Progress in Organic Coatings 111 (2017) 29–37

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Progress in Organic Coatings

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

Superhydrophobic coating of silica with photoluminescence properties MARK

synthesized from rice husk ash
⁎
M.U.M. Junaidia,b, S.A. Haji Azamana, N.N.R. Ahmada, C.P. Leoa, , G.W. Lima, D.J.C. Chana,
H.M. Yeec
a
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
b
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603, Kuala Lumpur, Malaysia
c
Faculty of Civil Engineering, Universiti Teknologi MARA, 13500 Permatang Pauh, Penang, Malaysia

A R T I C L E I N F O A B S T R A C T

Keyword: Water penetration into concrete can cause the degradation of concrete strength, leading into structure failure.
Superhydrophobic Superhydrophobic coatings on concrete received tremendous attention in the recent years as these coatings repel
Photoluminescent water like lotus leaves. In this work, rice husk ash (RHA) was used to prepare the superhydrophobic coating. Rice
Ash husk was calcined at 550 °C and 650 °C to form silica particles with a small amount of carbon residue. RHA 550
Concrete
sample showed slightly higher photoluminescence (PL) intensity than RHA 660 sample as shown in fluorescent
images and PL spectra. Such difference could be related to the variation of carbon content measured using
scanning electron microscope-energy-dispersive X-ray spectroscopy. The carbon residue in nano size was
detected in transmission electron microscope images. RHA with PL properties was further mechanochemically
modified using 1H,1H,2H,2H-perfluorodecyltriethoxysilane (HFDS) or stearic acid in ethanol. However, PL
properties of RHA 550 was slightly reduced due the successful grafting of hydrophobic groups on silica particles.
The modified RHA in ethanol was later spray coated on a layer of commercial adhesive to form superhyrophobic
coatings on glass slides and concrete. The superhydrophobic coating on concrete with the water contact angle as
high as 157.7° was recorded.

1. Introduction coatings at Cassie-Baxter state requires the creation of surface rough-

The ingression of water into concrete not only causes the destructive
expansion, but also results in the penetration of corrosive chloride ions.
Hence, concrete degradation and structure failure due to the ingression
of water into the hydrophilic concretes with pores and micro-cracks
should be prevented. Different types of water resistant materials can be
used to alter the surface energy on the concrete surface, pores and
cracks for reducing concrete wetting. In the recent years, superhydro-
phobic coatings with water contact angles larger than 150° have been
promoted since the superhydrophobic coatings can repel water dro-
plets, dew drops and even dust particles [1]. The superhydrophobic
coatings enhanced the anti-wetting, anti-corrosion, anti-icing, anti-
contamination and self-cleaning properties of concrete to combat the
adverse weather conditions [2–5].
A wide range of hydrophobic chemicals can be used to reduce the
surface energy of concrete, including silane, siloxanes and silicones [6].
These silicon based chemicals contains the hydrophobic alkyl groups to
prevent wetting. However, the water repellence of superhydrophobic
ness to capture a thin layer of air which can minimize water contact [1].
Many roughness creation methods such as sol-gel [7], self-assembly [8],
templating [9], lithographic patterning [10], chemical etching [11],
electrospinning [12] and chemical vapour deposition [13] have been
reported. The addition of nanoparticles remains to be popular since it is
time and cost saving. Expensive equipment or rigorous condition is not
required as well. Hence, the popular formulation of superhyrophobic
coatings usually consists of the hydrophobic polymer and the inorganic
nanoparticles dispersed in the solvent. Various types of hydrophobic
polymers were recently studied in the development of superhydropho-
bic coatings [14]. The superhydrophobic thin film made of polyviny-
lidene fluoride (PVDF) and SiO2 nanoparticles with fluoroalkyl groups
was successfully coated on the glass surface using the surface functio-
nalizing agent, aminopropyltriethoxysilane [14]. The superhydropho-
bic PVDF coating not only exhibited the satisfactory durability, the
surface hydrophobicity was maintained even after UV irradiation.
Incorporating the TiO2 nanoparticles with fluoroalkyl groups into PVDF
coating, the superhydrophobic surface could be easily turned into

