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pubs.acs.org/Langmuir

Hierarchical Surface Architecture of Plants as an Inspiration for


Biomimetic Fog Collectors
M. A. K. Azad,*,† W. Barthlott,† and K. Koch‡

Nees Institute for Biodiversity of Plants, Rheinische Friedrich-Wilhelms-University of Bonn, Venusbergweg 22, 53115 Bonn,
Germany

Faculty of Life Sciences, Rhine-Waal University of Applied Sciences, Marie-Curie Straße 1, 47533 Kleve, Germany
*
S Supporting Information

ABSTRACT: Fog collectors can enable us to alleviate the water crisis in certain arid regions of
the world. A continuous fog-collection cycle consisting of a persistent capture of fog droplets and
their fast transport to the target is a prerequisite for developing an efficient fog collector. In regard
to this topic, a biological superior design has been found in the hierarchical surface architecture of
barley (Hordeum vulgare) awns. We demonstrate here the highly wettable (advancing contact
angle 16° ± 2.7 and receding contact angle 9° ± 2.6) barbed (barb = conical structure) awn as a
model to develop optimized fog collectors with a high fog-capturing capability, an effective water
transport, and above all an efficient fog collection. We compare the fog-collection efficiency of the
model sample with other plant samples naturally grown in foggy habitats that are supposed to be
very efficient fog collectors. The model sample, consisting of dry hydrophilized awns (DH awns),
is found to be about twice as efficient (fog-collection rate 563.7 ± 23.2 μg/cm2 over 10 min) as
any other samples investigated under controlled experimental conditions. Finally, a design based
on the hierarchical surface architecture of the model sample is proposed for the development of
optimized biomimetic fog collectors.

■ INTRODUCTION
Shortages of fresh water are a major problem affecting around 1
unguicularis) demonstrated a better efficiency of the plant
species.15
In the last few decades the only technology for collecting fog
billion people worldwide;1 the problem is most acute in arid,
has been large fog collectors (LFCs) made of polyolefin mesh;
semiarid tropical, and subtropical climates with limited or no
it has been used in 40 countries in South America, Europe,
rainfall at all. Fog is an important source of water that is often
Africa, and Asia where suitable regular fog is present.2,3,16 With
ignored. However, fog collection can be an elegant solution to the aim to increase the amount of fog collection, a multifunnel
meet the demand of water for afforestation, for irrigation, and fog collector has been proposed.17 Although the simulations
above all as a drinking water source for humans and animals in showed that the multifunnel fog collector is more efficient than
these areas.2−4 In the foggy regions, the dripping of water from the old design of the LFC, the design can be further improved
the foliage is one of most often seen phenomena. The by using elements based on the hierarchical architectures of
arrangement, density, type, and size of the foliage play an plants. Some studies have shown the potential of artificial silk
important role in the amount of fog drip. Plants having “needle- fiber,18−24 electrospun nanofibers,25−27 and hydrophilic−
like” structures, e.g., pine, redwood, and fir, are reported to hydrophobic cooperative surfaces/systems28−30 to collect fog.
collect a good amount of fog whereas the “leaflike” Inspired by the cactus spine,11 conical copper31 and zinc-
impermeable structures (no regular void space on the surface) oxide32 wire or artificial spines27 and fog-collecting imperme-
allow the moisture to flow around the surface of the leaf.5−7 able surfaces with cone arrays11,33−35 have been demonstrated.
Increased branchiness of plant species, such as narrow leaf Although the cone arrays were proved to be highly efficient for
syndrome, is reported to be an important trait to collect a continuous fog collection, there were not enough indications
fog.8−10 Tillandsia usneoides, Opuntia microdasys,11 and Cotula in these publications of how the structures can be implemented
fallax,12 all having hierarchical structures, have been demon- to build a large fog collector, with one exception,11 where the
strated to collect fog.9,13 Vogel and Müller-Doblies14 did an proposed prototype surface lacks void spaces that may result in
extensive study on eight monocot families and some Oxalis the hindrance to flow of the fog-carrying wind. The fog-carrying
species in some semidesert regions (Namaqualand and adjacent wind has the tendency to deviate the direction while
regions) of South Africa, where they demonstrated that these approaching an impermeable obstacle. This is why fog
plants did have “special morphological adaptations” of their
aerial parts that facilitate fog and dew collection. A comparison Received: July 1, 2015
of fog collection between a microstructured Namib grass Revised: November 11, 2015
(Stipagrostis sabulicola) and a Namib beetle (Onymacris

