Colloids and Surfaces A 561 (2019) 9–17

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Colloids and Surfaces A

journal homepage: www.elsevier.com/locate/colsurfa

Replicating and resolving wetting and adhesion characteristics of a Rose petal T

a a,b b b,⁎ a,⁎
Udita Uday Ghosh , Sachin Nair , Anuja Das , Rabibrata Mukherjee , Sunando DasGupta
a
Microscale Transport Processes Laboratory, India
b
Instability and Soft Patterning Laboratory, Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Pin 721302, West Bengal, India

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: A Rose petal is well known for a unique form of hydrophobicity, exhibiting simultaneously high apparent equilibrium
Structural superhydrophobicity contact angle (θ*) as well as high adhesion that hinders the rolling off of droplets. This behaviour is fundamentally
Bio-mimetic surface different than that commonly encountered in other bio-mimetic superhydrophobic surfaces (like a lotus leaf) that have
Contact angle hysteresis air entrapped in the solid-liquid contact zone (Cassie Baxter wetting state), thereby exhibiting low adhesion. Based on
Pinning
laser scanning confocal microscopy as well as underwater in-situ atomic force microscopy, we obtain high resolution
Wetting state
image of the water-substrate contact region (∼0.9–20 μm) which is significantly higher than that reported so far in the
literature. We clearly demonstrate that this unique "Petal effect" can indeed be attributed to the Cassie impregnating
wetting state, thereby resolving the prevailing ambiguity on this topic. We have also replicated the structure of the
actual rose petals using soft lithography on cross-linked polydimethylsiloxane (PDMS, Sylgard 184) and show that
both θ* as well as the adhesive properties of the replicated surface to be nearly identical to that of an actual petal. This
implies that the force of adhesion depends on the wetting state and the area of contact. Incidentally, the negative
replica of the petal, which is obtained as an intermediate during the replication process, exhibits slightly higher
adhesion and identical θ*, as compared to the actual rose petal and its positive replica. However, the prevalent wetting
state on the negative replica turns out to be Cassie like due to the presence of entrapped air. Both the negative and the
positive replica of the Rose petal can potentially be used as biomimetically fabricated sticky hydrophobic surface.

⁎
Corresponding authors.
E-mail addresses: rabibrata@che.iitkgp.ac.in (R. Mukherjee), sunando@che.iitkgp.ac.in (S. DasGupta).

https://doi.org/10.1016/j.colsurfa.2018.10.028
Received 4 September 2018; Received in revised form 7 October 2018; Accepted 8 October 2018
Available online 15 October 2018
0927-7757/ © 2018 Elsevier B.V. All rights reserved.
U.U. Ghosh et al.
1. Introduction
Wetting on meso and nano-structured surfaces has drawn much
research attention, ever since the identification of the Wenzel [1] and
the Cassie [2] states of wetting in 1940s. It is well understood that
surface patterning can be used as an effective tool to modulate the
wettability of a surface, including its possible transformation to a super
hydrophobic surface. The generic term super hydrophobicity is used to
designate a surface that exhibits high apparent contact angle (θ* 150°)
along with very low contact angle hysteresis (θCAH < 10°). The Cassie
Baxter state is attributed to the non-penetration of water within the
substrate features, which retain the entrapped air. In contrast, the liquid
– solid contact zone is fully wetted in Wenzel regime, and leads to
higher θCAH and lower θ* as compared to the Cassie state. Under
practical conditions, particularly over prolonged periods of time, col-
lapse of the entrapped air often leads to transition in the wetting state
from Cassie- Baxter to Wenzel, which is associated with a reduction in
θ* [3–5]. The entrapped air bubbles in Cassie configuration is con-
sidered to be the fundamental basis for super hydrophobicity of a sur-
face. However, there are some unique naturally occurring surfaces, such
as a Rose Petal which exhibit very high θ* along with moderate to high
θCAH, and therefore the wetting state on such surfaces cannot be ex-
plained either by the Cassie or Wenzel exclusively. In order to justify
such unique observations, Wang and Jiang defined a number of addi-
tional wetting states such as the Cassie Impregnating state on a hier-
archically patterned surface, the “Lotus” state or the special Cassie state
and the Gecko state on a surface comprising array of hair like features
[6,7].
While artificially fabricated super hydrophobic surfaces find wide
application as self-cleaning, [8] and anti-fouling coatings [9], drag re-
duction in microfluidic devices and so on [10], variety of naturally
occurring super hydrophobic surfaces are observed in the biological
world. The most notable example of this is the water repellence of lotus
leaves, which was discovered by Barthlott and Neinhuis in the early
1900s [11]. The super hydrophobicity of a lotus leaf is attributed to the
hierarchical structures comprising of nanometric hair-like features,
covered with a layer of wax, that are superimposed on the primary
micro-scale papillae (5–9 μm in diameter) [2,12,13].In contrast, a Rose
Petal, which has θ* almost as high as the lotus leaf, exhibits very high
θCAH. This phenomenon has been termed as the “Petal Effect” by Jiang
and co-workers and the observation has led to the coinage of the term
“pseudo-superhydrophobic surface” that refers to a surface that favours
attachment of water droplets, despite exhibiting θ* ≥ 150° [14,15].
