School of Multidisciplinary Engineering

Center for Materials Engineering

Seminar presentation on paper titled:

Fabrication of biomimetic robust self-cleaning super-hydrophobic wood

with canna-leaf-like micro/nanostructure through morph-genetic method
improved water-, UV-, and corrosion resistance properties
Original paper by: Yushan Yang, Huajie Shen, Jian Qiu
Elsevier, Journal of molecular structure, June 2020.

Presentation by: Abenezer Mengistu

Outline

1. Introduction

2. Experimental section

3. Results and discussions

4. Conclusion

5. Remarks

Abbreviations

BMSW: Biomimetic morphologies superhydrophobic wood

PDMS: Polydimethylsiloxane
OTS: Octadecyltrichlorosilane
PVB: Polyvinylbutyral
TEOS: Ethylsilicate
1. Introduction

 Natural organisms’ (Plans and Animals) biological topography shows a wonderful natural
surface of unique properties (super-hydrophobicity, self-cleaning, un-wettability), that
could be applied in different research fields.

 Up to now, many micro/nano-biomimetic structures have been developed through

different techniques, including sol-gel method, electrospinning, phase separation,
chemical etching, chemical vapour deposition, lithography and assembly.
 Natural wood, a low-cost, low-density, lightweight, high-performance and abundant
earth’s important resources, is ubiquitously used structural material in our daily
application such as indoor decoration, handicrafts, flooring, construction, furniture,
shipbuilding, and so on.

 Due to the large number of hydrophilic groups on the surface of wood, it has a strong
moisture absorption and water absorption characteristics, and will be deformed,
discoloured or decayed when it is adversely affected.
 Most researchers reported that robust superhydrophobic wood surfaces have been
developed, such as superparamagnetic, superhydrophobic, durable, robust, buoyant,
electromagnetic wave-absorbing wood, and so on.

 However, few researchers have focused on superhydrophobic wood surface outgrowth-

induced high-temperature, humidity, water, UV, and corrosion resistance properties. Such
material resistance over those of original wood exhibits potentially utilized value-added
applications in building and various industries.
 Based on the guidance of superhydrophobic surface construction theory, the use of surface
modification treatment to produce superhydrophobic wood has poor durability, complicated
production processes, expensive reagents and equipment.

 The application of bionic constructed super-wet interface materials is widely recognized, but
at present, there are still great challenges in the design, preparation and practical
application in wood technology.

 In this work, protective coating inspired by canna-leaf was fabricated using

Polydimethylsiloxane (PDMS) polymer as imprint to transfer the patterns from canna-leaf to
Polyvinylbutyral (PVB) composite coatings using nanoimprint lithography, and tested for
different properties.
2. Experimental section

Materials:

 Fresh canna-leaves (100 mm X 100 mm),

 Oven-dried and rinsed ash wood (200 mm X 10 mm X 5 mm),

 Polydimethylsiloxane (PDMS), Acetone, Absolute alcohol, Tetraethylorthosilicate (TEOS),

Octadecyltrichlorosilane (OTS)?, self-made Polyvinylbutyral (PVB) composite.
Preparation of PDMS composite solution
 Take 20 ml PDMS solution
 n, poured in a 50 ml glass container, and then added 2 ml Curing agent (10:1 vol ratio) at ambient
room temperature under vigorously magnetic stirred for 0.5 h. Then static 3 h to eliminate air
bubbles, which the PDMS solution was obtained.

Preparation of template and as-prepared BMSW with a micro/nanostructure topography

 5g PVB solid are dissolved in 45 mL absolute alcohol in 100 mL glass containers at ambient
temperature under vigorous magnetic stirred for 0.5 h; solution is further heated at 60 0C under
vigorous magnetic stirred for 2h in electric-heated thermostatic oil bath. Then, 1 mL OTS solution
and 2 ml TEOS solution are further mixed in 18.6 mL absolute alcohol, and stirred at room
temperature evenly for many time. 0.5 mL OTS solutions and prepared mixed solution was
dissolved in preparation of mixed solution in a 100 mL glass container and placed in the electric-
heated thermostatic oil bath at 60 0C under vigorous magnetic stirred evenly for many time.
Added 0.5 ml OTS again, which the PVB solution was developed and solidified at ambient
temperature for 24 h for further use.
Preparation of template and as-prepared BMSW with a micro/nanostructure topography

