Engineering topics

Sivasankar, Vishal Sankar

Publications and source records attributed to Sivasankar, Vishal Sankar.

5 records

DOE OSTI2021

Simultaneous Energy Generation and Flow Enhancement (Electroslippage Effect) in Polyelectrolyte Brush Functionalized Nanochannels

Energy generation through nanofluidics is a topic of great nanotechnological relevance. In this work, we conduct all-atom molecular dynamics (MD) simulations of the transport of water and ions in a pressure-driven flow in nanochannels grafted with charged polyelectrolyte (PE) brushes and discover the possibility of simultaneous electrokinetic energy generation and flow enhancement (henceforth denoted as the electroslippage effect). Such PE-brush-functionalized nanochannels have been recently shown to demonstrate an overscreening (OS) effect (characterized by the presence of a greater number of screening counterions within the PE brush layer than needed to screen the PE brush charges), a consequent presence of excess coions within the PE brush-free bulk, and a coion-driven electroosmotic (EOS) transport in the presence of small to moderate applied axial electric fields. Here, however, we find that the streaming current, which represents the current generated by the flow-driven downstream advection of the charge imbalance present within the electric double layer (EDL) that screen the PE brush charges, is governed by the migration of the counterions. This stems from the fact that the highest contribution to the overall streaming current arises from the region near the PE brush-water interface (where there is an excess of counterions), while the brush-free bulk yields a hitherto unreported, but small, coion-dictated streaming current. This downstream advection of the charge imbalance (and the resultant counterion-driven streaming current) eventually leads to the development of an electric field (streaming electric field) in the direction that is opposite to the direction of the counterion-driven streaming current. The streaming current and the streaming electric field interact to generate the electrokinetic energy. Equally importantly, this streaming electric field induces an EOS transport, which becomes coion-driven, due to the presence of excess coions in the brush-free bulk. For the case of nanochannels grafted with negatively charged PE brushes, the streaming electric field will be in a direction that is opposite to the pressure-driven transport, and hence the coion (or anion) driven EOS flow, will be in the same direction as the pressure-driven transport. On the other hand, for the case of nanochannels grafted with positively charged PE brushes, the streaming electric field will be in the same direction as the pressure-driven flow, and hence the coion (or cation) driven EOS flow, will again be in the same direction as the pressure-driven flow. Therefore, whenever there occurs the presence of the OS and the resulting coion-driven EOS transport in PE brush grafted nanochannels, regardless of the sign of the charges of the PE brushes, this EOS transport will always aid the pressure-driven transport and will cause the most fascinating increase in the net volume flow rate across the nanochannel cross section, which is the electroslippage effect.

overscreening↗

DOE OSTI2021

Thermoosmotic Transport in Nanochannels Grafted with pH-responsive Polyelectrolyte Brushes Modelled Using Augmented Strong Stretching Theory

In this paper, we develop a theory to establish that the thermoosmotic (TOS) effects, induced by the application of an axial temperature gradient, leads to a massive enhancement in liquid transport in nanochannels grafted with charged polyelectrolyte (PE) brushes. Here, we quantify the TOS transport by quantifying the induced electric field and the induced TOS flow field. The different components of the electric field, namely the ionic component, the thermal component, and the osmotic component, as well as the contributions of different ions to these components, are quantified. Furthermore, we express the TOS velocity as a combination of chemiosmotic (COS), thermal, and electroosmotic (EOS) components. The COS and the thermal components augment each other and the overall strength and direction of the TOS flow are dictated by the direction and the relative strength of the EOS component. Most importantly, we compare the cases of brush-grafted nanochannels with those of the brush-free nanochannels of identical surface charge densities: the TOS transport is massively augmented in the brush-grafted nanochannels attributed to the combination of the localization of the EDL (and hence any body force that depends on the EDL charge density) away from the nanochannel wall (i.e., the location of the maximum drag force) and the presence of a possible molecular slip (experienced by the liquid) along the brush surface.