⁎
Corresponding author.
E-mail address: chcpleo@usm.my (C.P. Leo).

http://dx.doi.org/10.1016/j.porgcoat.2017.05.009
Received 27 January 2017; Received in revised form 22 March 2017; Accepted 13 May 2017
0300-9440/ © 2017 Elsevier B.V. All rights reserved.
M.U.M. Junaidi et al.
hydrophilic under UV irradiation [15]. Thermal treatment could be
used to restore the superhydrophobic surface of PVDF/TiO2 coating. In
order to improve the durability of superhydrophobic coating, Wang
et al. [16] utilized polydimethylsiloxane (PDMS) which is a common
sealant to bond a mixture of SiO2 nanoparticles and fluoroalkylsilane
coating on glass slide via spray coating. The commercial adhesive
containing hydrocarbon resin had also been used to attach the hydro-
phobic silica nanoparticles on substrate strongly without the require-
ment of heat treatment at high temperature [5,17].
Besides looking into the chemical selection and roughness creation,
the sustainability of superhydrophobic coatings was further studied.
The SiO2 nanoparticles in waste ash [18–21] could be used to improve
the sustainability of superhydrophobic coating as reported in our
previous work [5]. Meanwhile, the cost effective and safe chemicals
such as fatty acids were used to modify the silica nanoparticles which
were later applied as the concrete admixture [22,23]. The green
solvent, water was even promoted by selecting the water soluble
fuoroacrylic copolymer as the hydrophobic agent [24]. Pantoja et al.
[25] emphasized that the solvent selection is important to disperse the
nanoparticles for roughness creation. The higher water contact angle
was achieved by using white spirit instead of ethanol or ethanol-water
to form the superhydrophobic bentonite coating. Moreover, the super-
hydrophobic coating with satisfactory transparency was successfully
synthesized by dip-coating a mixture of SiO2 and methyltrimethoxysi-
lane on polyurethane (PU) surface [26]. The PU/SiO2 coating with
three-dimensional networking structure allowed the light transmittance
as high as 94.38%. The multiple layer of silica coatings followed by the
chemical vapour deposition of 1H,1H,2H,2H-perfluorooctyltriethoxysi-
lane also resulted in the superhydrophobic coating with excellent
transparency [27]. The mesopores in silica nanosheets and the hollows
in silica nanospheres reduced the refractive index and increased the
light transmission. On the other hand, the photocatalytic properties of
the near superhydrophobic sol-gel coating of TiO2-SiO2 on bricks was
investigated [28]. This coating degraded at least 70% of methylene blue
strains within 4 h of light irradiation. Besides transparency and photo-
catalytsis, the luminescence of coating is interesting to be studied since
it is useful in safety signs and markings. Phosphors are the most
commonly used luminescent materials as they can convert energy into
electromagnetic radiation, generally in the visible energy range [29]. In
other words, phosphors emit photons when they are energized by an
external energy source such as sun light. The incoming radiation can be
converted to visible light by the presence of phosphor during dark.
Photoluminescent SiO2 materials were recently reported due to their
wide applications in the bioanalytical assays, labelling, chemical
sensing, lighting, drug delivery and etc. [30]. The luminescent silica
can be chemically produced from alkoxysilanes as well as physically
doped with the expensive dyes or metal activators [29]. Due to the
trapped carbon in the silica framework, rice husk ash (RHA) exhibited
photoluminescence (PL) as well [31]. Fluorescence sensing and imaging
could be helpful in the detection or analysis of corrosion in reinforced
concrete using these photoluminescent materials available in abun-
dance and low cost [32].
The major aim of this work is to synthesize superhydrophobic
coating with PL. The PL can be a useful indicator of coating presence
and even durability. The photoluminescent SiO2 nanoparticles from
RHA were used to engineer the superhydrophobic coating for concrete.
The effects of calcination temperature on the properties of RHA was
first studied. The effects of fluoroalkyl silane and stearic acid (SA) on
RHA and coating properties were further investigated. Furthermore, the
superhydrophobic coating was applied on the concrete cube.
2. Experimental
2.1. Materials
