Elucidating The Surface Geometric Design of Hydrophobic Australian - 2019 - Hel

Received:
8 October 2018
Revised:
Elucidating the surface
29 January 2019
Accepted:
1 March 2019
geometric design of
Cite as: Hua Guo,
Zonghan Xie, Jeremy Shaw,
hydrophobic Australian
Kingsley Dixon,
Zhong-Tao Jiang,
Chun-Yang Yin,
Eucalyptus leaves:
Xuemei Liu. Elucidating the
surface geometric design of
hydrophobic Australian
experimental and modeling
Eucalyptus leaves:
experimental and modeling
studies.
studies
Heliyon 5 (2019) e01316.
doi: 10.1016/j.heliyon.2019.
e01316
Hua Guo a, Zonghan Xie b, Jeremy Shaw c, Kingsley Dixon d, Zhong-Tao Jiang e,
Chun-Yang Yin f, Xuemei Liu g,∗
a
School of Engineering, Edith Cowan University, Joondalup, WA 6027, Australia
b
School of Mechanical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia
c
Centre for Microscopy, Characterization & Analysis, The University of Western Australia, Crawley, WA 6009,
Australia
d
School of Molecular and Life Sciences, Curtin University, Bentley, WA 6102, Australia
e
School of Engineering & Information Technology, Murdoch University, Murdoch, WA 6150, Australia
f
Newcastle University in Singapore, SIT Building@Ngee Ann Polytechnic, 537 Clementi Road #06-01, Clementi,
599493, Singapore
g
Department of Infrastructure Engineering, The University of Melbourne, Parkville, VIC 3010, Australia
∗
Corresponding author.
E-mail address: [email protected] (X. Liu).
Abstract
Three Australian native Eucalyptus species, i.e., Eucalyptus woodwardii,