However, the precise wetting mechanism on a petal surface is far from
being resolved [16]. Microscopically, a rose petal possess hierarchical
structures comprising of large size micro papillae (average diameter is
15 μm and height is 5–6 μm) which are fully covered with cuticular
folds with periodicity ≈700 nm. Jiang et al. attributed simultaneous
high values of θ*and CAH on a Rose Petal to the Cassie Impregnating
Wetting state, which means that the water meniscus is conformal with
Table 1
Literature review of the techniques used for determination of the wetting state on strongly hydrophobic and adhesive surfaces resembling rose petal surface.
Authors Measurement Technique Measurement Resolution
Jiang et al [14] Schematic representation
Bhushan et al. [17] Optical microscope Schematic representation
Jiang et al. [19] X-ray micro-tomography 50 μm
(Micro-CT)
Teisala et al. [20] Optical microscopy 10 μm
Gao et al. [16] Optical microscopy 200 μm
Present study Confocal microscopy 0.9–20 μm
and in-situ underwater AFM
imaging.
Colloids and Surfaces A 561 (2019) 9–17
the micro papillae but fails to penetrate the nanoscale secondary folds,
where air remains entrapped. In simple terms the wetting state can be
considered as one that is globally Wenzel at the length scale of the
larger features (papillae) but locally is Cassie at the length scale of the
smaller folds. [14] Subsequently, Bhushan et al. also confirmed that
rose petals indeed exhibit a Cassie Impregnating Wetting state, which
they attributed to several geometric parameters such as the periodicity
of the micro- papillae, their peak to base height, peak radius and so on
[17,18].While the original papers lacked in-situ images of the contact
zone, and the wetting state was concluded from indirect evidences, in a
recent paper Jiang used in situ high-resolution X-ray micro-computed
tomography (Micro-CT) to ascertain the wetting state on the surface of
a Rose petal [19]. However, the claim about the Cassie Impregnating
Wetting State on a rose petal has been contradicted by two recent pa-
pers which propose contradicting wetting states, adding more confusion
to the topic! [16,20] Based on in-situ optical microscopy, Teisala et al.
proposed that the water layer adheres to the nano folds only at areas
close to the top of the micro- papillae, and the space between the bumps
close to their base remains parched [20]. Their conclusion is based on
the progressive disappearance of the micro papillae under water when
low surface energy water – alcohol mixture is introduced. However,
since they have used an optical microscope, they could not asses the
vertical plane at which the water meniscus was propagating. As a result,
what they might have observed is simply the penetration of the me-
niscus within the nano folds! On the other hand, based on optical mi-
croscopy, Gao et al. showed an unstable wetting regime on a rose petal
surface, comprising of large air cushions spanning several micro pa-
pillae, and other areas where the papillae are fully submerged. They
argue that these air cushions form due to the accumulation of air that is
dislodged from the area between the papillae. However, they also
mentioned that the air cushions become smaller in size with time,
particularly as the moving air cushions migrate towards the periphery
and dissipate to the surrounding. We strongly believe that the ob-
servation reported in this article actually represents the initial unsteady
state that may prevail on the surface of a rose petal when a droplet is
dispensed onto it. However, with time these air cushions disappear, and
a uniform wetting state below the entire droplet is observed. Also,
based on the resolution of an optical microscope it is not possible to
clearly observe whether the submerged droplets are in Wenzel state or
Cassie impregnating state [16].
Thus, it is clear from the preceding discussion that there are open
questions and lack of direct convincing evidence on the precise wetting
state on a Rose petal. Even though the micro CT image by Jiang
showing the wetting state on a Rose petal (Fig. 3B of Ref. [19] is con-
vincing, it is still a low magnification image covering around 20 micro
papillae. While the image clearly shows that the wetting state is not
Cassie, it is not possible (based on the resolution of the image) to
convincingly conclude if there is any tiny air pocket between two
successive papillae as claimed by Teisala et al. [20] or the liquid me-
niscus is totally conformal with substrate contour. The key studies on
Suggested wetting state on Rose petal
Impregnating Cassie
globally Wenzel at papillae locally Cassie at nano- folds
Impregnating Cassie
Classical Wenzel state at the papillae. Absence of air cushion.
Adherence of water layer to the nano folds only at areas close to the top of the micro- papillae,
and the space between the bumps close to their base remains parched.
Existence of submerged and air-filled micro- papillae together.
