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-

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

⁎
Corresponding author.
E-mail address: [email protected] (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. Progress in Organic Coatings 111 (2017) 29–37

hydrophilic under UV irradiation [15]. Thermal treatment could be located at Kuala Selangor, Malaysia. Citric acid and ethanol were
used to restore the superhydrophobic surface of PVDF/TiO2 coating. In purchased from Merck, Malaysia. On the other hand, 1H,1H,2H,2H-
order to improve the durability of superhydrophobic coating, Wang perfluorodecyltriethoxysilane (HFDS) from Gelest Inc. and SA
et al. [16] utilized polydimethylsiloxane (PDMS) which is a common (C18H36O2) at the analytical grade with 95% purity from Sigma
sealant to bond a mixture of SiO2 nanoparticles and fluoroalkylsilane Aldrich were used as the hydrophobic modifier. The commercial
coating on glass slide via spray coating. The commercial adhesive adhesive, 3 M Spray Mount™ Artist’s adhesive was used in spray
containing hydrocarbon resin had also been used to attach the hydro- coating.
phobic silica nanoparticles on substrate strongly without the require-
ment of heat treatment at high temperature [5,17].
2.2. RHA preparation and characterization
Besides looking into the chemical selection and roughness creation,
the sustainability of superhydrophobic coatings was further studied.
The rice husk was chemically washed according to literature [33].
The SiO2 nanoparticles in waste ash [18–21] could be used to improve
The raw rice husk was first washed with tap water, then it was further
the sustainability of superhydrophobic coating as reported in our
rinsed with distilled water up to 3 times. After drying at 110 °C for 24 h,
previous work [5]. Meanwhile, the cost effective and safe chemicals
20 g of rice husk was immersed in 500 ml of citric acid solution (5 wt.
such as fatty acids were used to modify the silica nanoparticles which
%) and stirred for 2 h at 50 °C. The rice husk was then filtered, rinsed
were later applied as the concrete admixture [22,23]. The green
and dried before calcination. In order to generate the photoluminescent
solvent, water was even promoted by selecting the water soluble
silica, the washed rice husks were calcined in a muffle furnace
fuoroacrylic copolymer as the hydrophobic agent [24]. Pantoja et al.
(Carbolite) at two different calcination temperatures, 550 °C and
[25] emphasized that the solvent selection is important to disperse the
650 °C for 6 h under the heating rate of 10 °C/min and atmospheric
nanoparticles for roughness creation. The higher water contact angle
condition as reported by Liu et al. [31]. RHA calcined at 550 °C was
was achieved by using white spirit instead of ethanol or ethanol-water
denoted as RHA 550 while RHA calcined at 650 °C was denoted as RHA
to form the superhydrophobic bentonite coating. Moreover, the super-
650 (Table 1). The RHA samples were examined using scanning
hydrophobic coating with satisfactory transparency was successfully
electron microscope equipped with energy-dispersive X-ray spectro-
synthesized by dip-coating a mixture of SiO2 and methyltrimethoxysi-
scopy (SEM-EDX, Quanta FEG 450) which was operated at an accel-
lane on polyurethane (PU) surface [26]. The PU/SiO2 coating with
erating voltage 5 kV and transmission electron microscope (TEM,
three-dimensional networking structure allowed the light transmittance
CM200 FEG Philips). RHA samples were sonicated in ethanol, dispersed
as high as 94.38%. The multiple layer of silica coatings followed by the
onto a carbon grid and air dried prior to TEM imaging.
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 2.3. Silica modification, coating and characterization
in silica nanospheres reduced the refractive index and increased the
light transmission. On the other hand, the photocatalytic properties of The RHA samples calcined at 550 °C were further modified using
the near superhydrophobic sol-gel coating of TiO2-SiO2 on bricks was HFDS and SA and they are designated as RHA 550 HFDS and RHA 550
investigated [28]. This coating degraded at least 70% of methylene blue SA, respectively. The modification involved mechanochemical grafting
strains within 4 h of light irradiation. Besides transparency and photo- which was conducted in the ball milling machine (PM 100, Retsch,
catalytsis, the luminescence of coating is interesting to be studied since Germany). The chemical grafting and size reduction occurred simulta-
it is useful in safety signs and markings. Phosphors are the most neously by grinding 2 g of RHA in the HFDS/ethanol mixture (volume
commonly used luminescent materials as they can convert energy into ratio 1:50 ml) for 1 h or 50 ml of SA/ethanol solution (8 mM) for 5 h at
electromagnetic radiation, generally in the visible energy range [29]. In 600 rpm. The unmodified and modified RHA samples were also
other words, phosphors emit photons when they are energized by an characterized using Fourier Transform Infrared (FTIR) spectroscopy
external energy source such as sun light. The incoming radiation can be (Nicolet Nexus 670, Thermo Scientific, USA) in order to investigate the
converted to visible light by the presence of phosphor during dark. chemical properties. The spectra were generated from 32 scans within
Photoluminescent SiO2 materials were recently reported due to their the wavenumber range of 425–4000 cm−1 at a resolution of 4.00 cm−1.
wide applications in the bioanalytical assays, labelling, chemical The fluorescent and microscopic images of these RHA samples were
sensing, lighting, drug delivery and etc. [30]. The luminescent silica recorded using a fluorescence microscope (365 nm, Olympus BX53,
can be chemically produced from alkoxysilanes as well as physically Japan). RHA samples dispersed in ethanol at a concentration of 0.1 g/
doped with the expensive dyes or metal activators [29]. Due to the ml were used to prepare the slides for imaging. Meanwhile, PL intensity
trapped carbon in the silica framework, rice husk ash (RHA) exhibited of the unmodified and modified RHA samples was quantified using a
photoluminescence (PL) as well [31]. Fluorescence sensing and imaging spectoflourometer (Perkin Elmer Lambda S55 spectrofluorometer using
could be helpful in the detection or analysis of corrosion in reinforced a Xe lamp). The PL measurement was conducted using RHA samples
concrete using these photoluminescent materials available in abun- dispersed in ethanol at a concentration 4.5 × 10−9 mg/ml. The spectra
dance and low cost [32]. were scanned under 365 nm light excitation.
The major aim of this work is to synthesize superhydrophobic The superhydrophobic coating was formed by spray coating the
coating with PL. The PL can be a useful indicator of coating presence ethanol solution containing the modified RHA on a layer of adhesive
and even durability. The photoluminescent SiO2 nanoparticles from which was pre-coated on the glass slide. A layer of adhesive coating was
RHA were used to engineer the superhydrophobic coating for concrete. sprayed on the glass slide before the ash coating was applied. The same
The effects of calcination temperature on the properties of RHA was coating method was applied on the concrete cubes
first studied. The effects of fluoroalkyl silane and stearic acid (SA) on
RHA and coating properties were further investigated. Furthermore, the Table 1
Description of all RHA samples applied in this work.
superhydrophobic coating was applied on the concrete cube.
Sample Description
2. Experimental
RHA 550 Calcined RHA at 550 °C
RHA 650 Calcined RHA at 650 °C
2.1. Materials
RHA 550 HFDS Calcined RHA at 550 °C and grafted with HFDS
RHA 550 SA Calcined RHA at 550 °C and grafted with SA
The raw rice husk was collected from Padiberas Nasional Berhad,