© XXXX American Chemical Society A DOI: 10.1021/acs.langmuir.5b02430


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collectors, or effective fog-collecting trees, have an open needle-like structures (NLSs) were arranged vertically in such a way
structure with collecting surfaces a millimeter or less wide. that there were gaps (width + 5−10% of the width of the awns/Ns/
Therefore, we propose a meshlike structure as a viable solution. NLSs) between the needles. The samples were prepared in such a way
In our previous study36 we demonstrated the positive influence that their effective surface areas remained close to each other. About
50−55% of the surface area of each prepared 2 × 2 cm2 sample was
of microstructure and superhydrophilicity on fog collection. We
occupied by the Ns/NLSs and the rest was free to get rid of the
demonstrate here the barbed DH awns of Hordeum vulgare as a impedance of the fog flow. Therefore, the samples have equivalent
model to develop optimized fog collectors based on a high fog- effective surface areas for fog collection. The measurement of the
capturing capability and an effective water transport. The surface area coverage by the Ns/NLSs was calculated from the images
hierarchical architecture of the model sample also provides a of the samples by Photoshop CS3. For the first set of samples, we used
solution for the problem of the clogging of fog droplets intact Ns/NLSs, whereas for the second set, the needles of Abies and
observed in an earlier study.37 To be noted, when the droplets, Sequoia were cut to reach as close to the diameter of the Hordeum awn
attached to the fiber surfaces of a mesh or net, block the void as possible. The Tillandsia leaves (NLSs) of smaller diameter close to
space between the fibers and consequently hinder the flow of Hordeum awn were also selected for the second set as well. Samples of
the fog-carrying wind, the phenomenon is defined as 2 × 2 cm2 were prepared as previously described.
“clogging”. A comparison of fog-collection efficiency of the Hydrophilization. Dry Hordeum awns were dip-coated with a
water-based polymer solution containing TiO2 (titanium dioxide)
samples with and without barbs has been conducted here for
nanoparticles (TA 2202, Nadico Technologie GmbH, Langenfeld,
the first time. We also propose a possible design to develop Germany), followed by drying at room temperature for ∼48 h. After
optimized fog collectors.