Eucalyptus pachyphylla and Eucalyptus dolorosa, were investigated, for the first
time, with respect to the hydrophobicity of their leaves. It is well established that
these leaves exhibit exceptionally high water repellency, in addition to an
extraordinary ability to retain water, albeit their specific wetting mechanisms are
still poorly understood. To identify the critical factors underlying this
phenomenon, the surface topography of these leaves was subjected to micro-
https://doi.org/10.1016/j.heliyon.2019.e01316
2405-8440/Ó 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article Nowe01316
examination (SEM). Micro- and nanometer scale surface roughness was revealed,
resembling that of the quintessential “lotus effect”. Surface free energy analysis
was performed on two models based on the surface topographies of the study
Eucalyptus species and lotus, in order to study wetting transitions on these
specific microscopic surface features. The influence of surface geometrical
parameters, such as edge-to-edge distance, base radius and cylindrical height, on
surface free energy with different liquid penetration depths was studied with
these two models. Larger energy barriers and smaller liquid-solid contact areas
were more influential in the calculations for the lotus than for Eucalyptus. The
information obtained from these two models may be useful for guiding the
design of novel artificial surfaces in the collection and transport of micro-volume
liquids.
Keywords: Structural biology, Plant biology
1. Introduction
Many biological surfaces, such as plant leaves, bird feathers and animal furs, exhibit
strong water repellency in order to adapt to environmental conditions. A typical
example is the adaxial surface of the lotus leaf Nelumbo nucifera, which remains
completely dry while floating on water. The wetting characteristics of the lotus
leaf include high contact angles and low contact angle hysteresis [1, 2, 3, 4], attrib-
uted largely to a hierarchical surface structure. These properties have formed the ba-
sis of many surface-critical applications; for example, self-cleaning [5, 6, 7],
corrosion prevention [8], drag reduction [9] and fouling control [10]. Recently,
high contact angle hysteresis was observed for certain rose petals exhibiting high
contacts angles [11]. These petals contain micro-bumps with relatively wide spacing
and small peak-to-base heights. Consequently, a composite wetting scenario prevails
e that is, the Wenzel process [12] is dominant on the micro-structure level, allowing
water to enter the asperities, therefore leading to a high contact area and high adhe-
sion; and the Cassie mode [13], rules on the nano-structure level, maintaining high
water contact angles. Such unique wetting behavior may lead to applications in mass
and heat transport [14] or microfluidic devices [15].
The contact angle, commonly used to quantify the wettability of a solid surface, is a
function of two independent variables: the surface energy of the solid controlled by
its chemical composition and bonding states, and the surface roughness. Evidence
has shown that the presence and three-dimensional (3D) geometry of surface pat-
terns can markedly alter the wetting responses of a surface. For example, micro-
structured features, in the form of pores and posts on a leaf surface, can increase wa-
ter contact angles substantially. Recent studies revealed that nano-structured rough-
ness can further enhance the water repellency and help maintain a robust composite
2 https://doi.org/10.1016/j.heliyon.2019.e01316
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wetting [11, 16, 17, 18, 19]. Therefore, understanding the relationships between sur-
face geometric parameters and wetting properties may assist in the development of
new types of surfaces with enhanced integrated characteristics.
Eucalyptus, a plant species found widespread across temperate, arid and tropical
ecosystems in Australia, is well adapted for coping with environmental extremes.
It is widely noticed that Eucalyptus leaves, especially those shiny juvenile leaves,
present considerable water repellency with water forming spheres on the leaf surface
and the droplets tend to adhere to the leaf surface even when the leaf is turned upside
down. This is a sharp contrast compared to the lotus leaf, on which water forms per-
fect spheres that roll off readily even when the leaf is slightly tilted. The special
wettability of Eucalyptus leaves may inspire and trigger relevant applications other
than superhydrophobicity or self-cleaning. However, the wetting properties of Euca-
lyptus leaves have never been studied in detail, with only an investigation of surface
leaf waxes undertaken in 1970 of 315 Eucalyptus species for taxonomic purposes
[20]. Here, three Australian native Eucalyptus species with a prominent waxy-
white leaf form were comprehensively studied with emphasis on elucidating the
link between the surface micro-structures and leaf surface hydrophobicity. In view
of this, physical models were proposed based on the dimensions of surface micro-
structure features observed on their leaves. Surface energy analysis was carried
out on two physical models to compare wetting scenario transition between the
Eucalyptus species and the lotus Nelumbo nucifera leaf. Energy barrier and energy
potential were quantitatively identified during the speculated wetting transition
process.
2. Experimental
2.1. Sample preparation
Fresh leaves of three Eucalyptus species, i.e., E. woodwardii, E. pachyphylla, and E.
dolorosa were collected from specimens growing in the nursery at the Western
Australian Botanic garden in Kings Park. Squares of 100 mm2 were carefully
excised from the abaxial side of these leaves for optical observation and contact
angle measurements. Smaller squares of 4 mm2 cut from these leaves were freeze-
dried prior to SEM examination using an Emitech K775X Turbo Freeze Dryer
(Quorum Technologies Ltd, Kent, UK). The following time-temperature path was
adopted: holding at 120 C for first 5 min, then gradually rising to 65 C in a
period of 14 hours slowly increasing to room temperature over 10 hours.
To study the influence of nano-structural wax on the wettability of leaf surfaces, leaf
samples without wax were also prepared. Square specimens of 100 mm2 were firstly
cut from fresh Eucalyptus leaves, followed by immersing in 200 mL of chloroform
for 15 min to dissolve the wax layer from the specimen surface. The specimens were
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then washed three times with 5 mL of chloroform and dried in a fume hood for 2
hours to evaporate the solvent prior to wettability measurements.
2.2. Instrumentation
The contact angle measurements were performed at ambient temperatures using an
FTA 1000 Drop Shape Analysis system (First Ten Angstroms Inc., Virginia, USA)
equipped with an automated dispensing syringe and a computer-controlled tilt stage.
To ensure an even surface for water dispersal, leaf samples were fixed on the stage
by double-sided adhesive tape before the application of 5 mL water droplets. The
average water contact angles (n ¼ 5) was obtained by analyzing the sessile drop im-
ages using Drop Shape Analysis software affiliated with the goniometer. In order to
measure roll-off angles, the stage tilt angle was gradually increased at a speed of 1
deg/sec from 0 until the point where the water droplet started to move along the
stage.
For Scanning Electron Microscopy (SEM) analysis, specimens were mounted on

aluminum stubs with carbon tabs prior to sputter-coating with 10 nm carbon and
3 nm platinum. SEM imaging was conducted at 10 kV accelerating voltage and a
working distance of 10 mm using a field-emission SEM (Zeiss VP1555, Oberko-
chen, Germany). Other operating parameters were stipulated as follows: aperture
size ¼ 30.00 mm, signal ¼ SE2, gun vacuum ¼ 1.30exp10 Torr. Ten measure-
ments of surface features were performed on each SEM image, from which the
average and standard deviations values were derived.
3. Results and discussion