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DOE OSTI2020

Theoretical study on the massively augmented electro-osmotic water transport in polyelectrolyte brush functionalized nanoslits

In this paper, we demonstrate that functionalizing nanoslits with pH-responsive polyelectrolyte (PE) brushes can lead to extremely fast electroosmotic (EOS) water transport, where the maximum centreline velocity and the volume ow rate can be an order of magnitude larger than these quantities in identically charged brush-free nanochannels for a wide range of system parameters. Such an enhancement is most remarkable given that the brushes have been known to retard the transport by imparting additional drag on the fluid flow. We argue that this enhancement stems from the localization of the charge density of the brush-induced electric double layer (and hence the EOS body force) away from the nanochannel wall (or the location of the wall-induced drag force). This ensures a much larger impact of the EOS body force triggering such fast water transport. Lastly, the calculated flux values for the present brush-grafted nanochannels are found to be signi ficantly larger than those for a wide range of nanofluidic membranes and channels, suggesting that the brush functionalization can be considered as a mechanism for enabling such superfast nanofluidic transport.

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DOE OSTI2020

Strong stretching theory for pH-responsive polyelectrolyte brushes in large salt concentrations

Here, we develop a theory for describing the thermodynamics, configuration, and electrostatics of strongly-stretched, pH-responsive polyelectrolyte (PE) brushes in the presence of large salt concentrations. The aim of the paper, therefore, is to study the properties of a PE brush in a salt concentration regime (namely, large concentrations of several molars) that has been hitherto unexplored theoretically in the context of PE brushes but can be routinely encountered in molecular scale simulations of the problem. The brushes are modelled using our recently developed augmented Strong Stretching Theory (SST), while the effect of the presence of the large salt concentration is accounted for by including the contributions of three different types of non-Poisson–Boltzmann (non-PB) effects to the free energy description of the PE brush induced electric double layer (EDL). These non-PB effects are ionic non-mean-field ion–ion correlations, solvent polarization, and the finite size effect of the ions and water dipoles. We study the individual influences of these different effects and show that the ion–ion correlations and solvent polarization effect reduce the brush height which consequently enhances the monomer density and leads to an electrostatic potential distribution of the brush induced EDL that has a larger magnitude at near-wall locations and becomes zero at shorter distances from the wall. The finite size effect, on the other hand, increases the brush height and therefore, weakens the monomer density and leads to a smaller near-wall magnitude of the EDL potential that becomes zero at larger distances from the wall. In time, we consider the impact of all the three non-PB effects simultaneously and show that the ion–ion correlations and solvent polarization effect dominate the size effects and dictate the overall brush configuration and the EDL electrostatics. We also point out that the influence of all the three non-PB effects becomes the largest for a larger salt concentration and a smaller bulk pH. Finally, we compare our theoretical predictions with those obtained from our recently developed all-atom MD simulation model and obtain an excellent match.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Ionic diffusioosmotic transport in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory

In this paper, we study the diffusioosmotic (DOS) transport in a nanochannel grafted with pH-responsive polyelectrolyte (PE) brushes and establish brush-functionalization-driven enhancement in induced nanofluidic electric field and electrokinetic transport. The PE brushes are modelled using our recently developed augmented strong stretching theory (SST). We consider the generation of the DOS transport due to the imposition of a salt concentration gradient along the length of the nanochannel. The presence of the salt concentration gradient induces an electric field that has an osmotic (associated with the flow-driven migration of the ions in the induced electric double layer) and an ionic (associated with the conduction current) component. These two components evolve in a manner such that the electric field in the brush-grafted nanochannel is larger (smaller) in magnitude than that in the brush-less nanochannels for the case where the electric field is positive (negative). Furthermore, we quantify the DOS flow velocity and establish that for most of the parameter choices, the DOS velocity, which is a combination of the induced pressure-gradient-driven chemiosmotic component and the induced electric field driven electroosmotic transport, is significantly larger for the nanochannels grafted with backbone-charged PE brushes (i.e., brushes where the charge is distributed along the entire length of the brushes) as compared to brush-free nanochannels or nanochannels grafted with PE brushes containing charges on their non-grafted ends.

42 ENGINEERING↗