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(100 × 100 × 100 mm). The concrete cubes were prepared from a 3. Results and discussion
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). 3.1. The effects of calcination temperature
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 RHA samples calcined at 550 °C and 650 °C consist of two major
workability of fresh concrete, while the concrete was further cured for elements, namely silicone and oxygen as shown in SEM-EDX results
28 days based on BS 1881: Part 111: 1983. (Fig. 1). Carbon element was evidently shown in the SEM-EDX results of
The water contact angle of ash coating on glass slide and concrete both RHA 550 and RHA 650 samples as well. RHA 550 sample contains
was determined using a ganiometer (250-F1, Ramé-Hart Instruments 7.39% of carbon, while RHA 650 contains 5.18% of carbon. Rice husk
Co.). A drop of deionized water were placed on the coatings to measure usually contains 15–25 wt.% silica and a large amount of organic
water contact angle after 30 s. The average value of water contact angle compounds such as lignin, cellulose, and hemicellulose [34]. The
was determined using three replicated coatings on glass slides or carbon residue in RHA samples originated from these organic com-
concrete cubes. The coating morphology were studied using SEM pounds which were mainly released in the form of CO2 during
(HITACHI Tabletop Microscope instrument, TM-3000-Japan) operated calcination. The higher calcination temperature resulted in the lower
at 15 kV while the fluorescent images of coatings were captured using a carbon content in ash. The carbon element distributed in the ash
fluorescence microscope (Olympus BX61- UMWU2, Japan) 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)

