Sustained dropwise condensation of water requires rapid shedding of condensed droplets from the surface. Here, we elucidate a microfluidic mechanism that spontaneously sweeps condensed microscale droplets without the need for the traditional droplet removal pathways such as use of superhydrophobicity for droplet rolling and jumping and utilization of wettability gradients for directional droplet transport among others. The mechanism involves self-generated, directional, cascading coalescence sequences of condensed microscale droplets along standard hydrophobic microgrooves. Each sequence appears like a spontaneous zipping process, can sweep droplets along the microgroove at speeds of up to ∼1 m/s, and can extend for lengths more than 100 times the microgroove width. We investigate this phenomenon through high-speed in situ microscale condensation observations and demonstrate that it is enabled by rapid oscillations of a condensate meniscus formed locally in a filled microgroove and pinned on its edges. Such oscillations are in turn spontaneously initiated by coalescence of an individual droplet growing on the ridge with the microgroove meniscus. We quantify the coalescence cascades by characterizing the size distribution of the swept droplets and propose a simple analytical model to explain the results. We also demonstrate that, as condensation proceeds on the hydrophobic microgrooved surface, the coalescence cascades recur spontaneously through repetitive dewetting of the microgrooves. Lastly, we identify surface design rules for consistent realization of the cascades. The hydrophobic microgrooved textures required for the activation of this mechanism can be realized through conventional, scalable surface fabrication methods on a broad range of materials (we demonstrate with aluminum and silicon), thus promising direct application in a host of phase-change processes.
Sustained dropwise condensation of water requires rapid shedding of condensed droplets from the surface. Here, we elucidate a microfluidic mechanism that spontaneously sweeps condensed microscale droplets without the need for the traditional droplet removal pathways such as use of superhydrophobicity for droplet rolling and jumping and utilization of wettability gradients for directional droplet transport among others. The mechanism involves self-generated, directional, cascading coalescence sequences of condensed microscale droplets along standard hydrophobic microgrooves. Each sequence appears like a spontaneous zipping process, can sweep droplets along the microgroove at speeds of up to ∼1 m/s, and can extend for lengths more than 100 times the microgroove width. We investigate this phenomenon through high-speed in situ microscale condensation observations and demonstrate that it is enabled by rapid oscillations of a condensate meniscus formed locally in a filled microgroove and pinned on its edges. Such oscillations are in turn spontaneously initiated by coalescence of an individual droplet growing on the ridge with the microgroove meniscus. We quantify the coalescence cascades by characterizing the size distribution of the swept droplets and propose a simple analytical model to explain the results. We also demonstrate that, as condensation proceeds on the hydrophobic microgrooved surface, the coalescence cascades recur spontaneously through repetitive dewetting of the microgrooves. Lastly, we identify surface design rules for consistent realization of the cascades. The hydrophobic microgrooved textures required for the activation of this mechanism can be realized through conventional, scalable surface fabrication methods on a broad range of materials (we demonstrate with aluminum and silicon), thus promising direct application in a host of phase-change processes.
Electricity,[1] potable drinking water,[2] and information technology[3] count as
among the critical demands of modern human society. The diverse industrial
activities that endeavor to meet these needs, thermal power generation,[4] water desalination,[5] water harvesting,[6,7] and thermal management of electronic
devices[8] among others, involve heterogeneous
condensation of water as a critical physical process. It is well known
that hydrophobic and superhydrophobic surfaces cause water to condense
as distinct droplets that are periodically shed to achieve significant
improvement in the thermodynamic efficiency of this phase-change process
compared to hydrophilic surfaces wherein condensed water forms a continuous
liquid film.[9] Inspired by natural hydrophobic
surfaces capable of passive removal of droplets, multiple artificial
surfaces have been proposed, which achieve droplet shedding through
gravity by using hydrophobic substrates[9,10] or by causing
extreme sliding through lubricant-infused texturing.[11−14] Further enhancement in dropwise condensation has been achieved through
gravity-independent droplet removal by utilizing droplet coalescence-induced
jumping on superhydrophobic surfaces[15−18] or by causing directional droplet
movement with capillarity gradients.[19,20]In this
work, we investigate a mechanism that spontaneously sweeps condensate
droplets from hydrophobic surfaces without the need for the traditional
droplet removal pathways mentioned above. It involves a self-generated
cascading sequence of droplet coalescences along standard hydrophobic
microgrooves, which can proceed at a speed of up to ∼1 m/s
and can sweep droplets over large ridge areas between microgrooves.