evaporation of the solvent, the particles are bonded into a remaining
matrix that prevents the release of free TiO2 into the environment.
EXPERIMENTAL SECTION The average particle size of TiO2 is given as <8 nm (manufacturer’s
Plant Material. Plant material includes fresh and dry awns of information). The thickness of the coating, measured by an atomic
Hordeum vulgare L. (the rougher surface of the awn was directed force microscope (NanoWizard II, JPK Instruments, Germany), was
toward the fog source), leaves (needle-like structures (NLSs)) of ∼300 nm. In this article, we refer to hydrophilized dry Hordeum awns
Tillandsia usneoides (L.) L., and needles (Ns) of Pinus canariensis C. as “DH awns” (D for dry and H for hydrophilized).
Sm. (the round shape of the needle was directed toward the fog Contact Angle Measurement. Dynamic contact angle measure-
source), Abies bracteata (D. Don) Poit. (the upper surface was directed ments were carried out by a goniometer (DataPhysics OCA 20,
toward the fog source), Sequoia sempervirens (D. Don) Endl. (the Filderstadt, Germany) at room temperature (21 °C). To perform the
upper surface was directed toward the fog source), and Sequoiadendron measurements, the volume of a demineralized water droplet was
giganteum (Lindl.) J. Buchholz. A fresh and a DH awn (model species) increased from 1 to 2 μL, followed by a decrease from 2 to 1 μL at a
and other plant materials (Ns and NLSs) are shown in Figure S1a−g rate of 0.1 μL/s with a delay time of 5 s. Because of the very low
in the Supporting Information. All plants were cultivated in the surface area of the samples, we could only use 2 μL of water. We
Botanical Gardens of University of Bonn (BG-Bonn). calculated the contact angle hysteresis from the advancing and
Sample Preparation. Samples (2 × 2 cm2) were prepared for receding contact angle values. The average and standard deviation of
each of the model plant species (Figure 1a). The needles (Ns) or the values were calculated from 5 measurements taken on each kind of
sample surface.
Light and Scanning Electron Microscopy. The analysis of the
fresh and/or dry sample surfaces was done by a Keyence VHX-1000
digital microscope (Keyence Corporation, Japan) and a Stereoscan
200 SEM (scanning electron microscope) (Cambridge, U.K.). Prior to
SEM analysis, the specimens were coated with gold for 30 s at 60 mA
(sputter coater, Balzers Union SCD040, BAL-TEC AG, Liechten-
stein).
Experimental Setup. Droplet deposition behavior on the surfaces
of the samples and their fog-collection efficiency were analyzed with a
Figure 1. Schematic of the (a) sample and (b) setup for the fog- setup previously used by Azad et al.36 and its extension. The samples,
collection experiment. Adapted with permission from ref 36. which were mounted vertically in an artificial fog stream, had a
Copyright 2015 IOP Publishing. distance of 17 cm (Figure 1b) from the outlet of an ultrasonic
humidifier (Honeywell, BH-860E; fog output maximum 0.4 L/h). The
velocity of the fog flow was measured (by a Testo 416 anemometer,

Table 1. Structural characterization of the samples

sample structural characteristics


barbed Hordeum vulgare width of the awns: 708 ± 113 μm, barb (Figure 2a, b); length: 173 ± 26 μm with an apex angle (2α) of 22 ± 3°; tilted angle of the
awns (DH awn) barbs with the main axis of the awns: 37 ± 4°; distance between two barbs: 370 ± 106 μm on both sides and approximately twice in
the middle of the awn in some areas and irregular in some other areas
Hordeum vulgare width of the awns: 706 ± 108 μm; barb length: 163 ± 21 μm with an apex angle (2α) of 19.4 ± 2.9°; tilted angle of the barbs with the
(fresh awn) main axis of the awns: 31 ± 4°; distance between two barbs: 349 ± 107 μm on both sides and approximately twice in the middle of
the awn in some areas and irregular in some other areas
Ns Pinus canariensis width of the Ns: 913 ± 87 μm
Abies bracteata width of the Ns (intact): 1374 ± 100 μm; for the second set of samples, Ns were cut to a width of 717 ± 75 μm
Sequoia width of the Ns (intact): 2645 ± 175 μm; for the second set of samples, Ns were cut to a width of 814 ± 54 μm
sempervirens
Sequoiadendron Ns have conelike structures on the main axis; diameter of the Ns: 1074 ± 91 μm (see Figure S2 for details)
giganteum
NLSs Tillandsia diameter of the NLSs: 600−1800 μm; for the second set of samples, NLSs with diameter of 600−800 μm were used
usneoides

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Figure 2. SEM of (a) a DH awn of Hordeum vulgare shows hierarchical surface architecture resulting from a combination of the microstructures (e.g.,
barbs and microgrooves) of different dimensions; (b) a single barb attached to the microgrooved main axis of the awn; (c) microgrooves of the awn
surface; waxy surfaces of the needles of (d) Abies bracteata and (e) Sequoiadendron giganteum.

