This Article describes the use of capillary pressure to
initiate and control the rate of spontaneous liquid–liquid flow through
microfluidic channels. In contrast to flow driven by external pressure, flow
driven by capillary pressure is dominated by interfacial phenomena and is
exquisitely sensitive to the chemical composition and geometry of the fluids
and channels. A stepwise change in capillary force was initiated on a
hydrophobic SlipChip by slipping a shallow channel containing an aqueous
droplet into contact with a slightly deeper channel filled with immiscible oil.
This action induced spontaneous flow of the droplet into the deeper channel. A
model predicting the rate of spontaneous flow was developed on the basis of the
balance of net capillary force with viscous flow resistance, using as inputs
the liquid–liquid surface tension, the advancing and receding contact angles at
the three-phase aqueous–oil–surface contact line, and the geometry of the
devices. The impact of contact angle hysteresis, the presence or absence of a
lubricating oil layer, and adsorption of surface-active compounds at
liquid–liquid or liquid–solid interfaces were quantified. Two regimes of flow
spanning a 104-fold range of flow rates were obtained and modeled
quantitatively, with faster (mm/s) flow obtained when oil could escape through
connected channels as it was displaced by flowing aqueous solution, and slower
(micrometer/s) flow obtained when oil escape was mostly restricted to a
micrometer-scale gap between the plates of the SlipChip (“dead-end flow”).
Rupture of the lubricating oil layer (reminiscent of a Cassie–Wenzel
transition) was proposed as a cause of discrepancy between the model and the
experiment. Both dilute salt solutions and complex biological solutions such as
human blood plasma could be flowed using this approach. We anticipate that flow
driven by capillary pressure will be useful for the design and operation of
flow in microfluidic applications that do not require external power, valves,
or pumps, including on SlipChip and other droplet- or plug-based microfluidic
devices. In addition, this approach may be used as a sensitive method of
evaluating interfacial tension, contact angles, and wetting phenomena on chip.
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