We explain the underlying physics for these coalescence cascades through
careful high-speed in situ observations of condensation at a microscale
and identify design rules for their consistent realization. Such droplet
sweeps present an alternative approach for gravity-independent refreshment
of the condensing surface while requiring only facile and scalable
surface fabrication on a wide range of materials, including metals,
thus avoiding a more elaborate surface preparation necessary in many
of the traditional approaches for passive droplet removal from the
surface.[17,21]
Results and Discussion
Hydrophobic Microgrooved Surface
We investigate the
condensation of water on hydrophobic microgrooved surfaces as shown
in Figure . We fabricate
such microgrooves primarily on a metal (aluminum) due to the obvious
importance of metals in energy applications. Figure A shows the morphology of such a microgroove
as obtained through conventional milling in aluminum followed by adding
a hydrophobic coating. Similar microgrooves can also be obtained from
silicon through standard etching methods (see the Experimental Section and Section S1). Figure B shows
the hydrophobicity of the surface at a microscale as observed through
in situ condensation observation using ESEM.
Figure 1
(A) Microgroove machined
in aluminum and coated with polytetrafluoroethylene (PTFE). (B) Hydrophobicity
of the microgroove toward condensed microdroplets as observed in ESEM.
The vapor pressure was set at 0.87 kPa, and the cooling stage was
set at 2 °C. (See the Supporting Information for details on ESEM observations.)
(A) Microgroove machined
in aluminum and coated with polytetrafluoroethylene (PTFE). (B) Hydrophobicity
of the microgroove toward condensed microdroplets as observed in ESEM.
The vapor pressure was set at 0.87 kPa, and the cooling stage was
set at 2 °C. (See the Supporting Information for details on ESEM observations.)
Coalescence Cascade
The mechanism
manifests itself as a self-propagating, cascading sequence of droplet
coalescence events advancing in a zipping manner during condensation
of water on a standard hydrophobic microgrooved surface, as shown
in Figure A. Condensation
on such microgrooved surfaces proceeds through spatially uniform nucleation
and growth of condensate droplets within and outside the microgrooves.
The nucleation and growth of droplets inside and outside the microgrooves
is likely to be similar due to similarity in curvature, chemistry,
and roughness of surfaces inside and outside the microgrooves.[17,22] Eventually, when a microgroove is filled with the condensate at
any location, a droplet growing outside the microgroove on the ridge
may coalesce with the condensate in the microgroove (Figure , panels i and ii). Unexpectedly,
however, instead of such coalescence causing the removal of only this
individual droplet from the ridge, we observe that such an individual
coalescence event can trigger a rapid sequence of similar coalescence
events along the length of the microgroove.[23] High-speed imaging reveals a cascading coalescence sequence that
proceeds at speeds of up to 1 m/s while sweeping condensate droplets
from a large area along the ridge in a zipping-like motion (see panels
ii–ix in Figure A). As indicated by the gravity vector in the first panel, this effect
can also proceed against gravity. The sequence eventually culminates
with the microgroove filled with the condensate collected from the
coalescing droplets and any excess condensate located in multiple
bulges along the filled length of the microgroove (panels ix and x
in Figure A). The
small bulges eventually collapse into the microgroove (panel xi in Figure A) collecting the
excess condensate in a single large bulge (not visible in the figure)
at the completion of the coalescence sequence.
Figure 2
Microdroplet coalescence
cascade. (A) High-speed microdroplet coalescence sequence along a
∼100 μm wide and ∼200 μm deep hydrophobic
microgroove. Substrate: aluminum; coating: polytetrafluoroethylene
(PTFE). The yellow color indicates the coalescence cascade progress. g indicates gravity. The scale bar represents 200 μm.
Images are captured at 10,000 fps (frames per second) (Movie S1). (B) High-speed snapshots captured
at 250,000 fps demonstrating the spontaneous initiation and sustenance
of the coalescence sequence. The scale bar represents 100 μm.
The white arrow indicates the viewing direction for (C). (See the Experimental Section and Section S2 for details of the experimental setup and procedure.) (C)
Schematics corresponding to images in (B). Droplet 1 spontaneously
coalesces with the condensate meniscus pinned at microgroove edges
and initiates the coalescence sequence [see yellow arrows in panel
ii in (B) and (C)]. As this coalescence proceeds, the meniscus rises
[by amplitude as shown in the inset figure in panel iii of (C)]. This
appears as a capillary ripple traveling along the microgroove meniscus
[panels ii–iv in (B)]. The oscillating meniscus first catches
droplets 2 and 3 [green arrows in panel v in (B) and (C)], which in
turn triggers the coalescence of droplet 4 [pink arrows in panel vi
in (B) and (C)] thus propagating the coalescence sequence. (Movie S2.)