RT for 24h

RT for 24h

70 0C for 4h

Figure 1: Schematic illustration template transfer technology for the replicated process of the BMSW.
 The mechanism of the condensation reaction of hydrophobic monodispersed nano-SiO2
microspheres can be expressed by the reaction in Equations (1) - (3):

 According to previous results, a possible mechanism could be as follows. First,

tetraethylorthosilicate (TEOS) is hydrolysis to SiO2 in aqueous ammonia. Hydrophobic

monodisperse nano-SiO2 microspheres are formed by the alcohol condensation and

water condensation reaction.
Characterizations

 The surface morphology of the original wood, the canna-leaf, PDMS template and BMSW was
characterized by a scanning electron microscope (SEM).

 The chemical composition of BMSW was determined by energy dispersive spectroscopy (EDS).

 The crystalline structures of BMSW were identified by X-ray diffraction (XRD).

 Surface chemical compositions of BMSW were characterized by Fourier transformation infrared

(FTIR) spectroscopy.

 Measurement of the thermal stability performance using a thermogravimetric and differential thermal
analyser (TG-DTA).

 Optical water contact angles (WCA) measurements were done at ambient room temperature using
demonized? water as measurement liquid.
3. Results and discussion
Hill-like (Papillae) Inverse canna-leaf
Structural and morphological characterization: structures like structure

The average diameter of

the grooves bottom, sides
and top was 6.42 µm,
13.37 µm and 4.74 µm
respectively.

Figure 2: SEM images of specimens of (a) original wood surface, (b) canna-leaf surface, (c) the first time replicated
canna-leaf like template surface, a second replicated canna-leaf-like wood surface with (d) its low magnification and (e)
its high magnification, and (f) EDS spectra of BMSW.
Chemical components, element analysis

1H,1H,2H,2H-Perfluorodecyltriethoxysilane

TEOS

Figure 3: The diagram of reaction mechanisms of the hydrophobic nano-SiO 2.

 The diffraction peaks at about 2θ of 160, 220 were
assigned to the crystalline region of cellulose in the
wood. And all the new strong diffraction peaks at
about 47.50, 57.40 and 76.40 were observed for the
BMSW. Moreover, there are no other diffraction
peaks, which indicates the solution was prepared
with high purity.

Figure 4: XRD patterns spectra of SiO2, original

wood and BMSW

Figure 5: FTIR patterns spectra of SiO2, original wood and
BMSW
The main absorption bands correspond to
 3500-3200 cm-1 : O-H
 ~2927 cm-1: -CH3
 ~1730 cm-1: C = O
 1350-1180 cm-1: C-F and
 1000-808 cm-1: Si-O-Si stretching vibrations ,
The main absorption peaks corresponds to
 3400 cm-1 : -OH
 3200 cm-1 : C-H bond in BMSW surface
 2927 cm-1 : C-H3 bond of lignin
 1698 & 1574 cm-1 : C=O bonds
 1350-1180 cm-1 : C-F groups of the PVB composite
 803 cm-1 : Si-O and Si-CH3 bond stretching vibration
Thermally stability analyses

The results supported that the

samples were almost all
decomposed, and the mass
percentage of pyrolysis remainder of
original wood and BMSW is about
19.94% and 9.22%. The thermal
stability performance of the BMSW
was significant.

Figure 4: (a) TG and (b) DTG curves of the original wood and BMSW, respectively .

3 step drops and 3 peaks.

