Electrical circuits from capillary flow driven evaporation deposition of carbon nanotube ink in non-porous V-grooves

Low cost pliable electronics portend the advancement of novel inexpensive microfluidic electrochemical devices. In the direct printing approach, the manner of deposition of conductive material from a liquid suspension to ensure electrical continuity is crucial. We describe here an approach in which V-groove networks that make up the path of circuitry are first scribed on non-porous inexpensive surfaces. Liquid drops of carbon nanotube ink are then placed on the surface adjacent to the V-grooves to enable wicking to produce the electrical circuit. This method essentially bypasses the need for inkjet printing. We investigate the basic efficacy of the conductive networks developed using this approach and demonstrate its use in generating electrically driven liquid flow of particles in a simple open capillary channel.     

Capillary and van der Waals forces between uncharged colloidal particles linked by a liquid bridge

This work presents a theoretical study of the forces established between colloidal particles connected by means of a concave liquid bridge, where the solid particles are partially wetted by a certain amount of liquid also possessing a dry portion of their surfaces. In our analysis, we adopt a two-particle model assuming that the solids are spherical and with the same sizes and properties and that the liquid meniscus features an arc-of-circumference contour. The forces considered are the typical capillary ones, namely, wetting and Laplace forces, as well as the van der Waals force, assuming the particles uncharged. We analyze different parameters which govern the liquid bridge: interparticle separation, wetting angle, and liquid volume, which later determine the value of the forces. Due to the dual characteristic of the particles' surfaces, wet and dry, the forces are to be determined numerically in each case. The results indicate that the capillary forces are dominant in most of the situations meanwhile the van der Waals force is noticeable at very short distances between the particles.     

Stretching liquid bridges with bubbles: the effect of air bubbles on liquid transfer

Liquid bridges containing bubbles are relevant to industrial printing and are also a topic of fundamental scientific interest. We use flow visualization to study the stretching of liquid bridges, both with and without bubbles, at low capillary numbers. We find that whereas the breakup of wetting fluids between two identical surfaces is symmetric about the bridge midpoint, contact line pinning breaks this symmetry at slow stretching speeds for nonwetting fluids. We exploit this observation to force air bubbles selectively toward the least hydrophilic plate confining the liquid bridge.     

Use of electrokinetic measurements for characterization of columns used in capillary electrochromatography

The separation mechanism in capillary electrochromatography (CEC) is a hybrid differential migration process, which entails the features of both high-performance liquid chromatography (HPLC) and capillary zone electrophoresis (CZE), i.e., chromatographic retention and electrophoretic migration. The focus of this paper is on the use of electrokinetic data, such as current, electroosmotic flow (EOF) and column efficiency measurements, that are readily available, for an improved understanding of CEC separations. A framework is presented here for the use of this data for evaluation of a variety of performance parameters including, conductivity ratio, interstitial EOF mobility, porosity, and zeta potential. This framework is applied for characterization of two monolithic columns with different chemistry that were manufactured in-house. The above-mentioned performance parameters were calculated for the two columns and it is found that the poly(VBC-EGDMA-SWNT) monolithic column with the GPTMS-PEI coating offers a significantly improved flow distribution in comparison to the poly(VBC-EGDMA) monolithic column. This observation is confirmed by performing separation of peptides on the two columns and height equivalent of a theoretical plate (HETP) measurements on the resulting peaks. It is shown that following our approach leads to an improved understanding of the separations achieved with the columns and to better column design.     

Surface-directed capillary system; theory, experiments and applications

We present a capillary flow system for liquid transport in microsystems. Our simple microfluidic system consists of two planar parallel surfaces, separated by spacers. One of the surfaces is entirely hydrophobic, the other mainly hydrophobic, but with hydrophilic pathways defined on it by photolithographic means. By controlling the wetting properties of the surfaces in this manner, the liquid can be confined to certain areas defined by the hydrophilic pathways. This technique eliminates the need for alignment of the two surfaces. Patterned plasma-polymerized hexafluoropropene constitutes the hydrophobic areas, whereas the untreated glass surface constitutes the hydrophilic pathways. We developed a theoretical model of the capillary flow and obtained analytical solutions which are in good agreement with the experimental results. The capillarity-driven microflow system was also used to pattern and immobilize biological material on planar substrates: well-defined 200 microm wide strips of human cells (HeLa) and fluorescence labelled proteins (fluorescein isothiocyanate-labelled bovine serum albumin, i.e., FITC-BSA) were fabricated using the capillary flow system presented here.     