Lenzkirch, Germany) to be ∼1.6 m/s at 17 cm from the outlet. The Surface Wettability. The presence of wax crystals on the
setup was in a chamber (length/width/height =100 × 90 × 180 cm), surfaces of Pinus, Abies, Sequoiadendron, etc. (Figure 2d−e) and
which is called a fog chamber. During the experiments, the a thin wax film39−41 on the surface of fresh Hordeum awn leads
temperature and the relative humidity inside the chamber were 19− to their hydrophobicity,42 as exhibited by the droplet behavior
20 °C and 75−85%, respectively. on the surface during the fog-collection experiment (see Figure
A D90 Nikon camera with a Medical-Nikkor 120 mm objective and
S3). The degree of wettability of the samples is shown in Table
a charge-coupled device (CCD) camera attached to the goniometer
were used for imaging.
2. The barbs were too tiny to place droplets on them to
Measurement of Fog-Collection Efficiency. The amount of
water collected by the samples over 10 min was measured to Table 2. Surface Wettability of All the Samples
determine their efficiency. Although the samples have an equivalent receding
effective surface area (50−55% of 2 × 2 cm2), a slight difference in advancing contact contact angle contact angle
their areas where the fog was coming into contact with them was also sample angle (θadv) (θrec) hysteresis (CAH)
taken into consideration during the calculation. A control experiment Hordeum vulgare 16 ± 2.7 9 ± 2.6 7 ± 1.8
(5 times each of 10 min) was also conducted without mounting the (DH awn)
samples. Hordeum vulgare 112 ± 2.9 84 ± 3.6 28 ± 1.2


(fresh awn)
Tillandsia 0 0
RESULTS usneoides
Structural Characterization of the Samples. Structural Pinus canariensis 114 ± 4 78 ± 5.6 31 ± 6.4
characteristics of the samples are presented in Table 1. The Abies bracteata 120 ± 2.8 94 ± 2.6 25.8 ± 2.4
awns of Hordeum vulgare (both DH and fresh) have barbs Sequoiadendron 115 ± 7 85 ± 3.9 29.5 ± 5.3
giganteum
(conical structure), the needles of Sequoiadendron giganteum Sequoia 94 ± 2.7 60 ± 4.5 33.5 ± 4.2
have barblike conical structures, and the other samples do not sempervirens
have barbs.
Surface Microstructures. The awns of Hordeum, fresh or measure the contact angle. Therefore, the contact angles for the
dry, have similar surface microstructures. A combination of the awn samples shown here were measured only on the surface of
microstructures of different dimensions result in the the main axis of the awns. However, we assume that barb
hierarchical architecture.38 They have barbs (Figure 2a, b) on surfaces will have a similar wettability to those on awn surfaces
both sides as well as along the midsection of the awns and have because of similar surface chemistry.
microgrooves on the surfaces of the awns (Figure 2b, c). Comparison of Fog-Collection Efficiency. Barbed
Moreover, SEMs in Figure 2b, c show that the thin coating samples were found to be more effective than the samples
(∼300 nm) of TiO2 does not fill the microgrooves (groove without barbs (Figure 3). Highly wettable (θadv = 16° ± 2.7 and
height = 3−3.6 μm). Wax crystals are visible on the θrec = 9° ± 2.6) DH awns showed a higher efficiency than
hydrophobic surfaces of the needles of Abis and Sequoiadendron hydrophobic fresh awns (θadv = 112° ± 2.9 and θrec = 84° ±
(Figure 2d, e). 3.6). The efficiency of superhydrophilic (contact angle = 0°)
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Figure 3. Amount of water collected by 2 × 2 cm2 samples over 10


min (S* = Sequoiadendron). (In the first set of samples, intact Ns/
NLSs were used but the diameters/widths of Tillandsia, Abies, and
Sequoia were too large (Table 1) compared to that of the Hordeum
awns. In the second set the widths of the Ns of Abies and Sequoia were
reduced by cutting, and Tillandsia NLSs of smaller diameter were used.
Ns/NLSs in each 2 × 2 cm2 sample in both sets occupied similar
percentage of area and therefore an equivalent effective surface area for
fog collection.)