Impregnating Cassie state confirmed on positive replica. Cassie Baxter wetting state on
negative replica.
10
U.U. Ghosh et al.
this topic and their main propositions are summarized in Table 1 below
It is evident from Table 1 that the previous studies have mostly
conjectured the wetting state based on optical microscopy and have
provided a schematic of the probable wetting state. Moreover, studies
cited as Ref. [14,17] contradict with those cited as ref. [16,19,20].
Thus, there exists considerable open questions surrounding the wetting
state on a rose petal or generally speaking, on strongly hydrophobic
adhesive surfaces. The present study attempts to address this by the (a)
use of sophisticated confocal microscopy interfaced with (b) In-situ
AFM imaging in two different surrounding media, that is air and under-
water to ascertain the presence of air cushions in the negative replica.
We have performed measurements on a Soft Lithographically fab-
ricated positive replica of fresh Rose petals, the reasons for which are
mentioned later. However, we have performed control experiments on
actual Rose petals as well, to check that the wetting characteristics on
the actual petals and on the positive replicas are identical. Till date, no
other paper has presented the level of magnification at which we have
examined the liquid-solid contact zone on a rose petal or its positive
replica.
In addition to this, we also show that the negative replica of the rose
petal comprising of array of micro wells, which is obtained after the
first imprinting step as an intermediate also exhibits nearly identical θ*
and θCAH as that observed on the positive replica, despite the mor-
phology of the two replicas being totally different. We show that the
wetting regime on the negative replica is very close to the Cassie state,
though it exhibits very high CAH. This observation is unique, as the
Cassie- Baxter wetting state is usually associated with low adhesion. We
have tried to resolve this unique observation based on in-situ AFM
imaging of the actual meniscus and feel that the strong adhesion is
probably attributed to a concave shape of the liquid – air interface over
each micro-well. Our finding on the negative replica leads to the claim
of a new wetting regime which is analogous to a sticky - Cassie state.
Fig. 1. Schematic showing the double moulding replication technique used for fabrication of rose petal replicas - (a) Negative replica and (b) Positive replica
respectively.
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Colloids and Surfaces A 561 (2019) 9–17
2. Materials and methods
2.1. Fabrication of biomimetic replica
In order to avoid the sample degradation with actual rose petals
with time, particularly due to drying, as well as for using a particular
dye (discussed later) the surface structures on the rose petal were first
replicated on an elastomer surface (cross-linked PDMS) following a
two-step replica moulding process. Glass slides (25 mm × 25 mm) were
subjected to ultrasonic cleaning in acetone and water for removal of
adsorbed surface impurities. These slides are then dried in a hot-air
oven for about an hour for complete removal of moisture. For replica-
tion, fresh rose petals were obtained from a nearby nursery in
Kharagpur, India. These rose petals are then trimmed into square pieces
(10 mm × 10 mm) and attached to the cleaned glass slides using a
double-sided adhesive tape. A fixed amount (0.1 g) of degassed pre-
polymer solution of Sylgard-184 (10:1(w/w), base: cross-linker) is then
poured over the rose petal to maintain uniform thickness of the elas-
tomer. [21] This entire setup is then kept in an air oven at 35oC for 36 h
for the elastomer to completely cross-link. A low curing temperature is
essential to eliminate possible damage to the rose petals. Post curing,
the cross-linked elastomer is peeled off from the petal surface (frame a3,
Fig. 1).
The negative replica serves as the master template for the second
step of replica moulding. A thin Sylgard layer is replica moulded using
the negative replica as the stamp. However, in order to prevent cohe-
sive adhesion between the stamp and the Sylgard layer to be patterned,
the negative replica is first subjected to UVO exposure in a UVO
chamber (Novascen, USA). During this stage, the surface is exposed to
highly energetic oxygen radicals that convert the methyl groups in
Sylgard 184 to silanol groups. Although this conversion is limited to the
top-most layer (∼ 100 nm) of the Sylgard 184 elastomer, it prevents
U.U. Ghosh et al.
cohesion and helps separating the two layers. Thereafter, annealing was
performed for 3 h at 100oC for complete cross-linking of the Sylgard
layer. [22]
2.2. Surface characterization
The topographical features of the patterned surfaces were char-
acterized using Field Emission Scanning Electron Microscopy (JEOL,
FE-SEM, Model No: JSM-7800 F) wherein the substrates were coated
with a thin conducting layer of platinum and were scanned in the high
vacuum mode at 2 kV and an Atomic Force Microscopy (AFM, Agilent
Model-5500, PPP-NCL, Nanosensors Inc., USA, Pico View software,
v:1.14) in the intermittent contact mode with a silicon cantilever,
Fig. 2.