The raw rice husk was collected from Padiberas Nasional Berhad,
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Progress in Organic Coatings 111 (2017) 29–37
located at Kuala Selangor, Malaysia. Citric acid and ethanol were
purchased from Merck, Malaysia. On the other hand, 1H,1H,2H,2H-
perfluorodecyltriethoxysilane (HFDS) from Gelest Inc. and SA
(C18H36O2) at the analytical grade with 95% purity from Sigma
Aldrich were used as the hydrophobic modifier. The commercial
adhesive, 3 M Spray Mount™ Artist’s adhesive was used in spray
coating.
2.2. RHA preparation and characterization
The rice husk was chemically washed according to literature [33].
The raw rice husk was first washed with tap water, then it was further
rinsed with distilled water up to 3 times. After drying at 110 °C for 24 h,
20 g of rice husk was immersed in 500 ml of citric acid solution (5 wt.
%) and stirred for 2 h at 50 °C. The rice husk was then filtered, rinsed
and dried before calcination. In order to generate the photoluminescent
silica, the washed rice husks were calcined in a muffle furnace
(Carbolite) at two different calcination temperatures, 550 °C and
650 °C for 6 h under the heating rate of 10 °C/min and atmospheric
condition as reported by Liu et al. [31]. RHA calcined at 550 °C was
denoted as RHA 550 while RHA calcined at 650 °C was denoted as RHA
650 (Table 1). The RHA samples were examined using scanning
electron microscope equipped with energy-dispersive X-ray spectro-
scopy (SEM-EDX, Quanta FEG 450) which was operated at an accel-
erating voltage 5 kV and transmission electron microscope (TEM,
CM200 FEG Philips). RHA samples were sonicated in ethanol, dispersed
onto a carbon grid and air dried prior to TEM imaging.
2.3. Silica modification, coating and characterization
The RHA samples calcined at 550 °C were further modified using
HFDS and SA and they are designated as RHA 550 HFDS and RHA 550
SA, respectively. The modification involved mechanochemical grafting
which was conducted in the ball milling machine (PM 100, Retsch,
Germany). The chemical grafting and size reduction occurred simulta-
neously by grinding 2 g of RHA in the HFDS/ethanol mixture (volume
ratio 1:50 ml) for 1 h or 50 ml of SA/ethanol solution (8 mM) for 5 h at
600 rpm. The unmodified and modified RHA samples were also
characterized using Fourier Transform Infrared (FTIR) spectroscopy
(Nicolet Nexus 670, Thermo Scientific, USA) in order to investigate the
chemical properties. The spectra were generated from 32 scans within
the wavenumber range of 425–4000 cm−1 at a resolution of 4.00 cm−1.
The fluorescent and microscopic images of these RHA samples were
recorded using a fluorescence microscope (365 nm, Olympus BX53,
Japan). RHA samples dispersed in ethanol at a concentration of 0.1 g/
ml were used to prepare the slides for imaging. Meanwhile, PL intensity
of the unmodified and modified RHA samples was quantified using a
spectoflourometer (Perkin Elmer Lambda S55 spectrofluorometer using
a Xe lamp). The PL measurement was conducted using RHA samples
dispersed in ethanol at a concentration 4.5 × 10−9 mg/ml. The spectra
were scanned under 365 nm light excitation.
The superhydrophobic coating was formed by spray coating the
ethanol solution containing the modified RHA on a layer of adhesive
which was pre-coated on the glass slide. A layer of adhesive coating was
sprayed on the glass slide before the ash coating was applied. The same
coating method was applied on the concrete cubes
Table 1
Description of all RHA samples applied in this work.
Sample Description
RHA 550 Calcined RHA at 550 °C
RHA 650 Calcined RHA at 650 °C
RHA 550 HFDS Calcined RHA at 550 °C and grafted with HFDS
RHA 550 SA Calcined RHA at 550 °C and grafted with SA
M.U.M. Junaidi et al.
(100 × 100 × 100 mm). The concrete cubes were prepared from a
homogenized mixture of coarse aggregate (1264.8 kg/m3), fine aggre-
gate (595.2 kg/m3), cement (380 kg/m3) and free water (190 kg/m3).
The ratio of free water to cement (w/c) was fixed at 0.5. The slump test
was conducted according to BS 1881: Part 102: 1983 to determine the
workability of fresh concrete, while the concrete was further cured for
28 days based on BS 1881: Part 111: 1983.
The water contact angle of ash coating on glass slide and concrete
was determined using a ganiometer (250-F1, Ramé-Hart Instruments