Tillandsia was higher than that of any other hydrophobic


samples (see contact angle in Table 2) and hydrophilic Sequoia.
Needles of Sequoiadendron and Sequoia showed the least Figure 4. Mechanism of fog droplet capture and transport by the DH
efficiency among the samples. DH awns of Hordeum were awns: capture, then coalescence, followed by the transport to the
found to be the best among the samples analyzed here. The target. The first cycle (a−g) takes about 15−25 s, and afterward every
control experiment (without mounting the samples) showed cycle (h−l or m−o) takes 4−10 s, depending on the width of the awns.
that 10 ± 4 μL of fog settled down in the container, which is From (c−f) the droplet is getting larger, and (g) shows the downward
negligible. movement of the droplet. (h−l) or (m−o) show the next similar
Fog Collection by the Samples with Barbs. The cycles; (p) two droplets increasing in size, one anywhere in the middle
and another at the bottom of the awn; the gap between two droplets
mechanism of fog collection on DH awns is shown cyclewise forming on the DH awn is also shown. (q) Magnified image of a
in Figures 4 and 5; parts a−g in Figure 4 represent the first portion of (p) shows the movement of fog droplets from the tip to the
cycle and parts h−l and m−o represent the next cycles of fog base of the barbs. Scale bar: (a−p) 650 μm, (q) 300 μm.
droplet capture and transport, respectively. The droplets that
hit the surface, with the exception of the barbs of the awn
(DH), spread and/or followed the grooves. A second
mechanism occurred when droplets hit the barbs; in this
case, the droplets captured on the barbs moved from the tip to
the base. As a direct consequence of the process, an
enlargement of a droplet encompassing a small area of the
awn was observed (Figure 4c−f). The droplet pulled other
adjacent water droplets accumulated at the base of the barbs
toward itself.
With the increase of the amount of water in the droplet, it
moved downward (shown by the horizontal dotted lines in Figure 5. Size of the droplet at the bottom is increasing over time (a−
d). It pulls the water film on the awn. Hence, the fog droplets captured
Figure 4c−g, j−l, and n−o). The droplets moved to the bottom by all the barbs above are moving downward with the film (shown by
of the awn, when large enough (shown by the vertical dotted the white arrows in b−d). Another drop anywhere from the middle of
arrows in Figure 4g, l, o) after a time frame of between 4 and 25 the awn moving downward (shadow can be seen) shown by the arrow
s. The first cycle of fog collection on the DH awn, starting with (e); droplet about to start dripping shown by the arrow (f); scale bar 1
drop formation to falling downward (Figure 4a−g), took 15− mm.
25 s depending on the width of the awns. The subsequent
cycles (shown in Figure 4h−l and m−o) took 4−10 s direction from Figure 5a−d) by pulling the droplets from the
depending on the width of the awns. The cycle continues. nearby barbs and the surface of the awn, resulting in the
Over a length of 2 cm, mostly in one place, rarely in two, the formation of a film on the DH awn. Simultaneously, other
droplet(s) was seen to form and there was obviously a droplet larger droplets forming continuously anywhere in the middle of
at the tip (Figure 4p). A magnified image of a portion of Figure the awn were also combining with the droplet at the bottom
4p is shown in Figure 4q to demonstrate the movement of fog (the shadow and the arrow in Figure 5e). Therefore, both the
droplets from the tip to the base of the barbs. water film flow and the droplets falling from anywhere in the
Figure 5 describes the final collection of water from the middle of the awn resulted in the enlargement of the droplet at
bottom of the awns. The droplet moved to the bottom of the the bottom, as well as continuous dripping after about every
awn, and there the droplet increased in size (shown in the 27−58 s from the bottom (Figure 5f).
D DOI: 10.1021/acs.langmuir.5b02430
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The hydrophobic awns did not have an efficient capture of NLSs, they showed moderate fog-collection efficiency (Figure
fog droplets because of the saturation of the barbs due to the 3). It is to be noted that the amount of water remaining on the
accumulation of water at their bases (Figure 6a). However, in surface was less than those of the hydrophobic samples, e.g.,
Hordeum vulgare (fresh awn), Abies bracteata, etc., but one of
the highest among all the samples due to their absorption of
water in the NLSs.
Droplets remained pinned to the surfaces of Abies bracteata,
Pinus canariensis, and Sequoiadendron giganteum (Figures 6b and
S3a, b in Supporting Information) until they were large enough
to be dominated by the gravitational force, which is consistent
with the contact angle and CAH (Table 2) of the surfaces. The
illustration of the droplet behavior on a needle of Abies
bracteata is shown in Figure 6b. It showed similar droplet
behavior to that of the hydrophobic Hordeum awn. Pinus
Figure 6. Fog droplet behavior on a fresh hydrophobic awn of canariensis also showed similar behavior (Figure S3a), but the
Hordeum vulgare (a); hydrophobic needle of Abies bracteata (b). Fog droplets on the needles were more elongated than those of