3.1. Leaf surface wettability
Special wetting features, namely high contact angles and strong water adhesion,
were exhibited by the leaves of all three Australian native Eucalyptus species.
This is similar to the findings on the petals of Rosa, cv. Bairage [11] and in sharp
contrast with the wetting condition of the lotus leaf, Nelumbo nucifera characterized
by high contact angles but negligible water retention.
The water contact angles of the study species (Fig. 1), when compared with that of
lotus leaves (160.4 0.7 ) [21], can be considered as strongly hydrophobic. Given
that the lotus is an emergent aquatic plant and the fact that the species of Eucalyptus
thrive in drier environments, it is surprising that these Eucalyptus spp. exhibit such
high levels of leaf hydrophobicity. Conversely, strong adhesion was observed on all
three Eucalyptus species, before wax removal, between the water droplet and the leaf
surface, with the droplet adhering firmly to the surface when it was gradually tilted
from 0 to 180 (Figure not shown here). This adhesion may be due to a large contact
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Fig. 1. Experimental water contact angles of Eucalyptus leaves before and after wax removal.
area between the water and the leaf surface. Water retention on fresh leaves is
believed to help maintain surface hydration following a rainfall or evening dew
event by providing the leaf with an additional source of moisture, particularly since
many Eucalyptus species are exposed to periods of low rainfall.
The surface morphologies of three Eucalyptus leaves are shown in Fig. 2. Generally
speaking, the entire surface of these leaves is covered by fine nanometer scale wax of
different forms and microscopic papillae and stomata, forming at least two length
scales of roughness. On the micrometer level, hemisphere-like papillae arranged
in a quasi-hexagonal pattern appear on the leaf surfaces of all three Eucalyptus spe-
cies. Different wax morphologies, however, can be identified at the nanometer level.
Needle-like wax particles of approximately 5 mm in length and 200 nm in diameter
are aggregated on the leaf surface of E. woodwardii (Fig. 2a), while string-like wax
covers the papillae of E. pachyphylla (Fig. 2b) and flake-like wax is found on E.
Fig. 2. SEM images of three Eucalyptus leaves at two magnifications: (a) Eucalyptus woodwardii with
optical images of water droplets shown in the inset, (b) Eucalyptus pachyphylla, and (c) Eucalyptus do-
lorosa. Scale bars: (1) 20 mm and (2) 2 mm.
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dolorosa (Fig. 2c). These multi-scale structures have some morphological similarity
to that of the lotus [21]. However, there is a major difference: for lotus leaves, the
wax forms fine, nanometer-length short hairs positioned upright to the surface, while
on these specific Eucalyptus leaves, wax features possess relatively large dimensions
lying loosely over the surface.
In order to resolve the role that the wax structure plays in the observed wetting prop-
erties, water contact angles on these Eucalyptus leaves were measured and compared
before and after wax removal (Fig. 1). For leaves free of wax, an average contact
angle drop of 12 1.7 was observed, which suggests a minor contribution to the
contact angles coming from the wax and that the leaf micro-structures impart an
inherent surface hydrophobicity.
The surface micro-structures of these Eucalyptus leaves appear to play a key role
in determining water contact angles, as high contact angles are still maintained
even after wax is removed. However, it should, be pointed out that the wax struc-
tures on the nanometer scale generally enhance the wetting robustness. For
example, synthetic hierarchical surfaces with varying micro-structure pitch values
and wax densities consisting of the nano-structures have been previously fabri-
cated [11]. On these artificial surfaces water contact angles did not change sub-
stantially on 23 mm pitch micro-structures across differing wax densities.
However, there was a drop in the contact angle on a 105 mm pitch micro-
structure when less wax was deposited. Based on the above observation and anal-
ysis, wetting states of both the Eucalyptus and the lotus Nelumbo nucifera leaves
may be modeled using their surface micro-structural parameters as input. The sur-
face morphology of Eucalyptus leaves can be considered as multiple hemispheres
sitting on a flat plane (Fig. 3a). Similarly, for the lotus [21], the leaf surface can be
visualized as a plane containing many cylinders, each with a hemispherical cap
(Fig. 3b). In both models, the radius of the hemisphere is denoted as r0, the height
of the cylinder as h0, and the edge-to-edge distance between two neighboring
micro-structures as 2d0. When h0 equals zero, the two models are essentially
identical.
The surface micro-structural parameters of both lotus and three Eucalyptus leaves,
such as r0, h0 and 2d0, were measured from SEM images and summarized in
Table 1. It is understood that the arrangement of the micro-structured features on
the leaf surface may affect the surface roughness, which in turn influences the contact
angle. Two most common arrangements of the microscopic hemispheres, namely
hexagonal and square patterns are considered here when calculating wetting proper-
ties. However, negligible difference (for example, <1% in contact angle) was
observed from these two patterns in this study. Therefore, only data from the hexag-
onal pattern is reported here.
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Fig. 3. Generalized physical models of microscopic surface features for: (a) Eucalyptus leaf with param-
eters adopted from Eucalyptus pachyphylla and (b) lotus leaf Nelumbo nucifera.
Table 1. Geometric parameters of micro-structures measured on the leaf surface

of lotus Nelumbo nucifera and three Eucalyptus species.
Samples Radius, r0 (mm) Height, h0 (mm) Distance, 2d0 (mm)
Lotus 5 0.5 5 0.5 10 1.2

