms and vapor mass transfer. We computed the boundary for the shape instability based on the temporal evolution of the computed radius. The model is valid for an arbitrary number of dissociable gases dissolved in the liquid. We also obtained absolute measurements for R(t) using two photodetectors and Mie scattering calculations. The robust technique used allows the estimation of experimental results of absolute R0 and P(a). The technique is based on identifying the bubble dissolution limit coincident with the parametric instability in (P(a),R0) parameter space. We take advantage of the fact that this point can be determined experimentally with high precision and replicability. We computed the equilibrium concentration of the different gaseous species and water vapor during collapse as a function of P(a) and R0. The model obtains from first principles the result that in sonoluminescence the bubble is practically 100% argon for air dissolved in water. Therefore, the dissociation reactions in air bubbles must be taken into account for quantitative computations of maximum temperatures. The agreement found between the numerical and experimental data is very good in the whole parameter space explored. We do not fit any parameter in the model. We believe that we capture all the relevant physics with the model.