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Leaf-mimicking polymers for hydrophobicity and high transmission haze

Article in Proceedings of the Estonian Academy of Sciences · November 2017

DOI: 10.3176/proc.2017.4.24

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 Proceedings of the Estonian Academy of Sciences, 4017, 66, 2,

Proceedings of the Estonian Academy of Sciences,

2017, 66, 4, 444–449
https://doi.org/10.3176/proc.2017.4.24
Available online at www.eap.ee/proceedings

Leaf-mimicking polymers for hydrophobicity and high transmission haze

Zhongjia Huanga*, Congcong Caia, Xinying Shib, Taohai Lic, Marko Huttulab, and Wei Caob*
a
School of Mechanical and Automotive Engineering, Anhui Polytechnic University, Wuhu 241000, China
b
Nano and Molecular Systems Research Unit, University of Oulu, P.O. Box 3000, FIN-90014, Finland
c
College of Chemistry, Key Lab of Environment‒Friendly Chemistry and Application in Ministry of Education, Xiangtan
University, Yuhu District, Xiangtan 411105, China

Received 24 April 2017, revised 10 July 2017, accepted 21 August 2017, available online 30 November 2017

© 2017 Authors. This is an Open Access article distributed under the terms and conditions of the Creative Commons Attribution-
NonCommercial 4.0 International License (http://creativecommons.org/licenses/by-nc/4.0/).

Abstract. Gifted with unique optical and hydrophobic properties, the plant leaves have been recently considered as micro/
nanostructure prototypes for functional surface engineering. Imprinting bio-inspired structures onto surfaces can yield in similar
functional properties than in the nature. In this article, we report on a simple and effective method to copy leaf surface structures
onto poly-(methyl methacrylate) sheets. The replicated surface structures reduce optical reflectance and enhance optical haze.
Besides, the artificial polymer sheets exhibit good hydrophobic properties. Correlation between optical haze and hydrophobicity
was studied.

Key words: bionic leaf replication, hydrophobicity, optical haze, contact angle.

1. INTRODUCTION recent studies both, experimental and theoretical results

*
demonstrated that the bio-mimicked structures have
During the ages of evolution, nature has developed good optical transparency and haze ratio [7,8] leading
unique characteristics for living creatures. Learning to efficiency increase when applied to photovoltaics.
from these structures may provide an effective way to On the other hand, leaves of both, aquatic and terrestrial
solve problems encountered by human beings. Plant plant species, exhibit hydrophobic properties [9,10]. Large
leaves produce most of the oxygen and organic matter contact angles against water make it easy to remove
on earth through photosynthesis. Typically, dedicated raindrops and dust from the leaf surfaces [11]. Such
micro/nanostructures are developed on leaf surfaces to hydrophobic properties are attributed to the surface
apt for different natural ambiences, for example lotus energy and surface roughness [12]. The latter, i.e.
leaves show a structure of nano bumps on conical papillae micro/nanostructures on the surface, is the key factor for
[1–4]. The typical size of such hierarchical structure is superhydrophobicity [13].
comparable to the wavelength of visible light, which Despite individual research progresses [7], systematic
offers particular optical properties to the plant leaves. studies on the correlation between the optical and
There have been plenty of researches focusing on hydrophobic properties are insufficient. In the application
mimicking the leaves and applying them as optical of anti-reflection films on solar cells, the hydrophobicity
functional films. For example, inspired by photosynthesis, should be also taken into account. A hydrophobic surface
the artificial films were used in photovoltaics to reduce can easily be kept uncontaminated from the rain and dust
the high reflection of bare silicon solar cells [5,6]. In to reduce photon loss, leading to a highly efficient light
harvesting process. Moreover, the leaf surface structures
*
Corresponding authors, hzj@ahpu.edu.cn, wei.cao@oulu.fi contribute to both, optical and hydrophobic properties, so
Z. Huang et al.: Leaf structure for functional polymer 445