E. woodwardii 8 0.8 0 14 2.8
E. pachyphylla 9 0.6 0 9 2.8
E. dolorosa 10 1.0 0 16 5.4
3.2. Analysis of surface free energy

When a water droplet is gently deposited on a surface, based on the surface energy
and roughness of the surface, one of the two classical wetting regimes can exist. In
the homogeneous Wenzel wetting, water fills in the asperities of the micro-structure
and maintains the maximum contact with the surface. As such, the contact angle is
expressed as [12]
cosqW ¼ r cosqY ð1Þ
where qW and qY are the Wenzel and Young contact angles, respectively. The
roughness factor, r, is defined as the ratio of the actual solid-liquid contact area
to its projected area on the horizontal surface plane. Alternatively, the heteroge-
neous Cassie model, characterized by the presence of air pockets between water
and the leaf surface [13], can be used to calculate the contact angles as
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cosqC ¼ rf f cosqY þ f 1 ð2Þ

where qC and qY are the Cassie and Young contact angles, respectively, rf is the
roughness ratio of the actual solid-liquid contact area and f is the fraction of the
solid-liquid contact area projected on the surface plane over the total surface
projection.
For this three-phase system, different surface energies exist for specific wetting sce-
narios. There are, therefore, energy barriers between various wetting states. A prin-
ciple of energy minimization is generally applied to determine the final wetting state.
That is, the liquid will wet the rough surface to the extent that the overall surface
energy of the system is minimized. A prerequisite for taking the final state of min-
imum energy is that the system can overcome the energy barriers lying between
different conditions in a certain environment, given that wetting is a continuous
physical process. Thus it is possible for the system to reach equilibrium before the
surface energy reaches minimum due to insurmountable energy barriers presented
without any external disturbance. In order to analyze the possibility of transition be-
tween different wetting states, it is necessary to consider the corresponding Gibbs
free energy analysis. The Gibbs free energy of a droplet on a surface can be
described as [22, 23]
G ¼ gLV SLV þ gSV SSV þ gLS SLS ð3Þ

where gij is the surface energy between the interface ij (solid, liquid and vapor), and
Sij is the contact area of the interface ij (solid, liquid and vapor).
Before substituting with mathematic expressions for these interfacial areas, certain
assumptions and reasonable approximations are required based on actuality: (a)
the influence of gravity can be neglected, as the radius of a water droplet used
here (5 mL, w1.0 mm) is usually less than the capillary length (w2.7 mm). Thus,
the droplet can be deemed to be spherical; (b) the radius of a water droplet is signif-
icantly larger than the surface roughness, and the radius of the liquid-vapor interface
meniscus, between surface reliefs, can be approximated to the radius of the water
droplet. Consequently, the liquid volume of entering the asperities of the micro-
structures can also be neglected, and the liquid-vapor interface meniscus can be
taken as planar, parallel to the surface horizontal plane; (c) the base of the spherical
droplet can be approximated as the projection of the liquid-solid contact on the sur-
face plane; (d) the contact line tension and potential energy are negligible as their
contributions to the total surface energy are insignificant. When relating to the
droplet volume V and contact angle q, the radius of the droplet R can be expressed
as [22]
3V 13 1
R¼ð Þ ð2 3 cos q þ cos3 qÞ 3 ð4Þ
p
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In a composite wetting state, the interfacial areas are calculated using rf and f, the
parameters defining the Cassie relationship. SLV consists of two parts: the external
spherical cap of the droplet and the liquid-vapor contact under the droplet.
SLV ¼ 2pR2 ð1 cos qÞ þ pR2 sin2 qð1 f Þ ð5Þ
SLS only contains the liquid-solid contact area under the droplet.
SLS ¼ pR2 sin2 q rf f ð6Þ
SSV also consists of two parts: the solid-vapor contact under and outside the droplet,
respectively. SSV-total is introduced here as the total solid-vapor contact area before
the droplet deposition. For a specific surface, SSV-total is constant.
SSV ¼ ðSsvtotal pR2 sin2 q rÞ þ pR2 sin2 q ðr rf f Þ ð7Þ
The Gibbs energy of a composite wetting system can be described by plugging Eqs.
(4), (5), (6), and (7) into Eq. (3)
2 1 2
Gcomposite ¼ gSV SSVtotal þ gLV ð3VÞ3 p3 ½FðqÞ 3 ½2 2 cos q sin2 q Fðf Þ ð8Þ
with
FðqÞ ¼ 2 3 cos q þ cos3 q ð9Þ
and
Fðf Þ ¼ rf f cosqY þ f 1 ð10Þ
For a droplet with a volume V and a well-defined solid surface, the surface energy of
the system changes with the contact angle q and its specific wetting condition (in
which these two parameters rf and f can be determined). The surface roughness ratio,
r, does not affect the value of Gcomposite due to its absence in Eq. (8). However, Eq.
(8) is a universal equation that remains valid for both composite and wetted regimes.
Similar to the conversion between Wenzel and Cassie relations, the function FðfÞ ¼
rf f cosqY þ f 1 for a composite regime can be simplified to FðfÞ ¼ r cosqY for a
wetted regime. Thus, the Gibbs energy for a wetted case (where there is no air trap-
ped under the droplet and thus no liquid-vapor and solid-vapor contact areas), can
also be obtained with the corresponding F(f) expression.
Supposedly the wetting transition from a composite case to a wetted case begins with
gradual penetration of liquid into the asperities. Let h be the penetration depth, r0 be
the micro-hemisphere base radius and d0 half of the edge-to-edge distance of the
micro-hemispheres in a hexagonal arrangement. h can be reasonably approximated
to r0 by h ¼ xr0 , where x is in the range of (0, 1) for the model of the Eucalyptus
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spp., and d0 can be approximated to r0. The wetting parameters for a composite case
can be expressed as
2r0 2
rf ¼ ¼ ð11Þ
2r0 h 2 h
and
p½r0 2 ðr0 hÞ pð2x x2 Þ