2.3. Measurement of contact angles
The wettability of the positive and negative replicas as well as the
actual rose petals were characterized using a Contact angle Goniometer
(OCA15 Pro, Dataphysics, Germany). The samples were placed on the
Goniometer stage and de-ionized water droplets of constant volume
(5 μL) were dispensed on them using a micropipette at multiple (at least
five) locations to evaluate the equilibrium contact angles. The average
values are listed in Table 1 along with the values of the contact angle
hysteresis (θCAH).
2.4. Laser scanning confocal microscopy for tracking the wetting states
A Rhodamine B (0.667 g/l) dyed water droplet (10 μl) was dis-
pensed on the substrates to discern the interfaces. These interfaces are
distinguished by the characteristic red colour caused by the localized
concentration of the dye at the liquid-solid interface. On an actual rose
petal, it becomes difficult to distinguish the dye containing water me-
niscus and therefore, confocal microscopy was used on the positive
replica of the rose petal. The contact line and the bulk regions were
observed separately for each droplet using an inverted laser scanning
confocal microscope (LEICA TCS SP5, Germany), with a 10X objective,
to form a z-stack of the interface. The schematic of the confocal ex-
perimental setup can be found in Figure S1 of the online supplementary
information. The lack or presence of Rhodamine dye in the contact zone
ascertains about the absence or presence of a liquid-air interface, that is
air pockets (Fig. 3).
2.5. Under water imaging using atomic force microscopy
The positive and the negative replicas were scanned under water
using the Atomic Force Microscopy. Underwater imaging of both the
Fig. 2. FESEM images showing the morphology of (a) a rose petal comprising of micro papillae covered with secondary nano-folds (b) negative replica showing an
array of micro wells embedded with the nano-folds (c) positive replica with the micro bumps and some nano-folds. Scale bar for all the frames: 10 μm. Insets show the
corresponding AFM images.
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Colloids and Surfaces A 561 (2019) 9–17
replicas was done using a liquid stage that was mounted directly to the
AFM sample plate. A two stage approach of the cantilever with inter-
mediate re-alignment was performed to take care of the refraction of
the laser beam at the water – air interface. The cantilever stopped at the
liquid – air interface of the liquid stage after the first approach. Beyond
this point a manual approach was performed till the liquid – substrate
interface. [23] Contrast in the feature dimensions in the images of the
respective replicas in air and that under water clearly revealed the
wetting states along the contact zone.
2.6. Evaluation of surface adhesion of the fabricated replica
A custom-made arrangement comprising of a positioning stand
(Thor Labs) to suspend a droplet of fixed volume (10 μL) from the
needle of the syringe and a high precision micro-electromechanical
balance (Sartorius, AG Gottingѐn, Germany) is used to quantify the
surface adhesion force.
The substrates were placed on the balance and the suspended dro-
plet is brought in close contact with the substrate till the weight of the
droplet is equivalent to that of a sessile droplet placed on the substrate.
Once this equilibrium weight is attained, the balance is initialized
(force = 0) as shown at the inset (a) in Fig. 5. Slowly, the droplet (using
the positioning stage) is pulled in the + z direction, away from the
substrate (inset b) and the corresponding deflections in the weight at
equal height intervals of 0.05 mm are recorded.
3. Results
3.1. Morphology of the fabricated replicas
The FESEM images in Fig. 2 show the morphology of the surface of a
rose petal, its negative replica and positive replica respectively. The
images reveal that the rose petal surface is densely populated with -
papillae. These micro-papillae are covered with a layer of submicron
features which are referred to as nano-folds as they extend from the
peak of the bump towards its base. This structural hierarchy is inverted
in orientation after the first replication stage, which consists of a colony
of micro-wells with inverted nano-folds placed at the bottom of the
wells. The corresponding AFM images are shown as insets in the re-
spective frames.
The AFM images (insets of Fig. 2) reveal that the height and base
diameter of the micro-papillae on a rose petal are ≈ 6 μm and ≈
18.8 ± 1.2 μm respectively. The nano-folds have a height of
450 ± 17 nm. Expectedly, the depth of the microwells in Fig. 2b is of
the same order as that of the height of the micro bumps. The height and
diameter of the bumps in the positive replica shown in Fig. 2c are
nearly identical to those seen in Fig. 2a, though the height of the nano-
U.U. Ghosh et al.
Fig. 3. Confocal images indicating the wetting state on the (A) positive replica is (A1) Impregnating Cassie at the periphery as well as in the (A2) droplet bulk
whereas on the (B) negative replica is (B1) Cassie Baxter in the droplet bulk and (B2) at the contact line. Scale bar: 20 μm.
folds is somewhat reduced to 256 ± 18 nm. The surface roughness
(Rrms) for the positive and negative replicas has been evaluated and is
found to be ∼ 1.270 μm and ∼ 1.175 μm respectively.