Co.). A drop of deionized water were placed on the coatings to measure
water contact angle after 30 s. The average value of water contact angle
was determined using three replicated coatings on glass slides or
concrete cubes. The coating morphology were studied using SEM
(HITACHI Tabletop Microscope instrument, TM-3000-Japan) operated
at 15 kV while the fluorescent images of coatings were captured using a
fluorescence microscope (Olympus BX61- UMWU2, Japan)
Fig. 1. SEM images and elements scanned graph for (a) RHA 550 and (b) RHA 650.
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Progress in Organic Coatings 111 (2017) 29–37
3. Results and discussion
3.1. The effects of calcination temperature
RHA samples calcined at 550 °C and 650 °C consist of two major
elements, namely silicone and oxygen as shown in SEM-EDX results
(Fig. 1). Carbon element was evidently shown in the SEM-EDX results of
both RHA 550 and RHA 650 samples as well. RHA 550 sample contains
7.39% of carbon, while RHA 650 contains 5.18% of carbon. Rice husk
usually contains 15–25 wt.% silica and a large amount of organic
compounds such as lignin, cellulose, and hemicellulose [34]. The
carbon residue in RHA samples originated from these organic com-
pounds which were mainly released in the form of CO2 during
calcination. The higher calcination temperature resulted in the lower
carbon content in ash. The carbon element distributed in the ash
samples appeared as the red dots in C distribution images. TEM images
(Fig. 2) of RHA 550 and RHA 650 samples showed the existence of large
particles with irregular size and small particles with circular shape.
RHA 550 contains more small particles than RHA 650. These small
particles could be related to the formation of carbon-based nanomater-
ials. Carbon-based nanomaterials especially carbon nanodot (CND)
M.U.M. Junaidi et al.
Fig. 2. TEM images and carbon distribution images generated from EDX for (a) RHA 550 and (b) RHA 650 particles.
below the size of 10 nm have been long studied due to their PL [35].
Most of the researchers believe that the PL emission of CND is caused by
the radiative recombination of excitons located at surface energy traps
although the PL of CND was not fully understood [36].
The PL intensity of RHA samples produced at different calcination
temperatures were observed using a fluorescence microscope. The
fluorescent images of RHA 550 sample and RHA 650 samples in
Fig. 3 showed the slight difference in term of fluorescence intensity.
The fluorescence intensity of RHA 550 particles was slightly stronger
than RHA 650 particles. The difference could be related to the
calcination temperature which caused the varied carbon content in
the ash samples [31]. In order to quantify the difference in these
fluorescent images, a spectrofluorometer was used to measure the PL
intensity of RHA 550 and RHA 660 samples. Fig. 4 presents the PL
spectra of the RHA samples calcined at different temperatures. The
emission peak at 365 nm appeared in these spectra under the excitation
of 435 nm light. Moreover, the PL intensity of RHA 550 was slightly
higher than RHA 650 samples. Liu et al. [31] reported that the rice husk
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Progress in Organic Coatings 111 (2017) 29–37
ash calcined at low temperatue emmitted the higher PL intensity
(225–415 nm) compared to the rice husk ash calcined at high tempera-
ture. They related the PL of RHA to the trapped carbon. From their
elemental analysis, RHA calcined at 700 °C yielded a carbon content of
0.084 wt.% whereas RHA calcined at 550 °C produced a carbon content
of 0.477 wt.% which resulted in the higher PL intensity. Graphene
quantum dots could be also hydrothermally synthesized from rice husk
carbon which was produced under the nonoxidation atmosphere [37].
However, PL in the range of 330–340 nm of porous silica prepared by
sol-gel route was related to the nonbridging oxygen hole centers of
surface hydroxyls [38]. The PL of this porous silica was associated with
the increase of −OH groups absorbed on the surface.
3.2. The effects of mechanochemical grafting
In this work, RHA 550 sample was further chemically modified into
hydrophobic SiO2 using HFDS or SA before spray coating on any
substrate. RHA 550 sample was chosen because it exhibited similar PL
M.U.M. Junaidi et al. Progress in Organic Coatings 111 (2017) 29–37