2
f¼ pffiffi ¼ pffiffiffi ð12Þ
2
3
ð2r0 þ 2d0 Þ2 8 3
while the wetted regime can be expressed as:
pr0 2 p
r ¼ 1 þ pffiffiffi 2 ¼1þ
pffiffiffi ð13Þ
2 3ðr0 þ d0 Þ 8 3
The function F(f) can be rewritten when substituting Eqs. (11) and (12)
pffiffiffi
4px cosqY ð2 xÞðp þ 2 3Þ
Fðf Þ ¼ FðxÞ ¼ pffiffiffi ð14Þ
ð2 xÞðp þ 2 3 þ 2pxÞ
It is assumed here that the transition between a composite and wetted state involves
gradual liquid penetration into the rough micro-structures. For each depth of pene-
tration, there is a specific contact angle for the droplet in order to achieve the min-
imum surface energy. At the thermodynamic equilibrium, the contact angle q equals
the Cassie contact angle qC and Eq. (8) can be used to calculate the Gibbs surface
energy
2 1 1
GCassie ¼ gSV SSVtotal þ gLV ð3VÞ3 p3 ½FðqÞ3 ð15Þ
with
FðqC Þ ¼ 2 3 cos q þ cos3 qC ð16Þ

2 1
In Eq. (15), both the first part on the right side, gSV SSVtotal and gLV ð3VÞ3 p3 are
positive and constant, the actual value of GCassie can be compared through F(qC),
given the exponent on F(qC) is 1/3. In these calculations, 104◦ was adopted as the
water contact angle on a flat surface covered by wax [22].
The value of F(qC) decreases as the penetration depth x increases from nil to 0.75. At
about 0.75, the minimum of F(qC) is obtained (3.951), which indicates the minimum
surface energy for this specific geometry and composite wetting. After 0.75, F(qC)
begins to increase slowly. This observation is similar to the case found on flat-top
microscopic cylindrical pillars. When x reaches unity, liquid touches the bottom
and the wetting scenario shifts from composite to wetted, for which the F(qW) value
can be calculated as 2.867 by employing Eqs. (13), (1), and (8). Subsequently, when
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a droplet is deposited gently on a surface characterized with microscopic hemi-