3.2. Wettability and contact angle hysteresis (CAH) analysis
The wettability of each type of surface shown in Fig. 2 is quantified
in terms of the apparent contact angle (θ*), advancing (θa) and receding
contact (θr) angles. We have measured the CAH based on the needle-in-
the-sessile-drop method, [24–26] which is specifically suitable for the
present study owing to the highly adhesive nature of the substrate that
prevents the drop from sliding, even at high tilt angles and is similar to
the adhesion test used thereafter.
To evaluate the static advancing and receding contact angles, de-
ionized water (Millipore) droplets are dispensed using an automatic
dispenser. Equal volumes (1 μL) of water droplets are dispensed here-
after with a corresponding increase in the contact angle and this process
is continued till the contact angle stabilizes at its maximum value.
Further addition of liquid causes the contact line to advance. The
contact angle just ahead of de-pinning is measured as the advancing
contact angle( a) . Similarly, for determination of the receding contact
angle the liquid is retracted in equal volumes (0.5 μL) from the droplet
till the three phase contact line starts to retract. The entire process is
repeated at least thrice on each type of samples and the average values
are reported in Table 2.
3.3. Determination of wetting states
The exact nature of the solid-liquid contact zone is probed using a
confocal microscope (Fig. 3) as well as in-situ under AFM imaging
(Fig. 4). Droplets containing Rhodamine dye having surface tension and
apparent equilibrium contact angles (γ∼ 72 mJ/m [2], θwater ∼ 136°)
nearly identical to de-ionized water are placed on the replica surfaces
and observed under the confocal microscope. The intensity of the red
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Colloids and Surfaces A 561 (2019) 9–17
colour emitted by the Rhodamine dye is an indicator of the preferential
adsorption of rhodamine on to the substrate surface. The top row
images are the x–y scans of the replicas whereas the bottom row are the
corresponding x–z and y–z images (orthogonal sections/slices) at the
same focal plane as presented in Fig. 3. The choice of the focal plane is
determined by the maximum focus that can be achieved at the parti-
cular location.
3.3.1. Wetting state on positive replica
The typical honeycomb pattern (of hexagonal structure) is visible
although the entire structure is showing a uniform deep red colour. This
implies that rhodamine has covered the bumps completely. It can be
clearly deduced by comparing the AFM images shown as Fig. 4(a) and
(b), which show the scan of the positive replica in air and water re-
spectively, that the vertical scale bar in both the cases is same, which
implies that the water meniscus is conformal to the contours of the
substrate pattern including the micro bumps. However, slightly reduced
roughness of the secondary folds in Fig. 4(b) implies that while water
conformally wets the micro-papillae it may not wet the secondary folds
completely. By combining the observations of the confocal and the
atomic force microscope, we can conclude with confidence that the
positive replica exhibits Impregnating Cassie regime of wetting.
The wetting state of water on positive replica can be further un-
derstood from the AFM images shown in Fig. 4 (a) and 4 (b). Not only
the morphology of the surface is nearly identical in both the frames, but
Table 2
Characterization of surface wettability.
Apparent Contact Angles Contact Angle Hysteresis
(θ*) CAH = ( a r)
Rose Petal 140.1 ± 5° 76 ± 5°
Negative Replica 136.8 ± 3° 70 ± 3°
Positive Replica 138.5 ± 2.6° 75 ± 1.3°
U.U. Ghosh et al.
Fig. 4. AFM images showing the surface topography of: (a and b) Positive replica of Rose Petal in Air and under water; (c and d) Negative replica of Rose Petal in Air
and under water. Insets in all the frames represent the corresponding phase images. (e) Schematic showing the wetting state on the Positive Replica of Rose petal
under water, particularly air pockets over each nano folds.
the vertical scale bar is ≈ 5 μm for both the frames. This indicates that
air and water cover the humps on the positive replica conformally in
the respective cases. In frame b, the intensity as well as the depth of the
nano-folds resting on the larger humps is lower, which implies that
water meniscus fails to penetrate in to the nano grooves. This in turn
results in air pockets trapped around the secondary nano-folds, as has
been schematically shown in frame (e) of Fig. 4. This observation allows
us to conclude that the wetting state on a positive replica of Rose petal
may be deemed as a superposition of globally Wenzel and locally Cassie
State of Wetting.
3.3.2. Wetting state on negative replica
A typical honeycomb pattern comprising of hexagons is evident
(Fig. 3, B1 and B2), wherein only the edges of each of these hexagons
shows a deep red colour, implying that rhodamine has access to the
edges only. The interior of each hexagon is less bright indicating the
absence of dye within the micro-wells. This implies that the negative
replica exhibits air-filled micro-wells as physically manifested by the
varying intensity of rhodamine from the edge to the interior of the
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Colloids and Surfaces A 561 (2019) 9–17
hexagon. These dye-enhanced pictures of the substrate surface under
the droplet suggest the wetting state to be Cassie-Baxter in the droplet
bulk.