Fig. 1. SEM images and elements scanned graph for (a) RHA 550 and (b) RHA 650.

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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]. ash calcined at low temperatue emmitted the higher PL intensity
Most of the researchers believe that the PL emission of CND is caused by (225–415 nm) compared to the rice husk ash calcined at high tempera-
the radiative recombination of excitons located at surface energy traps ture. They related the PL of RHA to the trapped carbon. From their
although the PL of CND was not fully understood [36]. elemental analysis, RHA calcined at 700 °C yielded a carbon content of
The PL intensity of RHA samples produced at different calcination 0.084 wt.% whereas RHA calcined at 550 °C produced a carbon content
temperatures were observed using a fluorescence microscope. The of 0.477 wt.% which resulted in the higher PL intensity. Graphene
fluorescent images of RHA 550 sample and RHA 650 samples in quantum dots could be also hydrothermally synthesized from rice husk
Fig. 3 showed the slight difference in term of fluorescence intensity. carbon which was produced under the nonoxidation atmosphere [37].
The fluorescence intensity of RHA 550 particles was slightly stronger However, PL in the range of 330–340 nm of porous silica prepared by
than RHA 650 particles. The difference could be related to the sol-gel route was related to the nonbridging oxygen hole centers of
calcination temperature which caused the varied carbon content in surface hydroxyls [38]. The PL of this porous silica was associated with
the ash samples [31]. In order to quantify the difference in these the increase of −OH groups absorbed on the surface.
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 3.2. The effects of mechanochemical grafting
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 In this work, RHA 550 sample was further chemically modified into
higher than RHA 650 samples. Liu et al. [31] reported that the rice husk hydrophobic SiO2 using HFDS or SA before spray coating on any
substrate. RHA 550 sample was chosen because it exhibited similar PL

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

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

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Fig. 5. FTIR spectra of different RHA samples.

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

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Fig. 7. PL intensity of RHA 550 HFDS and RHA 550 SA.

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
Fig. 8. Goniometer images of the static water droplets (5 μl) on the surface of (a) RHA adhesive. The coated concrete showed a water contact angle up to
550 HFDS and (b) RHA 550 SA coatings on glass slide. 157.7°. However, PL intensity of superhydrophobic ash coating should
be further improved for more practical use in construction and building.
commercial adhesive followed by RHA 550 HFDS coating. The water
droplets wetted the surface of unmodified concrete as usual since
Acknowledgements
concrete is porous and hydrophilic (Fig. 11). Meanwhile, the coated
concrete surface remained dry as the water droplets were unable to wet
The authors would like to convey great gratitude to the Ministry of
on the superhydrophobic surface. A water contact angle on the coated
Education Malaysia for their financial support via FRGS 2015-1 grant
concrete up to 157.7° was recorded. In literature, other researchers also
(Flood Disaster Management, 203/PJKIMIA/6071315) and My Brain 15
reported the blending of silica nanoparticles into the hydrophobic
(My Ph. D) scholarship awarded to Ms. Nor Naimah Rosyadah Ahmad.
polymers, poly(methyl methacrylate) (PMMA) dissolved in toluene or
Finally, the authors would like to express acknowledgment to Padiberas

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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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