spheres (r0 ¼ d0 ), liquid under the droplet simultaneously enters the asperities
and reaches a thermodynamic equilibrium at x ¼ 0.75 to achieve the minimum sur-
face energy for the composite regime (with local pinning and external energy input
neglected). Since the wetted case possesses lower surface energy than the composite
case, a transition occurs when the vibration energy of the droplet or an external en-
ergy input can surpass the energy barrier, which can be calculated as the surface en-
ergy difference between the two states of x z 0.75 and x z 1. This method of
energy barrier calculation agrees with a postulation that, on flat-top microscopic pil-
lars, the energy barrier is the energy difference between the non-filling (Cassie) and
complete-filling states [23].
The effect of edge-to-edge distance on the surface energy is studied by changing the
value of d0 based on a constant r0, and the calculated F(qC) values are shown in
Fig. 4. A lower minimum surface energy is obtained at a smaller depth for a smaller
d0. In addition, a larger energy barrier (marked as DG1 in Fig. 4a), which acts as an
indicator of hydrophobic stability, exists for the wetting transition for a smaller d0.
Therefore, a smaller d0, such as d0 ¼ 0, is favored to maintain a composite wetting
state.
A portion of the F(qC) curve in Fig. 4a is expanded with an extension of the F(q)
values at wetted regimes. After a minimum surface energy is reached, F(q) value
(or accordingly the surface energy) increases gradually with further liquid penetra-
tion before complete wetting of the asperities. Although not shown in Fig. 4b, the
F(q) values at the x range of (0.95, 1) can be reasonably postulated as being slightly
higher than the values acquired at x ¼ 0.95. The surface energy difference between
the composite state (with a minimum surface energy) and the wetted state, marked as
DG2 in Fig. 4b, can be considered as a transition potential or tendency. A larger en-
ergy difference, accompanied with a smaller barrier, reflects an easier composite-
wetted transition for a larger d0.
The energy barrier DG1 and energy potential DG2 for the wetting transition for
different d0 values are calculated using Eq. (15). The volume of the water droplet
is taken as 5 mL. The energy barrier is calculated as the difference between the lowest
energy and the energy at x ¼ 0.99, just before the wetting transition. The energy po-
tential is calculated as the difference between the lowest energy at a composite state
and the lowest energy at a wetted state. The results are shown in Table 2.
When d0 decreases from r0 to r0/4, the energy barrier increases from 0.52 nJ to 3.11
nJ, indicating enhanced hydrophobic stability or robustness. When d0 ¼ 2r0, the en-
ergy barrier is close to nil and a droplet deposited gently on such a surface will spon-
taneously enter the roughness to the thermodynamically-favored wetted state.
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Fig. 4. Influence of d0 on F(q) values: (a) F(q) at different penetration depths with different d0 values, (b)
F(q) at different penetration depths, 0.75 x 1. The F(q) values at the x range of (0.95, 1) are omitted.
When x ¼ 1, F(q) ¼ F(qW).
Table 2. Calculated energy barriers and energy potentials for different d0.
d0 DG1 DG2
Energy barrier, nJ Energy potential, nJ
0 7.33 4.05
r0/4 3.11 58.84
r0/2 1.56 83.24
r0 0.52 104.19
2r0 0.065 116.83
4r0 0.013 122.19
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In the model for the lotus, the existence of h0 leads to further extension of the pene-
tration depth x at the range of [1, 1 þ h0/r0]. With d0 being approximated to r0, the
wetting parameters for a composite case, in which the liquid level in the asperities is
below the microscopic hemisphere base, can be expressed as
2pr0 2 þ 2pr0 2 ðx 1Þ
rf ¼ ¼ 2x ð17Þ
pr0 2
and
pr0 2
f ¼ pffiffi3 ð18Þ
ð2r0 þ 2d0 Þ
2
2
while the wetted regime be expressed as:
pr0 2 þ 2pr0 h0
r ¼ 1 þ pffiffi3 ð19Þ
ð2r0 þ 2d0 Þ
2
2
The F(qC) values with x at the range of [1, h0) can be derived by combining Eqs. (9)
and (10) for the free surface energy expressions, and Eqs. (17), (18), and (19) for the
roughness factors. In Fig. 5a, the curve is the same as the Eucalyptus model in the
range of [0, 1). After further liquid penetration (x 1), F(qC) maintains increase with
a gradually decreasing slope. At the same range, the F(qW) value (corresponding to
the wetted surface energy and marked in blue), increases with x at a constant slope of
pffiffiffi
p=ð4 3Þ. At large depths of x (continued in Fig. 5b), the F(qC) value reaches a
maximum and then declines gradually even when x ¼ 10. The F(qW) value increases
with x and reaches a maximum at a much larger depth and then declines slowly. An
intersection is found for these two cures at x ¼ 4.6. After this point, the composite
regime is more thermodynamically-favored than the wetted regime.
It should be noted that Eq. (15) can only be used when the thermodynamic equilib-
rium is reached and the Cassie relationship is applicable. After x ¼ 2.05, the F(f)
value in Eq. (10) exceeds unity and no solutions for the contact angle will be found
to fulfill the equation of F(f) ¼ cosqC. The same issue occurs for calculating the min-
imum surface energy for a wetted scenario using the Wenzel relation when x > 7.4.
After these two specific points, only the original Eq. (8) can be adopted for the over-
all surface energy calculation and the results stand for situations when a thermody-
namic equilibrium cannot be reached.
Table 3 reveals that greater energy barriers and lower energy potentials are obtained
for greater h0 values. The change of h0 from 0 to r0 significantly elevates the energy
barrier from 0.86 to 4.22 nJ and decreases the energy potential from 104.16 to 74.28
nJ. When h0 > 1, all wetting conditions with the penetration depth of x > 2r0 face the