droplet behavior on the DH awn at different moments during fog Abies and Sequoiadendron due to higher CAH and the presence
collection; after (c) 30 s, (d) 60 s, and (e) 90 s free barbs are seen on
both sides of the awns. Scale bar = 1 mm.
of microgrooves. The droplets attached elongated after getting
larger and fused with similar droplets, forming a thick film on
the hydrophilic needles (see contact angle and CAH in Table
some instances it was observed that when a large droplet from 2) of Sequoia sempervirens.
the top fell down it hit other droplets on the way, leading to a In the second set of samples, the diameter of Sequoia and
cascade where the droplets further down the awn fell down Abies needles was reduced by cutting them. This resulted in the
together. Only then can a new cycle start on the awns increase of the sharpness and surface area of the edges of the
(especially on the barbs). The accumulated water at the bases needles. We also used Tillandsia NLSs of smaller diameter (see
of the barbs covered the barbs (Figure 6a) and reduced the fog Table 1). Although the effective surface area occupied by the
droplet capture by those barbs. For convenience, we name the Ns/NLSs remained the same (50−55% coverage), their fog
four larger droplets on the awn/needle (Figure 6a, b) d1, d2, d3,
collection increased by 7−13% (Tillandsia 7.3%, Abies 9%, and
and d4 from the top to the bottom, respectively. If d1 falls first it
Sequoia 12.6%). Despite the increase, only Tillandsia from them
will collect other droplets available on its way down. Similar
could reach the efficiency comparable to the barbed Hordeum
results were seen for d2 and d3; logically d4 cannot influence the
awn (fresh), but it was still only ∼60% of the efficiency of DH
downward movement of d1, d2, and d3.
In contrast, DH barbs followed a continuous fog-collection awns. However, the efficiency of Tillandsia decreased over time
cycle as they were never saturated (Figures 4, 5, and 6c−e) at due to the saturation of the whole NLSs, and therefore there
their bases. Due to a film formation, there was an overall were no free trichomes to catch fog droplets after a few
influence of the fog droplets on the DH awns. Droplets minutes. Moreover, a drastic decrease (Table 1) of the width of
captured on the barbs (DH awn) were subsequently trans- Sequoia Ns is a possible cause for a total of 12.6% increase of
ported to the base of the barbs followed by the transport fog collection (Figure 3).
downward (observed and documented by the CCD camera).
No droplets were seen attached on the sides of the awns
(observed and documented by the CCD camera and a camera
■ DISCUSSION
The size, form, and surface structure of the samples where fog
with Nikor medical lens). Even the film on the surface was not droplets can be captured are very important factors in fog
thick enough to reduce the void space between two awns
collection. The fog droplet carrying wind, while approaching an
(Figures 4, 5, and 6c−e) because the film was continuously
obstacle in front of it, tends to deviate its direction to the right
flowing downward due to the grooves directed from the top to
or left according to the space available. If the obstacle is a
the bottom and due to the gravitational force as well. Other
orientations of the awns, e.g., horizontal, upward orientation, meshlike structure, the edges of the fibers (i.e., the awns or
etc., resulted in a lower transport of water. Thus, a reduced needles of the samples in this study) play a crucial role in
efficiency was observed. capturing fog droplets. We not only checked the influence of
For 50% coverage of the sample of DH awns, no clogging edges of the Ns/NLSs but also controlled their diameter, as
was observed except at the bottom for a short time due to the closely as was possible, so that they were comparable in size.
fast transport of the tiny droplets from the tips of the barbs to The increase in fog collection by the modified samples is
their bases, followed by the downward movement. Even if we believed to be caused by the reduced diameter, increase of edge
increased the coverage by DH awns to ∼65%, we did not for higher impingement, and increase of sharpness and
observe any clogging, with the exception of at the bottom for a wettability of the edges due to cutting. Despite these measures
short period of time. being taken, the amount of water collected by Hordeum (DH)
Fog Collection by the Samples without Barbs. After was almost twice as high as any other samples. Here, an
2−5 min of effective fog capture by Tillandsia NLSs, the effective transport of the water captured played the major role
trichomes were saturated (Figure S4a, b in Supporting in keeping the barbs free to continuously capture more fog
Information) and remained attached to the NLSs. Con- droplets. The efficiency of the DH awns was attributed mainly
sequently, during the last half (5 min) of fog-flow duration, to the conical shape of the barbs; this generates a Laplace
the dripping of water from the NLSs of the sample reduced. pressure gradient between the two opposite sides of the drop
Nevertheless, due to their superhydrophilic trichomes43 on the on the barb.44 It can be described as follows,
E DOI: 10.1021/acs.langmuir.5b02430
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R2 2γ lubrication effect that increased the velocity of the drop motion