Microdroplet coalescence
cascade. (A) High-speed microdroplet coalescence sequence along a
∼100 μm wide and ∼200 μm deep hydrophobic
microgroove. Substrate: aluminum; coating: polytetrafluoroethylene
(PTFE). The yellow color indicates the coalescence cascade progress. g indicates gravity. The scale bar represents 200 μm.
Images are captured at 10,000 fps (frames per second) (Movie S1). (B) High-speed snapshots captured
at 250,000 fps demonstrating the spontaneous initiation and sustenance
of the coalescence sequence. The scale bar represents 100 μm.
The white arrow indicates the viewing direction for (C). (See the Experimental Section and Section S2 for details of the experimental setup and procedure.) (C)
Schematics corresponding to images in (B). Droplet 1 spontaneously
coalesces with the condensate meniscus pinned at microgroove edges
and initiates the coalescence sequence [see yellow arrows in panel
ii in (B) and (C)]. As this coalescence proceeds, the meniscus rises
[by amplitude as shown in the inset figure in panel iii of (C)]. This
appears as a capillary ripple traveling along the microgroove meniscus
[panels ii–iv in (B)]. The oscillating meniscus first catches
droplets 2 and 3 [green arrows in panel v in (B) and (C)], which in
turn triggers the coalescence of droplet 4 [pink arrows in panel vi
in (B) and (C)] thus propagating the coalescence sequence. (Movie S2.)The propagation of this zipping-like coalescence sequence
is achieved by the oscillations of the condensate meniscus inside
the microgroove, as elucidated through high-speed snapshots in Figure B and corresponding
schematics shown in Figure C. We observe that these oscillations are always initiated
from a completely filled part of microgroove wherein a meniscus pinned
at the edges of the microgroove exists. When a droplet growing in
the ridge area and near the microgroove edge, for instance droplet
1 in Figure B, coalesces
with the pinned meniscus, this otherwise stable meniscus[24] gets perturbed. The droplet has higher Laplace
pressure as compared to the condensate within the microgroove due
to the much higher curvature of the droplet. This causes the droplet
to drain into the condensate within the microgroove,[10] and the associated fluid inertia drives the meniscus beyond
its equilibrium position.[25] The resulting
competition between fluid inertia and surface tension results in a
perturbation with an amplitude of the order of ∼10 μm
(defined by h in Figure , panel iii; see Section S3 for details) that rapidly travels as a capillary ripple
across the width of the microgroove.[26] The
phase velocity u of the capillary–gravity
waves created at any interface is given by u2 = σk/ρ + g/k where σ and ρ are the surface tension and
density of water, respectively, and k = 2π/λ
is the wavenumber with λ as the wavelength of the capillary
ripple.[26,27] However, surface tension dominates at small
length scales relevant here, and thus the meniscus perturbation is
a pure capillary ripple traveling across the pinned meniscus at a
phase velocity of . While the coalescence
continues, the capillary ripple reflects from the pinned edge of the
meniscus and triggers transverse oscillations similar to those of
a sessile droplet with a pinned contact line.[25,28,29] Due to the small length scales involved,
these meniscus oscillations proceed with a short characteristic time
period ≈
10 μs thus necessitating high-speed imaging to capture them
(Section S4). This time period reflects
the fact that these meniscus oscillations are governed by a competition
between fluid inertial and capillary forces, similar to the time scale
of liquid droplet coalescence.[30,31] These meniscus oscillations
persist due to the relatively long relaxation time inherent in sessile
droplet coalescence[32−34] and catch further droplets along the edge of the
microgroove, as shown in Figure B,C, even before the original droplet coalescence event
is completed. This is evident from the initiation of coalescence of
droplets 2 and 3, much before the coalescence of droplet 1 is completed.
This process repeats, and the coalescence sequence propagates along
the microgroove. We observed that the overall speed of this propagation
depends upon the amount of condensate present in the microgroove immediately
prior to the initiation of the coalescence sequence. A microgroove
that is fully filled with condensate causes the sequence to proceed
at speeds as high as 1 m/s. The propagation speed is lower if the
microgroove is only partially filled with the condensate because,
in this case, the microgroove needs to be progressively filled by
advancing the meniscus within the microgroove in order to catch the
downstream droplets on the ridge. (See Section S5 for further details.)Irrespective of the state of
the microgroove before the initiation of the cascading coalescence
sequence, once initiated, the sequence propagates as long as droplets
are available within and outside the microgroove to feed the meniscus
advancing within the microgroove. This results in coalescence sequences
that can propagate for lengths more than 100 times the microgroove
width. Any coalescence event between the advancing meniscus and an
individual droplet induces oscillations that are essentially local.