Frames (c) and (d) of Fig. 4 further reveal the morphology of a
negative replica of Rose petal in air and under water. Notably, the scale
bar drops drastically from ≈ 6 μm in air (Fig. 4, frame (c)) to
about < 1 μm in Fig. 4, frame (d). This reduction in feature height is
due to non penetration of water meniscus inside the pits on the negative
replica, indicating direct evidence of Cassie state of wetting. This con-
jecture is further corroborated from the phase contrast image shown in
the inset of Fig. 4(d) which clearly captures the existence of the pits.
This means that the water meniscus is resting on different materials at
different places. While it is in direct contact with the solid surface over
the ridges between the pits, it is floating over air over the pits. This
leads to the contrast that is observed in the phase image. [27,28]
There have been prominent studies [29–31]concerning the wetting
transitions that occur on paraboloid microprotrusions. It is established
from these studies that there exists two geometric parameters - radius of
the micro-protrusion (R) and pitch (b) (spacing between two
U.U. Ghosh et al.
Fig. 5. Variation in the normal surface adhesive force for the master template
(rose petal) and the fabricated negative and positive replica. The maximum
adhesive force for the negative replica is evidently higher than the master
template and its positive replica. Droplet images at the inset indicate the spe-
cific point of adhesive force measurement, that is (a) Adhesion force is zero, the
droplet is placed on the substrate (b) droplet is pulled by the syringe and an
increase in the force of adhesion is observed (c) neck formation and (d) Droplet
detachment and the force of adhesion reduces to zero again.
protrusions) that define the wetting state over such surfaces and at a
critical ratio (R/b ∼2) of these parameters the wetting state undergoes
a transition from the composite to non-composite state, as be the case.
In accordance with the free-energy based analysis given in these re-
ports, the micro-wells and micro-bumps in the present study have base
radii of R = 11 μm and therefore the corresponding critical pitch for a
stable wetting state should be, bc = 5.5 μm. However, it is evident from
the AFM images that the pitch is less than 1 μm (b < 1 μm). This implies
that the wetting state should be composite (Impregnating Cassie and
Cassie-Baxter over the positive and negative replica respectively.) since
the actual pitch is lesser than the critical pitch. Clearly, this is in ac-
cordance to the experimentally observed wetting states observed using
confocal microscopy (Fig. 3).
It must be stated here that the dynamics of Wetting transition (WT)
is under explored [32–35]on such superhydrophobic and strongly hy-
drophobic surfaces owing to the time-scale (of the order of ∼ tens of
milliseconds) over which the transition occurs, which is extremely
difficult to capture in real time. Such high-speed imaging should also be
accompanied with the ability of post-processing the captured images. In
addition to this, the region of interrogation is of the order ∼ few μm
and in close proximity to the contact line over a structured surface.
These two requirements cannot be achieved with the existing experi-
mental set-up since a single x–y-z scan using confocal microscope that
requires ∼ few minutes. This mis-match in timescales of transition
event and imaging speed needs to be resolved to track wetting transi-
tions in the present study and will be investigated in the future.
3.4. Correlation of the wetting state with surface adhesion
The surface adhesion measurements (details in the experimental
Section 3.6) are used to evaluate the surface adhesion by the following
expression, F (surface adhesive force) = mg where, m is the mass of the
droplet (kg), g is the acceleration due to gravity (m/s2). This movement
of the stage leads to a gradual increase in the adhesive force (mani-
fested as loss in weight), till the location indicated by (c) in the Figure.
At this point the meniscus connecting the droplet and the substrate is
stretched to its maximum with a clear neck formation, indicating
maximum force sustained by the intact droplet, which is an indicator of
the adhesive strength between the droplet and the surface. Further re-
traction of the droplet leads to detachment of the droplet from the
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Colloids and Surfaces A 561 (2019) 9–17
needle and the adhesive force falls rapidly to zero (inset (d) in Fig. 5).
The force of adhesion F (in μN) is directly proportional to the area of
contact, A(in mm [2]) between the liquid-solid surface and is expressed
as [36],
F A (1)
F= k1A (2)
where k1 is the proportionality constant. According to Liu et al., the
proportionality constant k1 (Eq. 2) is represented as KI where K is a
constant and I depends on the surface property. Thus, one can correlate
F with A for a specific substrate as,
F= KIA (3)
Where, k1=KI
Further, one can re-arrange and write,
F= K̄I (4)
Where, K̄ = KA
However, the results presented in Fig. 5, demonstrate that the ad-
hesion strengths are nearly identical for the positive replica and the
original rose petal, underscoring that the role of surface property is not
significant. The situation becomes more interesting on the negative
replica, where A for both the cases (positive and negative replica) is
nearly identical based on the confocal (Fig. 3(b)) and in-situ atomic
force microscopy (Fig. 4 (d)) images. We have already argued that the
wetting state is Cassie-Baxter, as the water fails to penetrate the micro-
wells on the negative replica. Therefore, the contact area is limited only
to the 'inter-connected' edges between the micro-wells, as can be seen
from the confocal (Fig. 3(b)) and AFM images (Fig. 4(d)). This implies
that the interfacial contact area 'A' (Eq. (1)) for the negative replica is
much lower as compared to that between water and the positive re-
plica/actual rose petal. However, Fig. 5 shows that the force of adhe-
sion, Fmax (for the negative replica) is slightly higher than Fmax (positive
replica/rose petal). This is possible only when K̄ is much higher for a
negative replica as compared to that of the positive replica or an actual
rose petal. This provides a new insight over the recent findings by Liu
et al. that the proportionality constant k1 is a function of the wetting state.
