Conspectus
Nanofluidics is the study of fluids under nanoscale confinement,
where small-scale effects dictate fluid physics and continuum assumptions
are no longer fully valid. At this scale, because of large surface-area-to-volume
ratios, the fluid interaction with boundaries becomes more pronounced,
and both short-range steric/hydration forces and long-range van der
Waals forces and electrostatic forces dictate fluid behavior. These
forces lead to a spectrum of anomalous transport and thermodynamic
phenomena such as ultrafast water flow, enhanced ion transport, extreme
phase transition temperatures, and slow biomolecule diffusion, which
have been the subject of extensive computational studies. Experimental
quantification of these phenomena was also enabled by the advent of
nanofluidic technology, which has transformed challenging nanoscale
fluid measurements into facile optical and electrical recordings.
Our groups’ focus is to investigate nanoscale (2 to 103 nm) fluid behaviors in the context of fluid mechanics and
thermodynamics through the development of novel nanofluidic tools,
to examine the applicability of classical equations at the nanoscale,
to identify the source of deviations, and to explore new physics emerging
at this scale. In this Account, we summarize our recent findings regarding
liquid transport, vaporization, and condensation of nanoscale-confined
liquids.
Our study of nanoscale water transport identified an
additional
resistance in hydrophilic nanochannels, attributed to the reduced
cross-sectional area caused by the formation of an immobile hydration
layer on the surfaces. In contrast, a reduction in flow resistance
was discovered in graphene-coated hydrophobic nanochannels, due to
water slippage on the graphene surface. In the context of vaporization,
the kinetic-limited evaporation flux was measured and found to exceed
the classical theoretical prediction by an order of magnitude in hydrophilic
nanochannels/nanopores as a result of the thin film evaporation outside
of the apertures. This factor was eliminated by modifying the hydrophobicity
of the aperture’s exterior surface, enabling the identification
of the true kinetic limits inside nanoconfinements and a crucial confinement-dependent
evaporation coefficient. The transport-limited evaporation dynamics
was also quantified, where experimental results confirmed the parallel
diffusion–convection resistance model in both single nanoconduits
and nanoporous systems at high accuracy. Furthermore, we have extended
our studies to different aspects of condensation in nanoscale-confined
spaces. The initiation of condensation for a single-component hydrocarbon
was observed to follow the Kelvin equation, whereas for hydrocarbon
mixtures it deviated from classical theory because of surface-selective
adsorption, which has been corroborated by simulations. Moreover,
the condensation dynamics deviates from the bulk and is governed by
either vapor transport or liquid transport depending on the confinement
scale. Overall, by using novel nanofluidic devic...