These oscillations need to de-pin the meniscus within the microgroove
and advance it sufficiently to catch the next downstream droplet.
In the absence of such droplets, the oscillations are exponentially
attenuated by the bulk viscous dissipation within the liquid[10] with a characteristic time of , which is of
the order of ∼0.01 μs ≪ τc (Section S6). Here, η is the fluid viscosity,
and W is the microgroove width. However, the resulting
termination of the coalescence sequence is only temporary, and the
phenomenon self-initiates again when droplets become available through
continuous condensation.
Modeling and Swept-Droplet
Distribution
The coalescence sequence sweeps droplets of
a range of sizes from the ridge area as it propagates along the microgroove.
We investigate this aspect for varying microgroove geometries by analyzing
the size distribution of droplets swept during the coalescence cascades. Figure A shows such distributions
for four microgrooves with the same widths but increasing depths from
171 to 422 μm. The swept-droplet size is defined by droplet
diameter D as shown in inset of Figure A. The distributions are shown
in the form of beeswarm plots. Each plot, shown in a different colors
and centered about the corresponding microgroove width value on the x axis, describes the relative number of swept droplets
as a function of ordinate D for that microgroove.
We observe that the distributions are qualitatively similar across
the four microgroove depths. The distributions are biased toward smaller D values indicating that there are more numbers of smaller
droplets swept by the coalescence cascades. This is due to the inherently
much larger number of smaller droplets in the ridge area along the
microgroove edge compared to that of larger droplets, which is qualitatively
similar to the droplet distribution in planar surface condensation.[35] The microgroove geometry, however, affects the
largest droplets that can be swept by the coalescence cascade as evident
from the distributions extending to larger D values
for larger depths.
Figure 3
(A) Beeswarm distribution plots of swept droplet diameters
(D, defined in inset) for microgrooves of widths
of ∼100 μm and depths of ∼171 to 422 μm
machined in aluminum and coated with PTFE. The grey zone demarcates
the limit estimate Dcrit. Each beeswarm
plot is based on ∼300 measurements and is shown in different
colors for clarity. In the beeswarm distribution, the horizontal spread
at any ordinate D indicates the relative proportion
of droplets of diameter D swept by the cascading
coalescence sequence. The yellow zone below the Dcrit limit represents the range of droplet sizes swept
by the coalescence sequence progressing in a partially filled microgroove.
The orange zone above Dcrit indicates
droplet sizes swept by the coalescence sequence proceeding in a completely
filled microgroove or in the presence of a large bulge. (B) Schematic
illustrating that droplets with D < Dcrit (droplets 1, 2, and 3 in green) are readily absorbed
by the advancing meniscus [panels (i) and (ii)] due to a favorable
Laplace pressure difference with the microgroove meniscus (P1, P2, P3 > PM). A droplet with D > Dcrit (droplet 4 in red
with P4 < PM) forms a bulge. The bulge causes the sweeping of subsequent droplets
with D > Dcrit [e.g.,
droplet 5 in panels (iii) and (iv)]. PB represents Laplace pressures inside the bulge. The legend at the
bottom defines the color scheme for droplets.
(A) Beeswarm distribution plots of swept droplet diameters
(D, defined in inset) for microgrooves of widths
of ∼100 μm and depths of ∼171 to 422 μm
machined in aluminum and coated with PTFE. The grey zone demarcates
the limit estimate Dcrit. Each beeswarm
plot is based on ∼300 measurements and is shown in different
colors for clarity. In the beeswarm distribution, the horizontal spread
at any ordinate D indicates the relative proportion
of droplets of diameter D swept by the cascading
coalescence sequence. The yellow zone below the Dcrit limit represents the range of droplet sizes swept
by the coalescence sequence progressing in a partially filled microgroove.
