Electrocavitation in Nanochannels

A novel method has been developed to cavitate aqueous solutions, which is called electrocavitation. An axial voltage is applied in a nanochannel containing an aqueous solution with a stepwise conductivity gradient. A combination of electrical and viscous forces then generates a tension in the solution which, at sufficiently low pressures, causes it to cavitate. Measurement of the current during the experiment as well as optical observation provides knowledge on the time and axial position of cavitation, after which the pressure at the cavitation position can be calculated from a theoretical model in which also the ζ-potential is inserted, which is separately determined from electroosmotic flow experiments. It is found that generally the cavitation position coincides with the position of the conductivity step. In several experiments the cavitation pressure in successive experiments on the same channel became increasingly lower, suggesting a gradual removal of cavitation nuclei from the system. We calculated that pressures as low as −1630 bar ±10 % have been reached, close to theoretically predicted pressures for homogeneous cavitation. The platform performs reliably and can be easily controlled

Numerical investigation of micro- and nanochannel deformation due to discontinuous electroosmotic flow

Large pressures can induce detrimental deformation in micro- and nanofluidic channels. Although this has been extensively studied for systems driven by pressure and/or capillary forces, deflection in electrokinetic systems due to internal pressure gradients caused by non-uniform electric fields has not been widely explored. For example, applying an axial electric field in a channel with a step change in conductivity and/or surface charge can lead to internally generated pressures large enough to cause cavitation, debonding, and/or channel collapse. Finite electric double layers within nanofluidic channels can further complicate the physics involved in the deformation process. In order to design devices and experimental procedures that avoid issues resulting from such deformation, it is imperative to be able to predict deformation for given system parameters. In this work, we numerically investigate pressures resulting from a step change in conductivity and/or surface charge in micro- and nanofluidic channels with both thin and thick double layers. We show an explicit relation of pressure dependence on concentration ratio and electric double layer thickness. Furthermore, we develop a numerical model to predict deformation in such systems and use the model to unearth trends in deformation for various electric double layer thicknesses and both glass and PDMS on glass channels. Our work is particularly impactful for the development and design of micro- and nanofluidic-based devices with gradients in surface charge and/or conductivity, fundamental study of electrokinetic-based cavitation, and other systems that exploit non-uniform electric fields

Electrocavitation in Nanochannels

A novel method has been developed to cavitate aqueous solutions, which is called electrocavitation. An axial voltage is applied in a nanochannel containing an aqueous solution with a stepwise conductivity gradient. A combination of electrical and viscous forces then generates a tension in the solution which, at sufficiently low pressures, causes it to cavitate. Measurement of the current during the experiment as well as optical observation provides knowledge on the time and axial position of cavitation, after which the pressure at the cavitation position can be calculated from a theoretical model in which also the ζ-potential is inserted, which is separately determined from electroosmotic flow experiments. It is found that generally the cavitation position coincides with the position of the conductivity step. In several experiments the cavitation pressure in successive experiments on the same channel became increasingly lower, suggesting a gradual removal of cavitation nuclei from the system. We calculated that pressures as low as −1630 bar ±10 % have been reached, close to theoretically predicted pressures for homogeneous cavitation. The platform performs reliably and can be easily controlled

Solution titration by wall deprotonation during capillary filling of silicon oxide nanochannels

This paper describes a fundamental challenge when using silicon oxide nanochannels for analytical systems, namely the occurrence of a strong proton release or proton uptake from the walls in any transient situation such as channel filling. Experimentally, when fluorescein solutions were introduced into silicon oxide nanochannels through capillary pressure, a distinct bisection of the fluorescence was observed, the zone of the fluid near the entrance fluoresced, while the zone near the meniscus, was dark. The ratio between the zones was found to be constant in time and to depend on ionic strength, pH, and the presence of a buffer and its characteristics. Theoretically, using the Gouy-Chapman-Stern model of the electrochemical double layer, we demonstrate that this phenomenon can be effectively modeled as a titration of the solution by protons released from silanol groups on the walls, as a function of the pH and ionic strength of the introduced solution. The results demonstrate the dominant influence of the surface on the fluid composition in nanofluidic experiments, in transient situations such as filling, and changes in solvent properties such as the pH or ionic strength. The implications of these fundamental properties of silicon oxide nanochannels are important for analytical strategies and in particular the analysis of complex biological samples

Limits of miniaturization: Assessing ITP performance in sub-micron and nanochannels

The feasibility of isotachophoresis in channels of sub micrometer and nanometer dimension is investigated. A sample injection volume of 0.4 pL is focused and separated in a 330 nm deep channel. The sample consists of a biomatrix containing the fluorescently-labeled amino acids glutamate and phenylalanine, 20 attomoles of each. Isotachophoretic focusing is successfully demonstrated in a 50 nm deep channel. Separation of the two amino acids in the 50 nm deep channel however, could not be performed as the maximum applicable voltage was insufficient. This limit is imposed by bubble formation that we contribute to cavitation as a result of the mismatch in electro-osmotic flow, so called electrocavitation. This represents an unexpected limit on the miniaturization of ITP. Nonetheless, we report the smallest isotachophoretic separation and focusing experiment to date, both in terms of controlled sample injection volume and channel height