Evaporative micro-particle self assembly influenced by capillary evacuation

As evaporation does not incur energy introduction, the droplet coffee-stain patterning approach is attractive for biochemical tests conducted in the field or in third world environments. A practical strategy uses chemically functionalized microbeads for the coffee stain deposition process. From an application perspective, it will be necessary to minimize the coffee stain deposition time, as evaporation, depending on the volume of the droplet, can be a slow process. The introduction of a porous media will generate a capillary flow (or wicking) that removes any remnant liquid in the droplet, thus permitting it to be done inexpensively and in the field. Using optical profilometry, we were able to establish that polystyrene microspheres developed more copious and defined single ring coffee depositions than silica of the same size and concentration in a suspension. In analyzing the droplet capillary evacuation process with a porous media, we found the liquid bridge formed during the later stages to rupture and leave behind some liquid material for a second stage evaporation process. This was responsible for a two ring structure that was more visible with silica microspheres. A high degree of hysteresis of the contact angle was found to develop at the contact line in which values below 5° could be achieved. Dynamic observations showed the copious and dense packing of polystyrene particles to be more resistant to ring break up from the evacuation flow. Nevertheless, erosion of the back array portions of the ring was evident notwithstanding either type of microsphere used.     

How the capillary burst microvalve works

The capillary burst microvalve offers an attractive means to regulate microliquid flow owing to its simple structure and operation process. However, there existed no rigorous theoretical work to elucidate how the valve works and consequently to predict the valve-bursting condition. Therefore, here we report the theoretical investigation of how the capillary burst valve can stop the advancing liquid meniscus and when it bursts. We confirm our theory with experiments using a centrifugal microfluidic valve system fabricated by soft lithography.     

Capillary forces between two spheres with a fixed volume liquid bridge: theory and experiment

Capillary forces are commonly encountered in nature because of the spontaneous condensation of liquid from surrounding vapor, leading to the formation of a liquid bridge. In most cases, the advent of capillary forces by condensation leads to undesirable events such as an increase in the strength of granules, which leads to flow problems and/or caking of powder samples. The prediction and control of the magnitude of capillary forces is necessary for eliminating or minimizing these undesirable events. The capillary force as a function of the separation distance, for a liquid bridge with a fixed volume in a sphere/plate geometry, was calculated using different expressions reported previously. These relationships were developed earlier, either on the basis of the total energy of two solid surfaces interacting through the liquid and the ambient vapor or by direct calculation of the force as a result of the differential gas pressure across the liquid bridge. It is shown that the results obtained using these methodologies (total energy or differential pressure) agree, confirming that a total-energy-based approach is applicable, despite the thermodynamic nonequilibrium conditions of a fixed volume bridge rupture process. On the basis of the formulas for the capillary force between a sphere and a plane surface, equations for the calculation of the capillary force between two spheres are derived in this study. Experimental measurements using an atomic force microscope (AFM) validate the formulas developed. The most common approach for transforming interaction force or energy from that of sphere/plate geometry to that of sphere/sphere geometry is the Derjaguin approximation. However, a comparison of the theoretical formulas derived in this study for the interaction of two spheres with those for sphere/plate geometry shows that the Derjaguin approximation is only valid at zero separation distance. This study attempts to explain the inapplicability of the Derjaguin approximation at larger separation distances. In particular, the area of a liquid bridge changes with the separation distance, H, and thereby does not permit the application of the "integral method," as used in the Derjaguin approximation.     

Subatmospheric electrospray interface for coupling of microcolumn separations with mass spectrometry

A modular subatmospheric electrospray interface with fiber optic UV detection close to the electrospray tip was developed for coupling of microcolumn separation techniques with mass spectrometry. The interface was based on a liquid junction with a removable microelectrospray tip. The electrospray tip was enclosed in a subatmospheric chamber attached in front of the sampling orifice of the mass spectrometer. The inlet of the liquid junction was maintained at atmospheric pressure, and thus no pressure drop developed across the separation column. The flow rate of the electrosprayed liquid from the liquid junction reservoir was adjusted by the pressure in the electrospray chamber. In this approach, a continuous and stable electrospray could be achieved without the use of an external pump. Since the electrospray did not depend on fluid delivery from the separation column, coated capillaries without electroosmotic flow as well as capillaries with electroosmotic flow could be used for capillary electrophoresis. In addition, the interface was found to be effective with capillary liquid chromatography. The use of a fiber optic UV detector placed close to the exit of the separation column provided additional detection information and a simple means of troubleshooting. The interface did not significantly influence the quality of the separation, even with columns generating several hundred thousand theoretical plates. Peptide samples in the submicromolar concentration range were detected, corresponding to a limit of detection in the attomole range.     