The orange zone above Dcrit indicates
droplet sizes swept by the coalescence sequence proceeding in a completely
filled microgroove or in the presence of a large bulge. (B) Schematic
illustrating that droplets with D < Dcrit (droplets 1, 2, and 3 in green) are readily absorbed
by the advancing meniscus [panels (i) and (ii)] due to a favorable
Laplace pressure difference with the microgroove meniscus (P1, P2, P3 > PM). A droplet with D > Dcrit (droplet 4 in red
with P4 < PM) forms a bulge. The bulge causes the sweeping of subsequent droplets
with D > Dcrit [e.g.,
droplet 5 in panels (iii) and (iv)]. PB represents Laplace pressures inside the bulge. The legend at the
bottom defines the color scheme for droplets.A droplet is swept from the ridge by the advancing meniscus
within the microgroove when the Laplace pressure for the coalescing
droplet PD is higher than that for the
advancing condensate meniscus inside the microgroove, PM. This condition allows us to estimate an upper bound Dcrit for D as D < Dcrit = [(1/2W + 1/4H) sin (θ – π/2) + 1/4H]−1 where H is the microgroove
depth and θ is the advancing contact angle of the meniscus inside
the microgroove. Dcrit(H, W, θ) signifies the maximum droplet size
that can be swept by a coalescence cascade occurring in a partially
filled hydrophobic microgroove of depth H, width W, and contact angle θ. This limit is estimated based
on the Laplace pressure difference between the advancing meniscus
within the microgroove and the droplet on the ridge area at the microgroove
edge that is about to coalesce with it (see Section S7 for details). As depicted in Figure A, this value bounds most of the droplet
size distribution for the microgroove geometries tested. Further,
this upper bound increases as the depth of the microgroove increases
due to reduction in the relative Laplace pressure of the meniscus
inside the microgroove with an increase in the depth of the microgroove. Dcrit is shown as a grey-colored zone in Figure A due to the inherent
uncertainty in estimating the angle θ. Most of the swept droplets
lie below this limit (yellow-colored zone of the figure). Panels i–iii
in Figure B schematically
illustrate the sweeping of droplets with D < Dcrit by the advancing meniscus in the microgroove.
However, a few droplets with D > Dcrit are also swept by the coalescence sequence as shown
by the data points in the orange zone above the Dcrit limit in Figure A. Recognizing that the Dcrit value above does not account for local variations in meniscus curvature,
we speculate that these larger droplets are swept when the coalescence
sequence proceeds in a completely filled part of the microgroove.
In such a state, the condensate morphology in the microgroove results
in a relatively lower PM as compared to
partially filled regions of the microgroove (see Section S7 for details). Additionally, any bulges formed during
the coalescence sequence or a prior presence of a large droplet along
the microgroove can create a low-pressure sink that aids in the sweeping
of the droplets with D > Dcrit. Consider, for example, the sweeping of droplet 5 due
to the creation of a bulge in Figure B (panels iii and iv).
Periodicity
of the Coalescence Cascade
When the coalescence sequence
concludes, the low-pressure sink provided by the single large bulge
(Section S8) triggers a spontaneous withdrawal
of the condensate from the microgroove as elucidated in Figure A,B. Subsequently, condensation
restarts in the resulting dewetted length of the microgroove, and
the cycle consisting of the coalescence sequence and spontaneous dewetting
of the microgroove through condensate withdrawal is repeated all over
again (Movie S3). Such bulges grow as they
collect the condensate from the microgroove and coalesce with neighboring
droplets outside the microgroove, eventually evolving into large drops
(panels i and ii in Figure C), which are then shed from the surface under gravity (Movie S4). Due to the multiple coalescences required
to grow these drops to the eventual departure size, these drops are
larger than the Dcrit limit for droplet
sweeping from the ridge area for an individual coalescence cascade.
In essence, a body force is required only once every few occurrences
of the coalescence sequence–condensate withdrawal cycle to
shed the large drops. This periodic cycle can sweep a large surface
area over time compared to conventional dropwise condensation on planar
hydrophobic samples (see Section S9). Although
the zipping-like coalescence cascades cause wetting of the microgroove,
it is unlike the wetting of microtextures observed in the case of
droplets much larger in size than surface microfeatures and involving
a change of the wetting state of the droplet from the Cassie–Baxter
to the Wenzel state.[36] In our work, the
condensate droplets under consideration are of the same or smaller
length scale than that of the microgrooves and always have the same
wetting state as that on a planar hydrophobic surface. Additionally,
unlike the irreversible change of the large-drop wetting state from
Cassie–Baxter to Wenzel, the wetting of microgrooves described
here is reversible as the morphology of the microgrooves causes its
spontaneous dewetting due to the withdrawal of condensate as elucidated
above.