same maximum energy barrier (4.22 nJ) arising from this specific geometry. Before x
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Fig. 5. F(qC) values for the lotus model at different penetration depths of x: (a) 0 x 2, the composite
state is marked by red (left vertical axis) and the wetted state is marked by blue (right vertical axis); (b) 2
x 10, the composite state is marked by red and the wetted state is marked by blue. Three black ar-
rows denote turning points on surface energy at x ¼ 2.05, 4.6 and 7.4, respectively.
Table 3. Calculated energy barriers and energy potentials for different h0.
h0 DG1 DG2
Energy barrier, nJ Energy potential, nJ
0 0.86 104.16
r0/4 2.24 96.30
r0/2 3.28 88.65
3r0/4 3.88 81.37
r0 4.22 74.28
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reaches 7.4r0 and after the energy barrier is overcome, a wetted regime with lower
surface energy will be adopted by the system. However, neither a composite regime
nor a wetted regime will be thermodynamically-favored with a liquid penetration
deeper than 7.4r0. In this case, the droplet will adopt the composite state with a
much smaller x at a thermodynamic equilibrium.
The geometrical parameters presented in Fig. 3 can be adopted to compare the en-
ergy barriers and energy potentials of wetting on Eucalyptus and lotus leaves. For
Eucalyptus pachyphylla, r0 ¼ 2d0 ¼ 9 mm and h0 ¼ 0, the energy barrier and energy
potential are 1.56 nJ and 83.24 nJ, respectively. For lotus, 2r0 ¼ 2d0 ¼ 2h0 ¼ 10 mm
and these two values are 4.22 nJ and 74.28 nJ, respectively. The energy barrier for a
wetting transition on a lotus leaf is nearly three times that of a Eucalyptus pachy-
phylla leaf. The liquid-solid contact area, SLS, is also compared between these two
models, as the contact area is expected to be strongly associated with the water-
leaf adhesion. Given that the minimum surface energies at a composite state for
the two models are obtained at a similar liquid penetration depth ratio (x z 0.75,
Figs. 4 and 5a), the radii of a 5 mL water droplet on these two models are calculated
using Eqs. (4), (11), and (12). For Eucalyptus and lotus models, the radii are found to
be 1.074 mm and 1.065 mm, respectively. After substituting Eq. (6) with the radii,
the liquid-solid contact areas were calculated to be 0.908 mm2 and 0.298 mm2,
respectively. Therefore, for a water droplet of 5 mL, the liquid-solid contact area
on the Eucalyptus spp. is three times that on the lotus leaf. Even though several as-
sumptions and approximations have been made on the energy analysis and calcula-
tions, the results can be used to describe qualitatively the stability of hydrophobicity
and the surface adhesion for two different kinds of hydrophobic leaves in nature.
Further work will be focused on verification of these results by experimental data
on micro-fabricated surfaces and the wetting prediction of multiple roughness on
these models.
It was the first time that geometrical models were proposed based on the surface mor-
phologies of Eucalyptus leaves and lotus leaves to analyze quantitively two different
wetting phenomena observed in nature. Energy potential for wetting transition was
also identified at the first place in the surface free energy curve. This methodology of
free energy analysis using geometrical models could be useful for wettability calcula-
tions and evaluation of surfaces on the micro-meter level roughness. Further work will
be focused on verification of these results by experimental data on micro-fabricated sur-
faces and the wetting prediction of multiple roughness levels on these models.
4. Conclusions
Considerable hydrophobicity and strong adhesion were found on the leaves of three
Australian native Eucalyptus species. Multi-scale roughness, namely, micro-
Article Nowe01316
structural bumps and nano-structural wax, was revealed by SEM on these leaf sur-
faces. Physical models were proposed based on the surface morphologies to gain a
deeper understanding of the wetting mechanisms of Eucalyptus leaves in compari-
son to the lotus leaf, Nelumbo nucifera. Surface energy analysis on these two models
shows the changes of minimum surface energy with stepwise liquid penetration into
the asperities of the microscopic roughness. Lower minimum surface energy was
found on a smaller edge-to-edge distance of the micro-structures in both models.
The wetting transition from a composite state to a wetted state was quantitatively
identified using energy barrier and energy potential as criteria. Greater cylindrical
length below the microscopic hemisphere in the lotus model increases the energy
barrier for the wetting transition, which is beneficial for hydrophobic stability.
The strong water adhesion on Eucalyptus leaves was also explained by a relatively
larger liquid-solid contact area than for lotus leaves.
This study represents a novel attempt to understand the unique wetting behavior of
Eucalyptus leaves using a hemisphere-top model, given the facts that these Euca-
lyptus species present a different wetting scenario from the famous “lotus effect”.
These findings could be potentially useful for guiding the design of man-made sur-
faces with tailored wetting properties. The potential applications behind the Euca-
lyptus model will be but not limited to micro-liter mass transport or microfluidic
devices instead of superhydrophobicity and self-cleaning.
Declarations
Author contribution statement
Hua Guo: Conceived and designed the experiments; Performed the experiments;
Analyzed and interpreted the data; Contributed reagents, materials, analysis tools
or data; Wrote the paper.
Zonghan Xie: Analyzed and interpreted the data; Contributed reagents, materials,
analysis tools or data; Wrote the paper.
Zhong-Tao Jiang: Conceived and designed the experiments; Contributed reagents,