Fig. 3. Microscopic images of (a) RHA 550 without UV light, (b) RHA 550 with UV light, (c) RHA 650 without UV light and (d) RHA 650 with UV light.

intensity at a lower calcination temperature in comparison to RHA 650.
The FTIR spectrum of RHA samples calcined at 550 °C exhibited OeH
stretching at 3383 cm−1, SieOeSi vibrational stretching at 1076 cm−1
and SieO vibrations at 800 cm−1 (Fig. 5) [39]. These absorption peaks
are consistent with the typical FTIR spectra of the SiO2 samples. In this
work, the RHA samples were further modified in mechanochemical
reaction. Two new peaks appeared at 2960 cm−1 and 2854 cm−1 in the
FTIR spectrum of RHA 550 SA sample due to the symmetric and anti-
symmetric stretching vibrations of eCH. These peaks indicated the
successful grafting of hydrocarbon groups on silica [23]. After ball
milling RHA with HFDS, a new peak occurred at 1201 cm−1 due to the
introduction of the eCF groups [5].
Fig. 6 shows the fluorescence images RHA 550 samples modified
with the hydrophobic agent, either HFDS or SA. Apparently, the
fluorescence intensity of RHA 550 HFDS sample reduced signification
after grafting. The PL intensity of the modified RHA particles was
further measured. From the PL graph (Fig. 7), the highest PL intensity at
365 nm was recorded for RHA 550 sample without modification
followed by RHA 550 SA and RHA 550 HFDS samples. However, the
broad peak in the range of 400–500 nm grew when RHA 550 sample
was modified. The PL emission of CND with shorter wavelength was
related to the intrinsic state emission or electron-hole recombination,
while the PL emission of CND with longer wavelength was linked to the
defect state emission or surface energy traps [40]. The PL properties of
CND could be easily varied by changing the surface functional groups,
but other researchers mainly focused on amino-containing groups [41].
This is because the water soluble properties of CND are required in the
common applications of CND.

Fig. 4. PL intensity of RHA samples calcined at different temperatures.

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M.U.M. Junaidi et al. Progress in Organic Coatings 111 (2017) 29–37

Fig. 5. FTIR spectra of different RHA samples.

3.3. Hydrophobicity coatings using the modified RHA
The images of water droplet on RHA 550 HFDS and RHA SA
coatings were captured in Fig. 8. As expected, the surface tension of
eCH2 and eCH3 groups in the alkyl chain are higher than fluorocarbon
groups (–CF2 and eCF3), resulting in less hydrophobic effect compared
to HFDS. The surface energy of hydrophobic groups on silica particles
decrease in the following order: eCH2 (36 dyn/cm) > –CH3 (30 dyn/
cm) > CF2 (23 dyn/cm) > CF3 (15 dyn/cm) [1]. Furthermore, SEM
images of these coating surface in Fig. 9 shows the rough surface
formed by modified SiO2 particles, namely RHA 550 HFDS and RHA
550 SA. The significant difference in surface morphology between RHA
550 HFDS and RHA 550 SA coatings was not detected. The fluorescent
image of RHA550 HFDS coating on glass slide exhibited slightly lower
PL intensity compared to the fluorescent image of RHA 550 SA coating
on glass slides as expected (Fig. 10). In comparison to literature [42],
the PL intensity of ash coating requires further improvement.
RHA 550 HFDS coating with PL and superhydrophobic properties
was further coated on a concrete cube to study the feasibility of
superhydrophobic RHA coating on concrete. The concrete cubes with
a dimension of 100 mm × 100 mm × 100 mm was used to perform
this feasibility test. The concrete cubes were coated with a layer of

Fig. 6. Microscopic images of (a) RHA 550 HFDS without UV light, (b) RHA 550 HFDS with UV light, (c) RHA 550 SA without UV light and (d) RHA 550 SA with UV light.