The rheology of pseudoplastic fluids in porous media using network modeling

This paper considers the rheology of pseudoplastic (shear thinning) fluids in porous media. The central problem studied is the relationship between the viscometric behavior of the polymer solution and its observed behavior in the porous matrix. In the past, a number of macroscopic approaches have been applied, usually based on capillary bundle models of the porous medium. These simplified models have been used along with constitutive equations describing the fluid behavior (usually of power law type) to establish semiempirical macroscopic equations describing the flow of non-Newtonian fluids in porous media. This procedure has been reasonably successful in correlating experimental results on the flow of polymer solutions through both consolidated and unconsolidated porous materials. However, it does not allow an interpretation of polymer flow in porous media in terms of the flows on a microscopic scale; nor does it allow us to predict changes in macroscopic behavior resulting from variations at a microscopic level in the characteristics of the porous medium such as pore size distribution. In this work, we use a network approach to the modeling of non-Newtonian rheology, in order to understand some of the more detailed features of polymjer flow in porous media. This approach provides a mathematical bridge between the behavior of the non-Newtonian fluid in a single capillary and the macroscopic behavior as deduced from the pressure drop-flow rate relation across the whole network model. It demonstrates the importance of flow redistribution within the elements of the capillary network as the overall pressure gradient varies. As an example of a pseudoplastic fluid in a porous medium, we consider the flow of xanthan biopolymer. This polymer is important as a displacing fluid viscosifier in enhanced oil recovery applications and, for that reason, a considerable amount of experimental data has been published on the flow of xanthan solutions in various porous media.     

Enantiomer separation by capillary electrochromatography on a cyclodextrin-modified monolith

A chiral monolithic stationary phase was prepared by packing a capillary with bare porous silica and sintering the silica bed at high temperature. The resulting silica monolith was polymer-coated with Chirasil-Dex, a permethylated beta-cyclodextrin covalently linked via an octamethylene spacer to dimethylpolysiloxane. Subsequently, Chirasil-Dex was thermally immobilized on the silica support and a chiral monolith of very high stability (30 kV, more than 400 bar pressure) was obtained. The enantiomer separation of various chiral compounds by monolithic (rod) capillary electrochromatography (rod-CEC) was feasible. This method was compared with capillary liquid chromatography (LC) in a single-column mode using unified equipment. About two to three times higher efficiency was found in the rod-CEC mode as compared to rod-LC. The influence of pressure-driven flow support on efficiency, resolution, elution time and baseline stability was investigated. The amount and nature of organic modifier strongly influences efficiency and resolution.     

Determination of acid dissociation constants by capillary electrophoresis

Capillary electrophoresis affords a simple, automated approach for the measurement of pKa values in the range 2-11 at a throughput of less than 1 h per sample per instrument. Agreement with literature values is usually within 0.20 log units with a precision better than 0.07 log units. The attractive features of capillary electrophoresis for pKa measurements are: (1) conventional instrumentation with a high level of automation are suitable for all measurements; (2) because it is a separation method samples need not be of high purity; (3) samples of low water solubility with suitable chromophores are easily handled (detection limits in the microM range); (4) sample consumption per measurement is in the microgram range; and (5) since only mobilities are measured, exact knowledge of concentrations is not needed. The general approach can be extended to pKa measurements in aqueous-organic solvent mixtures and non-aqueous solvents with suitable calibration. The widespread use of absorbance detection in capillary electrophoresis means that the sample must have a suitable chromophore for detection. The main source of controllable error is the accuracy of buffer standardization and their stability in use, and uncontrollable error, the retentive interactions of the sample with the column wall. The latter seems to be a rare problem in practice for typical operating conditions.     

Microelectrospray interface with coaxial sheath flow for high-resolution capillary electrophoresis/mass spectrometry separation

We have fabricated a coaxial sheath liquid flow microelectrospray ionization (microESI) interface for capillary electrophoresis coupled with mass spectrometry (CE/MS). The ESI interface, which features a reduced probe diameter (130 microm i.d. x 174 microm o.d.) with a nebulizer-free format, can relatively easily electrospray a large amount of make-up sheath liquid (5-10 microL/min) over the long term (more than 80 runs) with a high degree of stability. The interface also provides higher separation qualities and improved detection sensitivities compared with a conventional ion spray (IS) interface.     

In-pore tensile stress by drying-induced capillary bridges inside porous materials

We present here some evidences that capillary liquid bridges are able to deform micrometric cylindrical pores by tensile stress. Brine-soaked filter membranes are submitted to drying conditions leading to NaCl precipitation inside the 5-10 μm pores. A close examination demonstrated that two forms of NaCl crystallites are successively generated. First, primary cubic crystals grow, driven by the permanent evaporation. When this angular primary solid gets near the pore wall, while the evaporation makes the pore volume to be partly invaded by air, capillary liquid can bridge the now-small gap between the halite angles and the pore wall. In a second step, these small capillary bridges are frozen by a secondary precipitation event of concave-shaped NaCl. The proposed interpretation is that the liquid capillary bridges deform the host matrix of the membrane, and the situation is fossilized by the growth of solid capillary bridges. A quantitative interpretation is proposed and the consequences towards the natural media outlined.     