materials, analysis tools or data.
Jeremy Shaw: Performed the experiments; Contributed reagents, materials, analysis

tools or data.
Kingsley Dixon: Contributed reagents, materials, analysis tools or data.
Chun-Yang Yin: Performed the experiments.
Xuemei Liu: Analyzed and interpreted the data; Wrote the paper.
Article Nowe01316
Funding statement
This work was supported by the Edith Cowan University Postgraduate Research
Scholarship.
Competing interest statement

The authors declare no conflict of interest.
Additional information
No additional information is available for this paper.
Acknowledgements
The authors thank Amanda Shade from Kings Park and Botanic Garden for helping
collect fresh leaf samples. The authors acknowledge the facilities, and the scientific
and technical assistance of the Australian Microscopy & Microanalysis Research Fa-
cility at the Centre for Microscopy, Characterisation & Analysis, The University of
Western Australia, a facility funded by the University, State and Commonwealth
Governments.
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Three Australian native Eucalyptus species, i.e., Eucalyptus woodwardii,

Keywords: Structural biology, Plant biology

For Scanning Electron Microscopy (SEM) analysis, specimens were mounted on

3. Results and discussion

Table 1. Geometric parameters of micro-structures measured on the leaf surface

Samples Radius, r0 (mm) Height, h0 (mm) Distance, 2d0 (mm)

Lotus 5 0.5 5 0.5 10 1.2

3.2. Analysis of surface free energy

cosqW ¼ r cosqY ð1Þ

cosqC ¼ rf f cosqY þ f 1 ð2Þ

G ¼ gLV SLV þ gSV SSV þ gLS SLS ð3Þ

SLV ¼ 2pR2 ð1 cos qÞ þ pR2 sin2 qð1 f Þ ð5Þ

SLS ¼ pR2 sin2 q rf f ð6Þ

SSV ¼ ðSsvtotal pR2 sin2 q rÞ þ pR2 sin2 q ðr rf f Þ ð7Þ

FðqÞ ¼ 2 3 cos q þ cos3 q ð9Þ

Fðf Þ ¼ rf f cosqY þ f 1 ð10Þ

p½r0 2 ðr0 hÞ  pð2x x2 Þ

while the wetted regime can be expressed as:

FðqC Þ ¼ 2 3 cos q þ cos3 qC ð16Þ

a droplet is deposited gently on a surface characterized with microscopic hemi-

while the wetted regime be expressed as:

Zhong-Tao Jiang: Conceived and designed the experiments; Contributed reagents,

Jeremy Shaw: Performed the experiments; Contributed reagents, materials, analysis

Kingsley Dixon: Contributed reagents, materials, analysis tools or data.

Chun-Yang Yin: Performed the experiments.

Competing interest statement

[3] T. Onda, S. Shibuichi, N. Satoh, K. Tsujii, Super-water-repellent fractal sur-

[4] M. Nosonovsky, B. Bhushan, Energy transitions in superhydrophobicity: low

[5] C. Neinhuis, W. Barthlott, Characterization and distribution of water-repellent,

[6] A. Nakajima, K. Hashimoto, T. Watanabe, K. Takai, G. Yamauchi,

[7] B. Bhushan, Y.C. Jung, K. Koch, Self-cleaning eﬃciency of artiﬁcial superhy-

[8] T. Liu, Y. Yin, S. Chen, X. Chang, S. Cheng, Super-hydrophobic surfaces

[9] G. McHale, M.I. Newton, N.J. Shirtcliﬀe, Immersed superhydrophobic sur-

[11] B. Bhushan, E.K. Her, Fabrication of superhydrophobic surfaces with high

[15] R. Ledesma-Aguilar, R. Nistal, A. Hernandez-Machado, I. Pagonabarraga,

[22] A. Marmur, Wetting on hydrophobic rough surfaces: to be heterogeneous or

[23] L. Barbieri, E. Wagner, P. Hoﬀmann, Water wetting transition parameters of

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