34
M.U.M. Junaidi et al.
Fig. 7. PL intensity of RHA 550 HFDS and RHA 550 SA.
Fig. 8. Goniometer images of the static water droplets (5 μl) on the surface of (a) RHA
550 HFDS and (b) RHA 550 SA coatings on glass slide.
commercial adhesive followed by RHA 550 HFDS coating. The water
droplets wetted the surface of unmodified concrete as usual since
concrete is porous and hydrophilic (Fig. 11). Meanwhile, the coated
concrete surface remained dry as the water droplets were unable to wet
on the superhydrophobic surface. A water contact angle on the coated
concrete up to 157.7° was recorded. In literature, other researchers also
reported the blending of silica nanoparticles into the hydrophobic
polymers, poly(methyl methacrylate) (PMMA) dissolved in toluene or
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Progress in Organic Coatings 111 (2017) 29–37
poly(alkyl siloxane) dissolved in white spirit to create the super-
hydrophobic surface on concrete with the high water contact angles
ranged from 150° to 162° [2]. PMMA coating without silica nanopar-
ticles only achieved the water angle less than 140°. Besides inorganic
nanoparticles, polyvinyl alcohol (PVA) fibers could be blended into
concrete to create the hydrophobic and icephobic properties [4]. By
adjusting the sand and PVA fiber amount, The low ice adhesion strength
was accomplished on the superhydrophobic concrete with a water
contact angle as high as 151°. The surface roughness of ultra-high
performance concrete could be also enhanced using the templating
effects of micro-pillared moulds made of polydimethylsiloxanes [3].
The superhydrophobic concrete with a water contact angle of 164° was
achieved after spray-coating with oligomeric siloxane in ethanol
solution. The mentioned works showed the importance of both surface
roughness and surface energy in the creation of superhydrophobic
surface on concrete.
4. Conclusions
RHA containing SiO2 particles and a small amount of carbon residue
was successfully converted into superhydrophobic coating via mechan-
ochemical modification and spray coating. The variation of PL intensity
emitted by RHA samples calcined at different temperature could be
related to the carbon content. The carbon residue in nano scale was
detected in EDX and TEM images. The emission peak at 365 nm
appeared in the PL spectra of RHA samples under the excitation of
435 nm light. The PL intensity of RHA calcined at 550 °C was slightly
higher than the PL intensity of RHA calcined at 650 °C. After mechan-
ochemical modification of RHA 550 sample using HFDS and SA,
fluorescence intensity of RHA reduced as shown in the fluorescent
images and PL spectra. This is because that different hydrophobic
groups such as −CH2, −CH3, −CF2 and −CF3 had been successfully
grafted on the silica particles as proven in the FTIR spectra. However,
the superhydrophobic coating could be only formed on glass slide and
concrete by spray coating RHA 550 HFDS on a layer of commercial
adhesive. The coated concrete showed a water contact angle up to
157.7°. However, PL intensity of superhydrophobic ash coating should
be further improved for more practical use in construction and building.
Acknowledgements
The authors would like to convey great gratitude to the Ministry of
Education Malaysia for their financial support via FRGS 2015-1 grant
(Flood Disaster Management, 203/PJKIMIA/6071315) and My Brain 15
(My Ph. D) scholarship awarded to Ms. Nor Naimah Rosyadah Ahmad.
Finally, the authors would like to express acknowledgment to Padiberas
M.U.M. Junaidi et al. Progress in Organic Coatings 111 (2017) 29–37

Fig. 9. SEM images of (a) RHA 550 HFDS and (b) RHA 550 SA coatings on glass slide.

Fig. 10. Fluorescent images of (a) RHA 550 HFDS and (b) RHA 550 SA coatings on glass slide.

Fig. 11. The water droplets placed on the (a) uncoated concrete surface and (b) RHA 550 HFDS coated concrete surface.

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