Influence of the Type of Contact between Particles Joined by a Liquid Bridge on the Capillary Cohesive Forces

The influence of the particle dimensions and type of interparticle contact on the magnitude of the capillary forces between the powder particles is studied on the basis of a model describing a capillary interaction of two particles joined by a liquid bridge. Various contact types were implemented using combinations of different particle shapes: spherical, conical, or plane. The meniscus of the bridge is described using a circular approximation; experimental results confirm that its use is justified. A method is developed for calculating the capillary forces and the amount of the liquid in the bridge with allowance for various parameters of the powder. The calculated results show that the dimensions of the particles and the type of their contact significantly affect the magnitude of the capillary forces.     

Mechanisms of equilibrium shape transitions of liquid droplets in electrowetting

Liquid droplets bridging the gap between two dielectric-coated horizontal electrode plates suffer breakup instabilities when a voltage applied between the electrodes exceeds a threshold. Interestingly enough, broken liquid bridges (i.e. a pair of a sessile and a pendant drop) can spontaneously rejoin if the voltage is still applied to the electrodes. Here we study the electro-hydrostatics of the liquid bridges in the joined or broken state and we illuminate the mechanisms of the shape transitions that lead to bridge rupture or droplet joining. The governing equations of the capillary electro-hydrostatics form nonlinear and free boundary problems which are solved numerically by the Galerkin/finite element method. On one hand, we found that capillary bridges become unstable at a turning point bifurcation in their solution space. The solutions past the turning point are unstable and the instability signals the bridge rupture. On the other hand, the separate droplets approach each other as the applied voltage increases. However, solutions become unstable past a critical voltage at a turning point bifurcation and the droplets join. By studying the relative position of the turning points corresponding to bridge rupture and droplet joining, respectively, we define parameter regions where stable bridges or separate droplets or oscillations between them can be realized.     

Heat of transport of dilute adsorbable gases in single pores and model porous media as a function of pore structure

A previous theoretical study of the heat of transport of a dilute adsorbable gas in a model pore, based on a new, more rigorous approach, is here extended to confirm and amplify the general features of the behavior predicted by the new approach in contradistinction to conventional theory. A simple analytical semiquantitative treatment is developed for moderate to high heats of transport and the effects of the form of the adsorption potential and of pore shape are elucidated. Some important aspects of pore structure in real porous media are then simulated by means of suitable simple capillary models. The results obtained permit a significant advance in the interpretation of experimental results.     

Forced imbibition-a tool for separate determination of Laplace pressure and drag force in capillary filling experiments

When a very thin capillary is inserted into a liquid, the liquid is sucked into it: this imbibition process is controlled by a balance of capillary and drag forces which are hard to quantify experimentally, particularly considering flow on the nanoscale. By computer experiments using a generic coarse-grained model, it is shown that an analysis of imbibition forced by a controllable external pressure independently quantifies the Laplace pressure and Darcy's permeability as relevant physical parameters governing the imbibition process. From the latter one may then compute the effective pore radius, effective viscosity, dynamic contact angle and slip length of the fluid flowing into the pore. In determining all these parameters independently, the consistency of our analysis of such forced imbibition processes is demonstrated.     

Finite system size effects in the interfacial dynamics of binary liquid films

We study the relaxation dynamics of capillary waves in the interface between two confined liquid layers by means of molecular dynamics simulations. We measure the autocorrelations of the interfacial Fourier modes and find that the finite thickness of the liquid layers leads to a marked increase of the relaxation times as compared to the case of fluid layers of infinite depth. The simulation results are in good agreement with a theoretical first-order perturbation derivation, which starts from the overdamped Stokes' equation. The theory also takes into account an interfacial friction, but the difference with no-slip interfacial conditions is small. When the walls are sheared, it is found that the relaxation times of modes perpendicular to the flow are unaffected. Modes along the flow direction are relatively unaffected as long as the equilibrium relaxation time is sufficiently short compared to the rate of deformation. We discuss the consequences for experiments on thin layers and on ultralow surface tension fluids, as well as computer simulations.     

Capillary electrophoresis coupled to time of flight-mass spectrometry of therapeutic peptide hormones

We have established a method for separation and characterization of a series of peptide hormones of pharmaceutical interest and wide therapeutical use by capillary electrophoresis-electrospray-mass spectrometry (CE-ES-MS) using a sheath flow interface. Several parameters were systematically investigated, such as concentration of the electrolyte, organic solvent and sheath liquid composition, gas flow rates and capillary position. Moreover, limits of detection, linearity, repeatability and day-to-day reproducibility of the proposed method were studied in order to obtain the main quality parameters.