Figure 4
Periodicity of the zipping-like cascading coalescence sequence: (A)
a single bulge and filled microgroove are formed after the conclusion
of the coalescence sequence (panel i). Subsequently, the bulge induces
dewetting of the microgroove through condensate withdrawal as indicated
by yellow arrows. Scale bar: 200 μm. Images are captured at
1000 fps. (B) Schematic showing the condensate withdrawal process
along with an overall pressure difference driving this process. (C)
Zoomed-out view of the sample wherein the coalescence cascades are
visible as intermittent dark ridge areas. Three bulges formed due
to such events are encircled in panel (ii). These bulges grow due
to repeated occurrences of the effect and coalescence with more droplets.
Eventually, the resulting large drops [encircled in panel (iii)] are
shed under gravity as indicated by yellow arrows. Drop 1 also moves
under gravity initially but is eventually absorbed into the microgroove
when it gets connected to a large drop pinned at the edge of the sample
via a filled microgroove (panels vii and viii). Scale bar: 2 mm. Substrate:
aluminum. Coating: PTFE. Images are captured at 50 fps.
Periodicity of the zipping-like cascading coalescence sequence: (A)
a single bulge and filled microgroove are formed after the conclusion
of the coalescence sequence (panel i). Subsequently, the bulge induces
dewetting of the microgroove through condensate withdrawal as indicated
by yellow arrows. Scale bar: 200 μm. Images are captured at
1000 fps. (B) Schematic showing the condensate withdrawal process
along with an overall pressure difference driving this process. (C)
Zoomed-out view of the sample wherein the coalescence cascades are
visible as intermittent dark ridge areas. Three bulges formed due
to such events are encircled in panel (ii). These bulges grow due
to repeated occurrences of the effect and coalescence with more droplets.
Eventually, the resulting large drops [encircled in panel (iii)] are
shed under gravity as indicated by yellow arrows. Drop 1 also moves
under gravity initially but is eventually absorbed into the microgroove
when it gets connected to a large drop pinned at the edge of the sample
via a filled microgroove (panels vii and viii). Scale bar: 2 mm. Substrate:
aluminum. Coating: PTFE. Images are captured at 50 fps.
Surface Design
To inspire rational design of surfaces for achieving this coalescence
sequence, we investigated water condensation on hydrophobic microgrooves
with aspect ratios (defined as H/W) spanning from 0.1 to nearly 4 with the ridge width kept constant.
We observed that long coalescence sequences are consistently exhibited
when (H/W) is larger than ∼1.6
and Dcrit is large enough such that [Dcritcos (θ – π/2)]/L > ∼ 0.3 as illustrated in the regime map shown
in Figure A. Here, Dcritcos (θ – π/2) represents
the droplet base diameter corresponding to Dcrit, and L is the ridge width. At smaller
aspect ratios or smaller Dcritcos (θ
– π/2) values, the microgrooves cannot sustain a progressive
meniscus movement necessary for the emergence of the cascading coalescence
sequence, and the overall condensation process approaches the case
of planar hydrophobic surfaces wherein such rapid droplet sweeping
is absent (Section S10). Additionally,
we observed that the maximum size of droplets swept by the liquid
zipping effect could be controlled by reducing the ridge width between
the microgrooves as shown in Figure B. As the ridge width is reduced below the Dcritcos (θ – π/2) limit,
the maximum size that the droplets can grow before they are swept
reduces,[20] resulting in direct control
over the swept droplet distribution.
Figure 5
(A) Regime map of the liquid zipping-like
coalescence sequence with varying aspect ratios (H/W) and a fixed ridge width for hydrophobic microgrooves
in aluminum. The numbers in green and red indicate aspect ratios for
the various microgroove geometries. The green data points correspond
to microgrooves for which the coalescence sequence is realized and
red data points represent microgrooves where the coalescence sequence
is absent. The contour lines correspond to the ratio [Dcrit cos (θ – π/2)]/L. Ridge width L is defined in the inset of (B).
Based on data points and contours, the microgrooves need to be designed
such that (H/W) > 1.6 and [Dcrit cos (θ – π/2)]/L > 0.3. (B) Control of swept droplet size through reduction
in microgroove ridge width L. Beeswarm distributions
of swept droplet diameters are shown in terms of base diameter D cos (θ – π/2) for ∼100 μm
wide and ∼200 μm deep microgrooves for ridge widths L of ∼480 and ∼240 μm (in blue), ∼180
μm (in black), and ∼90 μm (in orange). Dcrit cos (θ – π/2) for this
microgroove geometry lies in the range of ∼164–216 μm
as indicated by the grey zone. For L > Dcrit cos (θ – π/2), swept
droplet distributions (in blue) are unaffected by L. However as L is reduced, the swept droplet distribution
first becomes more uniform [see distribution in black for L ≈ Dcrit cos (θ
– π/2)], and subsequently, the maximum droplet swept
size is reduced when L < Dcrit cos (θ – π/2) (see distribution in
orange).