that certain relevance may exist between these two microscope (FESEM) and surface profilometer. Optical
aspects. Therefore, efforts should be devoted to figuring properties were measured by a transmittance and haze
out such relationships for possible leaf candidates. tester (WGT-S, Shanghai Physical Optics Instrument
Hydrophobic surfaces with optically transparent properties Co., Ltd). Hydrophobic properties were measured by
may facilitate to find a variety of applications. a wetting apparatus. Numerical simulation of light
In this work, we imprinted 32 kinds of leaf structures scattering was carried out by the finite-differential-time-
onto poly-(methyl methacrylate) (PMMA), of which we domain (FDTD) method with the software of Lumerical
mainly studied the sugarcane, maize and lotus leaf Solutions Inc.
replicas. All the bio-mimicked PMMA sheets show high
optical haze ratio (up to 80%), while the transmittance
varies depending on the morphologies. Computational 3. RESULTS AND DISCUSSION
simulations were also performed to clarify the interaction
between light and leaf structures. Bionic PMMA sheets Morphologies of the replicated sugarcane, maize and lotus
were found to have higher contact angles than the leaves exhibit distinct microstructures. The sugarcane
smooth ones. Based on this, the relationship between leaf surface (Fig. 1a) is composed of long concave strips
hydrophobicity and optical haze has been studied. (~20 µm width) with small randomly dispersed elliptical
pits. The major axis of those pits lies parallel to the
strips. The maize leaves (Fig. 1b) have similar concave
2. METHODS strips, but with elliptical stomata arranged on both sides.
There are also linear bumps filling the gaps of adjacent
A two-phase fabrication process was used to replicate protrusions. The lotus leaf (Fig. 1c) is typically a flat
the sugarcane, maize and lotus leaves. Firstly, a fresh surface, decorated with plenty of hierarchical protrusions,
and clean leaf was fixed at the bottom of a container, that is, nano bumps (see the inset) on top of conical
then polydimethylsiloxane (PDMS) was deposited on papillae (5‒10 µm). Fig. 1d‒f show the surface profile
the leaf surface. This process produced the negative of leaf structures in Fig. 1a‒c. It is possible to obtain the
structure of the original leaf. Then PMMA was poured height profile according to the colour scale. The sugarcane
onto the negative PDMS film. After polymerization, and maize leaves have much higher microstructures than
degasification and annealing in a vacuum oven, the lotus leaves.
PMMA was detached from the PDMS mold and it Based on the surface profile information, we
would copy all the fine structures of the leaf surface. established 3D models for the sugarcane, maize and
The morphologies of the bionic PMMA sheets were lotus leaves (Fig. 2a‒c). The nanoscale structures
characterized through field emission scanning electron (Fig. 1c) were ignored in the models. They are supposed

Fig. 1. SEM images and surface profile of replicated sugarcane, maize and lotus leaf structures. (a), (d) sugarcane; (b), (e) maize;
(c), (f) lotus. The inset shows a zoomed-in image on lotus leaf. The surface profiles of randomly selected square regions
(panel d, e, f) were taken on the replicated leaves but at different positions from SEM images, and the side lengths were marked in
each panel.
446 Proceedings of the Estonian Academy of Sciences, 2017, 66, 4, 444–449

Fig. 2. Numerical simulation of light interference with the leaf models: (a) sugarcane model; (b) maize model; (c) lotus model;
(d) simulation results of optical reflectance in the range of visible light.