ΔPbarb = − ∫R 1 (R + R 0)2
sin αdz on the surfaces.31,44 Nature also provides logic to support it.
Many lower plants, such as lichens, mosses, etc., and higher
where γ is the surface tension of water, R is the barb’s local plants, such as Bromeliads, epiphytic orchids, etc., have evolved
radius (Figure 7 shows two local radii (R1 and R2) of the barb at superhydrophilic surface property to uptake water.43,45,46
Moreover, the presence of microgrooves on the surface of
the awns improved the downward movement of water. In other
words, a faster transport on the surface has been achieved by
higher wettability along with the microgrooves.36,47,48 The
droplets that hit the grooved surface of the awns tend to fuse
with neighboring droplets and grow larger. Capillary forces
cause the droplets that accumulate at the base of the barbs, to
be pulled into the grooves. Then, their movement is influenced
by the energy barrier in different directions. The first thing that
helps downward movement is the vertical orientation of the
awns. The second thing is the zero-energy barrier parallel to the
groove direction.49 Therefore, the droplets form an elongated
filament shape in the aforementioned direction, where it finds
another similar source to follow the path until the end and a
Figure 7. Schematic of the movement of a water droplet (in blue) spontaneous spreading of water along the direction occurs as it
from the tip to the base of a barb. The region near the tip (radius R1) gathers sufficient momentum to do so.50−53 Furthermore,
of the barb has larger pressure than the base region (radius R2); thus
during the accumulation of the fog drops on the surfaces
water droplet moves from higher to lower pressure. The direction of
droplet movement is marked by an arrow. (actually condensation), heat transfer is an important issue.
Hydrophilic surfaces could be an advantage compared to the
hydrophobic surfaces in this respect.48 Therefore, directional
the two opposite sides of the drop), R0 is the radius of the drop, microgrooved surfaces with higher wettability enhance the
α is the half apex angle of the barb (Figure 7), and dz is the drainage performance along with a high rate of droplet
integration variable. The region near the barb’s tip (region with condensation and/or accumulation. To reduce re-entrainment
a smaller radius) has a larger Laplace pressure than that near in fog collection, highly adhesive superhydrophobic surfaces,
the base (region with a larger radius). The energy generated e.g., peanut leaf surface, have been studied by a research
from the pressure difference (ΔPbarb) drives the droplet to group.54 The surfaces remain occupied with the droplets
move from the tip to the base of the barb.11 attached on them unless the droplets have been influenced by
The combination of higher wettability and barbs on both the gravitational force. Moreover, this effect would have a
sides proved to be the major factors for a high capture rate. In negative influence for the hierarchically barbed samples by
our previous study,36 we showed that both microstructured and blocking the barbs.
superhydrophilic surfaces have higher capability to capture fog The meshes with 50% coverage theoretically remove 50% of
droplets than those of flat and/or hydrophilic or hydrophobic. the droplets approaching them.55 Although barbs on the edges