In order to probe the higher value of k1 on the negative replica,
which is responsible for an unique wetting state that has Cassie-Baxter
like wetting regime with entrapped air but exhibits high adhesion, we
focus on the shape of the water meniscus over each micro-well. It can be
inferred from the confocal (Fig. 3(b)) as well as the AFM (Fig. 4(d))
images that the shape of the water meniscus below a stationary sessile
droplet (i.e. without tensile stress/upward pull) over each micro-well is
'concave'. During the adhesion test, as the drop is pulled upwards by the
syringe, we conjecture that the meniscus over each micro well under-
goes an inversion from its initial concave configuration to a convex
shape along with the bulk of the liquid. This change in curvature is
associated with a change in the Laplace pressure. In qualitative terms,
the energy supplied to the water droplet during tensile pull is consumed
in the water meniscus inversion over each micro-well.
This additional pressure drop across a single inverted meniscus can
be estimated by the Young-Laplace equation as,
Pl Pv = (5)
where Pl and Pv are the pressure at the liquid and vapor phase re-
spectively, γ is the surface tension of the liquid (γ ∼ 72 mJ/m2) and κ is
the curvature of the meniscus. Thus the equivalent capillary force due
to inversion of meniscus over a single micro-well can be evaluated as,
Fcapillarymeniscus |singlemicro-well = Aliq. cap (6)
Where, Aliq.cap is the area of the liquid cap covering the micro-well. The
area of the liquid cap Aliq. cap is assumed to be equivalent to a circle with
the measured diameter of the micro-well, i.e. ≈ 20 μm and the curva-
ture K is estimated as the inverse of the depth of penetration by the
water meniscus (≈ 1.8 μm as evaluated from the under-water in-situ
U.U. Ghosh et al. Colloids and Surfaces A 561 (2019) 9–17

atomic force microscopy image, Fig. 4(d)). The contribution of capillary Hr

D
P2
force for inversion over a single micro-well as per Eq. (8) is D
Fcapillarymeniscus = 0.0183 μN. A droplet of 10 μL has a footprint (base Hr = C P2 (9)
diameter ∼2.25 × 10−3 m) with an equivalent area ∼ 5.09 × 10-12 m2
where C is a proportionality constant. In the present study, the micro-
and covers ∼ 9450 micro-wells (Refer to Supplementary Information,
fabricated pillars are replaced by the naturally occurring and soft-li-
Note S2 for details of micro well density estimation). Thus, the total
thographically replicated micro-bumps and wells. The inter-bump dis-
contribution to capillary force by 9450 micro-wells is
tance is significantly reduced and therefore the pitch is almost absent.
Fcapillarymeniscus |singlemicro-well = Aliq. cap × Number of micro-wells (7) For such closely spaced micro-bumps, we study the influence of varying
the pitch and the surface roughness (tuned using 'C') for pillars having
This leads to an overall capillary force contribution of 173.56 μN for the
diameter equivalent to the diameter of the soft lithographically fabri-
estimated 9450 micro-wells. The force of adhesion (Ftheo, NR = K ANR ) is
cated microbumps/microwells in this study. Here, the fSL (∼0.5) is
theoretically evaluated to be ∼ 27.83 μN (Refer to Supplementary In-
assumed to be a constant for all the surfaces.
formation, Note S2 for details.) considering Cassie-Baxter state of
It is evident that for a surface with structural hierarchy the mag-
wetting. However, the experimentally evaluated force of adhesion is ∼
nitude of CAH for a particular surface roughness (C = constant) varies
200μN. The difference in the theoretically and experimentally eval-
inversely with the pitch. In other words, CAH attains a maximum value
uated force of adhesion may thus be attributed to the additional ca-
for extremely low pitch or closely spaced structures and asymptotically
pillary force (∼ 173.56 μN) arising due to the menisci inversion as
reduces to zero with an increase in pitch. For example, it can be seen
described before. Thus we believe that such inversions contribute sig-
from Fig. 6 that the CAH becomes negligible for high pitch (P > 4 μm)
nificantly to the total adhesion of a droplet in the Cassie-Baxter state of
irrespective of surface roughness. For low pitch, the contribution of
wetting on such surfaces.
surface roughness dominates over the contribution of adhesion hys-
Therefore, on the negative replica we identify a new wetting regime,
teresis. A minor increase in surface roughness quickly escalates the
which may be termed as an Adhesive Cassie regime; where there are
magnitude of CAH. Thus, for a surface to exhibit strong hydrophobicity
entrapped air bubbles exactly like typical Cassie state but the strong
and high adhesion simultaneously, the structural hierarchy of closely
adhesion is attributed to the convex curvature of the water meniscus
knitted individual primary structures is a necessity and is true for the
over each micro-well during the adhesion strength test.
present study.