1. Small weight loss (weight loss 3.1%-6.30%) observed at 49.22 0C to 106.47 0C was attributed to the moisture from the
original wood and BMSW.
2. The original wood weight loss rate 75.77% and BMSW weight loss rate 56.77% observed at 106.47 0C to 400 0C due
to cellulose, hemicellulose and lignin.
3. The original wood for weight loss rate 13.87% and BMSW weight loss rate 12.54% observed at 400 0C to 800 0C
owing to the pyrolysis residues.
 Wettability performances (WCA)

Presence of -OH

SA 60

Low self-cleaning

Figure 6: (a) The static behaviour of water droplets on canna-leaf surface ; (b)-(g) the dynamic behaviour of water droplets
on canna leaf surface. Water droplet rolls off canna-leaf surface surface, after the slightest vibration (b) 0 s; (c) 0.5 s; (d) 1 s;
(e) 1.5 s; (f) 2s; (g) 2.5 s; The static behavior of the water droplets on the surface of (h) the original wood and (i) three
sections of BMSW, seven types of liquids: brine water, red wine, orange juice, black ink, tea, coca-cola and milk on the
surface of the (j) original wood and (k) BMSW;(l)-(m) The evolution process of the self-cleaning behaviour of BMSW (15 0).
 Water absorption properties

It was found that the moisture content of MBSW

sample increased to approximately 70% after the
MBSW sample was fully immersing in water to 30
days. After the specimen was fully immersing in
water to 120 days, the moisture content of MBSW
sample was still approximately 70%, whereas that
originally could absorb up to 187%.

Figure 7: Moisture content of original wood and MBSW

immersed in water at room temperature for different numbers
of days up to 120 days
 Corrosion resistance properties

As the pH increases from 1 to 7, the contact angle

decreases first and then increases. It is the smallest at
pH = 3 and the minimum WCA is 1530. As the pH is
increased from 7 to 14 the contact angle decreases
linearly to 1510 when pH = 14. The largest contact angle
is found at pH = 7 and is 1580. The WCA is above 150
for all cases and the MBSW shows super hydrophobic
characteristics over the entire pH range.
Figure 8: Robust superhydrophobic properties of MBSW
immersed in water with different pH values for 30 min
 Abrasion resistance properties

 Sandpaper (1500 meshes) was used to wear the

surface, and the super-hydrophobic characteristics
of the MBSW sample were tested after abrasion. A
150-gram weight is applied to the surface and
MBSW sample is dragged in one direction at a
speed of 10 mm s-1, with a cycle of 20 cm.

Figure 9: Robust superhydrophobic properties of

MBSW slide on sad paper with different length
  Sandpaper (1500 meshes) was used to wear the
surface, and the super-hydrophobic characteristics
of the MBSW sample were tested after abrasion The
surface of the MBSW sample was moved 20 cm in
one direction with varying weight.

Figure 10: Robust superhydrophobic properties of MBSW slide on sad paper with different weight
 UV resistance properties

 It can be seen from the figure that after 24 h of

ultraviolet irradiation, the surface contact angles of the
MBSW sample of the bionic banana leaves are greater
than 1500 showing excellent superhydrophobic
behaviour. The results show that the MBSW sample
have good UV resistance and stable wettability.

Figure 10: Robust superhydrophobic properties

of MBSW slide on sad paper with different weight
4. Conclusion

 Inspired by canna-leaf, using canna-leaf as a master and PDMS polymer material as the
imprint, through nanoimprint technology and silanization graft modification treatment, the
micro/nano groove edge structure on the surface of canna-leaf was successfully transferred.

 It is built on the surface of the wood to obtain a biomimetic morphologies anisotropic

superhydrophobic wood, which can effectively prevent water from entering.

 The different testes conducted has confirmed that the prepared MBSW samples are supper
hydrophobic, thermally stable, low moisture absorption, corrosion resistant, and abrasion
resistant.
5. Remarks
 In my point of view, the superhydrophobic properties of canna-leafs is not entirely
attributed to the micro/nano structures but also to some extent to the chemical
composition of the surface. The extracts from the leafs may have some effect of
hydrophobicity.

 False banana (Enset) leafs can be studied for similar effects.

 In some applications different factors like UV, Abrasion, Corrosion and so on may act
simultaneously on the structural wood. Computational modelling techniques can be used
to simulate those condition to study the interaction effect of different factors.

 By experimenting on locally available hydrophobic resources, I am planning to prepare

nano/micro structured coating for small scale wooden wind turbine blades. (podocarpus
falactus).
Thank you for your
attention!!