to play an important role in hydrophobic behaviours [12]. leaves help to reduce the reflectance and promote the
However, computational work reveals a limited influence light harvesting, while structures on butterfly wings
on the reflectance [8]. The simulated reflectance keeps interfere strongly with visible light, producing distinct
nearly unchanged after introducing nanostructures into a colours for the purpose of pairing or camouflaging.
microscale hemisphere model. We calculated the optical When light irradiates on the above PMMA sheets,
reflectance of the leaf structures as well as the smooth it will be reflected, absorbed and the rest will pass
PMMA sheet. There is no obvious peak for all the through. Lower reflectance will let more photons to get
models, suggesting that the models have similar into the leaves, but it would be also beneficial to get
reflective ability in the whole range of visible light. On a larger absorption area. The transmitted light will be
the other hand, all the reflectances are extremely low. scattered by the microstructures before it penetrates the
Plant leaves will benefit from such low reflectance leaves. Such wide angle scattering makes the transmitted
property, which lets more photons to be involved in the optical spot larger than the incident beam. That means,
photosynthesis. Also, it shows that the leaf surface when the sheets with a larger haze ratio are coated on
microstructures on the PMMA sheets reduced the re- silicon solar cells, more silicon area will be involved in
flectance in comparison with the smooth one (< 3% for the photovoltaic process, leading to higher photovoltaic
leaf structures and ~3.5% for smooth PMMA sheet). It efficiency. Fig. 3a shows the transmission haze for
is noteworthy that not all the bio-mimicked structures mimicked maize leaf. The laser beam with a diameter of
are in favour of anti-reflection. Different from patterns on 3 mm produced a ~20 cm spot after travelling through
plant leaves, specific naturally occurring nanostructures the PMMA. Fig. 3b illustrates the light scattering
(e.g. butterfly wings) could induce high reflectance mechanism on the microstructure patterned surfaces.
(varying from 65% to 98% with different incident angles) A maximum open-angle of 41º was found for the bionic
in visible light range [14]. Surface structures of plant maize leaf.

Fig. 3. Measurements of optical

transmission haze. (a) Incident laser
beam scattered by bionic maize leaf;
(b) schematic diagram of light scattering.
Z. Huang et al.: Leaf structure for functional polymer 447

The experimental results of transmittance and optical differ its application from the other two. The trend line in
haze ratio are well consistent with the expectation. Fig. 4 shows relationships between optical transmittance
Smooth PMMA sheet is highly transparent to the and haze ratio for PMMA sheets with different surface
incident light, but the haze ratio is extremely low (5.2%). structures, it suggests that the transmittance decreases
The microstructures on the bionic sheets greatly enhanced with the increase of optical haze.
the haze ratio along with a reduced transmittance. Among Water contact angle measurements have confirmed
the three leaf structures, maize leaf shows the highest that all three bionic PMMA structures are hydrophobic
haze ratio while lotus leaf has the best transmittance. (see Fig. 5). It suggests that the fabrication method is
Sugarcane leaf has poor transmittance, which would a general route to integrate optical and hydrophobic

Fig. 4. Relationships between optical transmittance and haze ratio for PMMA sheets with different surface structures.

Fig. 5. Contact angle measurements of four

PMMA sheets with different surfaces.
Bionic structures replicated from sugarcane
(a), maize (b) and lotus (c) leaves. Smooth
PMMA was also measured as reference (d).
448 Proceedings of the Estonian Academy of Sciences, 2017, 66, 4, 444–449

properties together. Though the PMMA is composed of PMMA. Lotus, sugarcane and maize leaves exhibit better
organic molecules, the smooth surface does not exhibit ability to repel water than the others. Remarkably, these
good hydrophobicity (Fig. 5d). When the water droplets three leaves also have relatively high optical haze. They
meet surfaces with micro- or nanostructures, the contact are therefore promising candidates for anti-reflection
area is limited. Based on Cassie’s model [15], the films, e.g. transparent coating on photovoltaic cells. The
droplets only contact the top of those spikes, bumps and one with the highest contact angle (130º) is photinia
papillae, with air trapped in the interspace. Smaller serrulata leaf, but the mediocre optical haze may make
contact area leads to a decreased free energy for the it unsuitable in many occasions. Study with all replicated
interface, providing a driving force to repel the droplets leaves shows that there is no strict correlation between
[16]. The shape, size and arrangement of the micro- hydrophobic ability and optical haze. A particular
structures contribute to the hydrophobicity, leading to micro/nanostructure may have strong interaction with
distinct contact angles on different bionic PMMA light of certain wavelength. Though it may not be an
surfaces. Compared to sugarcane (Fig. 5a) and maize ideal architecture for trapping air when contacting water
leaves (Fig. 5b), lotus leaf shows better hydrophobic droplets, it can act as a hosting matrix for nano-porous
property (Fig. 5c). As shown in Fig. 1f, the papillae complexes to enhance surface wettability through other
were closely and neatly dispersed. Those nano bumps materials engineering routes, such as screen-printing
on the papillae further reduced the contact area. Besides technique and solvothermal method [18,19].
the large static contact angle, droplets on such surface
also show a small sliding angle and thus can be easily
removed. It is worth noting that the contact angle on 4. CONCLUSIONS
bionic lotus surface is slightly smaller than previous
results directly measured on lotus leaves [17]. From the In summary, bionic PMMA sheets of sugarcane, maize
structure point of view, some of the nanoscale fiber-like and lotus leaves were replicated via an efficient and
features were missed during the replication process and low-cost method. Simulation and experimental results
this probably affected the hydrophobicity. Also, the reveal that the PMMA sheets with leaf surface structures
PMMA may have distinct ability to repel water from the have extremely low reflectance and relatively high
waxy epidermis of lotus leaves. transmission for visible light. Except for the replicated
Besides the aforementioned bio-mimicked leaves, maize leaf, sugarcane and lotus leaf replicas possess
another set of 28 plant leaves were replicated. Most good optical transmittance and haze ratio. We also
bionic PMMA sheets have enhanced optical haze ratio propose that distinct microstructures are required in
ranging from 55‒85%, while the hydrophobic properties order to repel water droplets and scatter light. This study
are of great difference (see Fig. 6). There are 13 PMMA also provides a clue that properly optimized surface
sheets which are hydrophilic, including the smooth structures could have better performance in both aspects.