There are several theoretical approaches that model the wetting
3.5. Effect of micro-well diameter variation on the adhesion strength of the
states on superhydrophobic surface with multi-scale roughness [38,39]
fabricated surface
and predict the evolution of the contact angles as a function of the
underlying geometric aspects of the structures. These are based on the
To investigate the effect of micro-well diameter on the adhesion
liquid penetration into these complex structures and predict that uni-
strength of the replica, the fabrication of different size of micro-wells
formity as well depth of liquid penetration [40] are important para-
can be brought about by varying the depth of the micro-well, altering
meters in determination and transition of the wetting states over these
the perimeter of the micro-well or by the alteration of the entire hier-
surfaces.
archical structure (micro-bumps with nano-folds) by drying rose petals.
We fabricated negative replicas of indigenous and foreign variety rose
petals to achieve the same. Adhesion tests were performed on these 4. Conclusions
replicas and the results (with details) are provided in the online sup-
plementary information, Note 4. In this article we have examine the wetting states on a rose petal
The major observations establish that the specific colour of a petal and its positive and negative replica (fabricated using soft lithography
stems from the colour pigments and is found to be a weak function of on cross-linked PDMS using laser scanning confocal microscopy and
the micro and nano-structures present on its surface. Therefore, the under water in-situ atomic force microscopy at a never before achieved
primary objective of varying micro-well diameter can be brought about resolution. Firstly, we show that all the three types of surfaces are
by using rose petals of different genus. Further, it has been observed strongly hydrophobic (θ*≈ 140°) but exhibit very high adhesion to a
from the fabricated negative replicas of the foreign variety of rose pe- sessile drop dispersed on it. In fact, the strength of adhesion on the
tals that the adhesion force is strongly dependant on the size of micro- actual rose petal and the positive replica are nearly identical, which
wells and even a slight variation of 2–3 μm in the micro-well diameter implies that the adhesion strength is attributed primarily to the
affects the resulting adhesive force. However, the variation in adhesion
force is random and direct correlation of only the micro-well diameter
with adhesion force is not straightforward.

3.6. Role of contact angle hysteresis on strongly hydrophobic adhesive

surface

The CAH can arise from two contributions - adhesion hysteresis

(AH) and surface roughness (Hr). These can be mathematically ex-
pressed as given by Equation [37] (1)
cos a cos r = AH + Hr = fSL (cos a0 cos r 0) + Hr (8)
where a 0 , r 0 are the advancing and receding angles on a smooth
surface (105° and 98° respectively for a smooth PDMS surface-deionized
water droplet system and a , r are the effective contact angles on a
rough surface, fSL is the fraction of solid-liquid area for a rough
/composite surface. Herein the roughness term has its origins in the
pinning of the contact line on the edges of the pillared surface. Fig. 6. Variation in contact angle hysteresis (CAH) with pitch and surface
Let D and P be the diameter and pitch of the pillars, then Hr can be roughness. The dotted lines [·····] indicate the CAH obtained experimentally for
expressed as, the fabricated replicas and original rose petal.

16
U.U. Ghosh et al.
hierarchical geometry of the substrate rather than its material proper-
ties.
Further, based on in-situ imaging we show that the wetting state on
the positive replica is Impregnating Cassie State, thereby, resolving
existing anomalies in the field. None of the earlier studies on this have
examined the water-substrate contact zone at a resolution that we could
achieve based on a combination of confocal microscopy and in-situ
AFM. Using the same instruments, we further resolved the wetting state
on the negative replica that it is similar to classical Cassie State, as
submerged air pockets are seen within every micro-well. However, the
surface exhibits even higher adhesion as compared to an actual Rose
petal or its positive replica, which is unusual for a surface exhibiting
Cassie State of wetting. We term the wetting state on negative replica as
the "Adhesive Cassie State".
Acknowledgements
SDG gratefully acknowledges the financial support provided by the
Indian Institute of Technology Kharagpur, India [Sanction Letter no.:
IIT/SRIC/ATDC/CEM/2013-14/118, dated 19.12.2013]. RM acknowl-
edges IIT Kharagpur for a project under the Challenge grant (SRIC
Code: VPP).
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