(A) Regime map of the liquid zipping-like
coalescence sequence with varying aspect ratios (H/W) and a fixed ridge width for hydrophobic microgrooves
in aluminum. The numbers in green and red indicate aspect ratios for
the various microgroove geometries. The green data points correspond
to microgrooves for which the coalescence sequence is realized and
red data points represent microgrooves where the coalescence sequence
is absent. The contour lines correspond to the ratio [Dcritcos (θ – π/2)]/L. Ridge width L is defined in the inset of (B).
Based on data points and contours, the microgrooves need to be designed
such that (H/W) > 1.6 and [Dcritcos (θ – π/2)]/L > 0.3. (B) Control of swept droplet size through reduction
in microgroove ridge width L. Beeswarm distributions
of swept droplet diameters are shown in terms of base diameter D cos (θ – π/2) for ∼100 μm
wide and ∼200 μm deep microgrooves for ridge widths L of ∼480 and ∼240 μm (in blue), ∼180
μm (in black), and ∼90 μm (in orange). Dcritcos (θ – π/2) for this
microgroove geometry lies in the range of ∼164–216 μm
as indicated by the grey zone. For L > Dcritcos (θ – π/2), swept
droplet distributions (in blue) are unaffected by L. However as L is reduced, the swept droplet distribution
first becomes more uniform [see distribution in black for L ≈ Dcritcos (θ
– π/2)], and subsequently, the maximum droplet swept
size is reduced when L < Dcritcos (θ – π/2) (see distribution in
orange).
Conclusions
We have elucidated a mechanism for passive removal of condensed
droplets involving self-generated coalescence cascades of droplets
along hydrophobic microgrooves. Such coalescence cascades offer an
unexplored pathway for enhanced dropwise condensation without requiring
traditional surface modification routes of passive condensate shedding
adopted to date, involving either the fabrication of superhydrophobic
textures, lubricant-impregnated textures, or surfaces with wettability
gradients. We have quantified the droplet sweeping size as a function
of microgroove geometry and have also proposed simple design rules
for consistent realization of these coalescence cascades. Lastly,
we have demonstrated control over the droplet removal size through
modification of geometrical parameters of the texture. This control
over the swept droplet size, and the fact that the periodic coalescence
sequence and condensate removal cycle can sweep large areas of surfaces
without the need for conventional droplet shedding modes (see Section S10) signals toward a potential to achieve
significant enhancement in efficiency of industrial processes involving
condensation. Additionally, we have noticed that droplets even as
small as ∼10 μm can sustain this sequential coalescence
sequence (see Movie S5), indicating that
it may be possible to realize this mechanism at even smaller scales
by further downscaling the overall microgroove dimensions with suitable
aspect ratios. This would be advantageous in miniaturized phase-change
applications such as micro heat pipes[37] and thermal diodes.[21] Moreover, since
this mechanism requires only standard hydrophobic (and not superhydrophobic)
microgrooves, it accords significant flexibility regarding the choice
of base material and coating for implementation in industrially relevant
operating conditions.[38]
Experimental Section
Materials
and Fabrication
Aluminum samples were cut from 1 mm thick
sheets (99.5% aluminum sheets, AW1085, Metal Service Menziken AG,
Switzerland), and the microgrooves of various aspect ratios were milled
into the sample. Subsequently, the samples were thoroughly cleaned
by ultrasonication first in acetone and isopropanol (Sigma-Aldrich)
and finally in DI water. The microgrooves were hydrophobized through
a coating of either polytetrafluoroethylene (PTFE) or trichloro-1H,1H,2H,2H-perfluorodecylsilan (FDTS) (Sigma-Aldrich). For PTFE coating, the
cleaned samples were first activated with oxygen plasma and then spray-coated
with PTFE dispersed in dichloromethane (1 wt %) (Sigma-Aldrich). The
PTFE dispersion (10 mL) was sprayed over a sample area of approximately
30 cm2. The samples were sprayed using a VL double-action,
internal mix, siphon-feed airbrush (Paasche, U.S.A.). The spray distance
from the substrate was approximately 10 cm, and the air pressure was
set at 430 kPa. Subsequently, the samples were cured in an oven at
400 °C for 30 min to form a uniform hydrophobic coating on the
sample. For a coating of FDTS, which forms a self-assembled monolayer
by attaching with the surface hydroxyl groups, FDTS was dissolved
in n-hexane (Sigma-Aldrich) to form a 1.43 mM solution.