Fig. 6. Relationships between contact

angle and haze ratio for PMMA sheets
with different leaf surfaces.
 Z. Huang et al.: Leaf structure for functional polymer 449

ACKNOWLEDGEMENTS 8. Huang, Z., Shi, T., Zhang, H., Zhang, M., Huttula, M.,
and Cao, W. A computational study of antireflection
structures bio-mimicked from leaf surface morphologies.
The authors acknowledge the financial support from
Sol. Energy, 2016, 131, 131−137.
Anhui Polytechnic University (No. 2016BJRC005). 9. Neinhuis, C. and Barthlott, W. Characterization and dis-
We thank Dr Hui Zhang and Soochow University for tribution of water-repellent, self-cleaning plant surfaces.
assisting the numerical simulation. We also thank Ann. Bot., 1997, 79, 667−677.
Dr Nan Wang and Nanjing University of Science and 10. Ganesh V. A., Raut, H. K., Nair, A. S., and Ramakrishna, S.
Technology for assisting the contact angle measure- A review on self-cleaning coatings. J. Mater. Chem.,
2011, 21, 16304−16322.
ments. X. Shi is grateful for the scholarship sponsored
11. Nakajima, A., Fujishima, A., Hashimoto, K., and Watanabe, T.
by China Scholarship Council. The publication costs of Preparation of transparent superhydrophobic boehmite
this article were covered by the Estonian Academy of and silica films by sublimation of aluminum acetyl-
Sciences and the University of Tartu. acetonate. Adv. Mater., 1999, 11, 1365−1368.
12. Feng, L., Li, S., Li, Y., Li, H., Zhang, L., Zhai, J.,
Song, Y., Liu, B., Jiang, L., and Zhu, D. Super-
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Kopeeritud lehepinna struktuur hüdrofoobsuse ja suure läbipaistvushajususe

saamiseks polümeeridel

Zhongjia Huang, Congcong Cai, Xinying Shi, Taohai Li, Marko Huttula ja Wei Cao
Tänu unikaalsetele optilistele omadustele ja hüdrofoobsusele on hakatud taimede lehti pidama sobivateks ees-
kujudeks funktsionaalsete mikro- ning nanostruktuursete pindade valmistamisel. Artiklis on kirjedatud lihtsat ja
efektiivset meetodit taimelehe pinnastruktuuri kopeerimiseks polümetüülmetakrülaadi kihtidesse. Kopeeriti suhkruroo-,
maisi- ja lootoselehtede struktuuri. Tulemusena vähenes valguse peegeldus polümeerikihilt ja suurenes kihti läbinud
valguse hajumine. Samuti suurenes pinna hüdrofoobsus. Tehti kindlaks korrelatsioon valguse hajumise ja hüdro-
foobsuse vahel.

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