Because of the influence of morphological differences in the of the fibers (as seen on the awn sample) only occupy a low
samples, the influence of their wettability on fog-collection space, they can capture a high percentage of the fog droplets
efficiency cannot be expected to be exactly similar to the earlier that would otherwise be lost if there were no barbs. Park et al.37
study. However, a higher efficiency of superhydrophilic (θ = showed that clogging would be a problem in hydrophilic
0°) T. usneoides than of the hydrophobic samples (see contact meshes. Provided that their samples contained no barbs, the
angles in Table 2) tends to show a similarity. In the case of droplets remained attached at the edges of the fibers, resulting
hydrophobic surfaces, such as fresh Hordeum awns and needles in clogging. The clogging observed only at the bottom of the
of Abies, Pinus, and Sequoiadendron, water droplets remained DH awn for a short period of time would not be a problem as it
attached to their surfaces (Figures 6a, b and S3a, b), resulting in did not hamper the flow of the fog. It should be noted that it is
a discontinuous fog-collection cycle.28 also possible to overcome this problem with design
If we deduct the amount of water remaining on the optimization (Figure 8). Therefore, even superhydrophilic
hydrophobic samples, their efficiency would be much lower, meshes of barbed fibers could solve the clogging problem.
i.e., 10−20% lower. It is to be noted that even after 30 min the
amount of water that remained on the surface would be the
same as it was after 10 min, but ultimately the presence of these
droplets influence the total amount of fog collection. If only the
amount of water collected in the container under the sample is
considered, excluding the water remaining on the sample after
10 or 30 min observation, again the DH awn is expected to be
the most efficient among the samples investigated, because it
retained the lowest amount of water on the sample.
The hydrophilization of the hierarchical architecture of the
barbed awn attributed higher wettability of the entire surfaces.
Higher wettability of the conical structures, as well as other Figure 8. Schematic of the proposed design of a part of a fog collector
parts of the awns allowed the droplets to spread. Consequently, (a); barbed vertical fibers having microgrooves from top to bottom
the presence of a precursor liquid film on the surface provided a (b); a single barb with an apex angle 2α (c).

F DOI: 10.1021/acs.langmuir.5b02430
Langmuir XXXX, XXX, XXX−XXX
Langmuir Article

Moreover, because of the higher wettability, the droplets University of Bonn, for providing plant samples and Axel
captured on the surface of the awns could not be blown away Hinnemann (Rhine-Waal University of Applied Sciences) for
by the wind, which has been shown to be a major problem for assistance in atomic force microscopy. We also thank Danica
the superhydrophobic surface of the mesh during fog Christensen (Nees Institute, University of Bonn), a native
collection.37 Thus, the superhydrophilic surface property also English speaker, for proofreading the manuscript.


would nullify the possibility of re-entrainment (loss of captured
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■ AUTHOR INFORMATION
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H DOI: 10.1021/acs.langmuir.5b02430
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