The samples were kept immersed in this solution for 120 min and subsequently
baked at 120 °C for 45 min.[17]Similar microgrooves were also fabricated in silicon by etching silicon
wafers through a Bosch process using the PlasmaPro Estrelas 100 deep
Si etcher (Oxford Instruments). Prior to that, a sacrificial layer
was applied by spin-coating and patterned with a UV mask aligner Karl
Suss MA6. It consisted of a positive photoresist (Microposit S1813).
The unexposed parts were washed away using a solution containing 80
wt % water and 20 wt % Microposit 351 developer. The photoresist residues
left under the etching process were subsequently removed by O2 plasma exposure at 600 W for 16 min (Q235 Microwave Plasma
Etcher, Omni Technologies, U.S.A.). The etched samples were made hydrophobic
by coating the sample with a thin layer of FDTS. The coating procedure
was same as that for aluminum samples except that the immersion time
was chosen as 2 min and the subsequent baking time was set as 10 min.[39]The PTFE-coated planar aluminum surface
showed an advancing contact angle of 119.7° ± 8.2°
and a contact angle hysteresis of 31.1° ± 4.8°. The
FDTS-coated aluminum surface showed an advancing contact angle of
111.3° ± 8.0° and a contact angle hysteresis of 37.8°
± 8.1°, and the FDTS-coated silicon surface had an advancing
contact angle of 119.8° ± 4° and contact angle hysteresis
of 43° ± 7.5°. The zipping-like coalescence cascades
were observed on all three types of samples, which indicated that
the occurrence of this effect is independent of the substrate material
as long as the microgroove aspect ratio is correctly selected and
all the surfaces of the microgroove are hydrophobic.
Experimental Setup
Figure A shows details of the custom-built experimental
setup. It consists of a boiler, a pressure-reducing valve, a Plexiglas
test chamber, a chiller, and a vacuum pump. Deionized (DI) water is
used as the working fluid. The boiler generates steam at 100 °C
and 1 bar by heating the DI water with two 2 kW electrical heaters.
The generated steam is supplied to the pressure-reducing valve through
an insulated steam line (shown in red). The pressure-reducing valve
(bellow valve, Swagelok) reduces the pressure of the steam, which
is then supplied to the test chamber. The test chamber is evacuated
using the vacuum pump prior to the supply of steam. This fluid circuit
is designed to be an open loop such that the condensate is drained
from the bottom of the test chamber. The sample is mounted in a vertical
orientation with the microgrooves also aligned vertically, that is,
parallel to gravity. During the experiment, the test chamber is maintained
at a constant steam saturation pressure of ∼50 mbar, the chiller
is set to a temperature of 10 °C, and the resulting sample temperature
is ∼29 °C, indicating a surface subcooling of 4 °C
(i.e., an oversaturation of ∼1.25).
Figure 6
(A) Schematic of the
experimental setup to induce condensation on the test sample. (B)
Optical setup for high-speed, high-magnification observation of the
domino effect. The lens L, shown as dashed lines, was removed for
imaging at high frame rates.
(A) Schematic of the
experimental setup to induce condensation on the test sample. (B)
Optical setup for high-speed, high-magnification observation of the
domino effect. The lens L, shown as dashed lines, was removed for
imaging at high frame rates.Figure B
shows a schematic of the optical microscope setup. A white LED is
used as the light source that is collimated by using an objective.
The collimated light is used to illuminate the sample using a beam
splitter and through a long working distance objective (Olympus UPlanFl
4X/0.13). The signal from the sample is recorded by a high-speed camera
(Photron Fastcam SA 1.1). The frame rate of the camera was adjusted
according to the temporal information required from optical observations.
For each frame rate setting, the maximum available image size setting
was used. For observations of condensation on the entire sample, frame
rates up to 250 fps were used. On the other hand, to temporally resolve
the high-speed capillary ripples on the meniscus pinned at the microgroove,
a frame rate of 250,000 fps was used. All images were captured with
a spatial resolution of ∼3.5 microns/pixel. Refer to Section S2 for details of the test chamber and
experimental protocol.