Applied Clay Science 132133 (2016) 290295

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Applied Clay Science

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

Research paper

A facile approach to fabricate self-cleaning paint

Linglin Zhou a,b, Sunyang Xu c, Guilong Zhang a,b, Dongqing Cai a,, Zhengyan Wu a,
a
Key Laboratory of Ion Beam Bioengineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences and Anhui Province, Hefei, Anhui 230031, People's Republic of China
b
University of Science and Technology of China, Hefei 230026, People's Republic of China
c
Hefei No. 1 High School, Hefei 230601, People's Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: A self-cleaning paint was developed by adding palygorskite (Pal) modied by amino silicon oil (ASO) and
Received 13 May 2016 aminopropyltriethoxysilane (APTES) to traditional paint (TP). Therein, ASO and APTES could effectively make a
Received in revised form 21 June 2016 Pal form with plenty of nano-clusters, and signicantly increase the roughness and amount of hydrophobic
Accepted 21 June 2016
groups on the surface of Pal. After this modication, the originally hydrophilic Pal was superhydrophobic and
Available online 1 July 2016
could be used as an effective hydrophobic agent to change the hydrophilic paint to super-hydrophobic one
Keywords:
with high self-cleaning ability. This work provides a facile approach to fabricate a self-cleaning paint so as to sig-
Palygorskite nicantly save the labor and lower the cost.
Amino silicon oil 2016 Elsevier B.V. All rights reserved.
Aminopropyltriethoxysilane
Hydrophobicity
Self-cleaning paint

1. Introduction hydrophobic agent, was added to TP and a super-hydrophobic paint

Most of the traditional paints (TPs) are hydrophilic and thus tend to
be contaminated by pollutants in water. The cleaning of these paints
needs manpower and is expensive. Therefore, it is important to develop
a kind of novel paint with high hydrophobicity and self-cleaning ability.
Various approaches have been used for fabrication of hydrophobic ma-
terials, including chemical vapor deposition (Zhang et al., 2004), sol-gel
processing (Shang et al., 2005; Huang and Lin, 2014), etching (Li et al.,
2009; Kim et al., 2009; Cao et al., 2008), phase separation (Nakajima
et al., 2000), molding (Choi et al., 2008) and so on. Some hydrophobic
materials have been fabricated, such as gold cluster lms (Zhang et al.,
2004), zinc oxide (ZnO) (Steele et al., 2010; Feng et al., 2004), aluminum
and its alloy (Guo et al., 2005), polymer materials (Han et al., 2005;
Didem and Thomas, 2000; Shang et al., 2005), celluloses bres (Tejado
et al., 2014) and so on. However, most of those methods and materials
were mainly used for the fabrication of hydrophobic coating rather
than hydrophobic paint. Additionally, most of these approaches
displayed complicated procedures and high costs, so that they were
not suitable for large-scale applications. Consequently, there is a need
for development of a simple and low cost approach to fabricate a hydro-
phobic paint. In this work, palygorskite (Pal) modied by amino silicon
oil (ASO) and aminopropyltriethoxysilane (APTES), as an effective
with high self-cleaning ability was obtained.
Pal, a clay mineral with a nanorod structure (Suhrez Barrios et al.,
1995), has gained extensive attention. Because of the physicochemical
performances, low cost and eco-friendly properties, Pal has been widely
used in environmental remediation (Huang et al., 2007; Zhang et al.,
2013; Frost et al., 2010; Shi et al., 2013) and agriculture (Cai et al.,
2013, 2014). Pal possessed plenty of hydroxyl groups on the rods sur-
face and thus displayed a hydrophilic property. Herein, ASO and
APTES could effectively modify the microstructure of Pal and decrease
the amount of hydroxyl groups on Pal surface, and immediately convert
the hydrophilicity of Pal to hydrophobicity. The resulting hydrophobic
Pal could be used as a high-performance agent to fabricate a super-hy-
drophobic paint. Compared with TP, such paint displayed high self-
cleaning properties.
This work aims to provide a facile, low-cost, and environmentally
friendly approach to fabricate a super-hydrophobic paint which could
have a huge application prospect in architecture, furniture, facility and
so on.
2. Materials and methods
2.1. Materials

The raw palygorskite powder (300 mesh) was provided by Mingmei

Corresponding authors. Co., Ltd. (Anhui, China). Paint was provided by Xiaomuwu Co., Ltd. (Si-
E-mail addresses: dqcai@ipp.ac.cn (D. Cai), zywu@ipp.ac.cn (Z. Wu). chuan, China). Other chemicals, analytical reagent grade without any

http://dx.doi.org/10.1016/j.clay.2016.06.015
0169-1317/ 2016 Elsevier B.V. All rights reserved.
 L. Zhou et al. / Applied Clay Science 132133 (2016) 290295
purication, were purchased from Sinopharm Chemical Reagent Com-
pany (Shanghai, China). Deionized water was used throughout this
work.
2.2. Fabrication of hydrophobic paint
Pal (4 g) was dispersed in 40 mL of ethanol. ASO (1.0 mL) was added
to the system under stirring (5000 rpm) for 5 min, and then 0.5 mL of
APTES was added under stirring (5000 rpm) for 5 min at room temper-
ature. Thereafter, the system was dried at 60 C and then ground to ob-
tain the Pal-ASO-APTES composite (300 mesh) named super-
hydrophobic Pal (SP). Finally, the SP powder was added to TP with a
weight ratio of 30% to get the hydrophobic paint.
2.3. Self-cleaning performance investigation
Hydrophobic Pal solution (0.1 g/mL) or hydrophobic paint (1.3 kg/L)
was coated on the surface of glass slide and dried at 60 C. Then a desig-
nated amount of methylene blue aqueous solution (5 g/L) or muddy
aqueous dispersion (10 g/L) was dripping at the top of the surfaces of
these two sloping slides (30), and the dripping process was recorded
by digital camera and camcorder.
2.4. Characterization
The contact angle (CA) was detected according to the sessile drop
method at room temperature. The morphology was observed on a scan-
ning electron microscope (SEM) (Sirion 200, FEI Co., U.S.A.) and a trans-
mission electron microscope (TEM) (JEOL-2010, JE Co., Japan). Wide-
angle X-ray spectra of the samples (powder) were recorded by using a
TTR-III X-ray diffractometer (XRD) (Rigaku Co., Japan) with Cu radiation
(40 kV, 200 mA, = 1.541867 , 2 = 3 to 70, scanning speed = 8/
min, step size = 0.0200). The samples were also characterized by a
Fourier transform infrared (FTIR) spectroscopy (iS10, Nicolet Co.,
Fig. 1. Digital photos of the water droplets on the coatings (A) and water contact angles (B) of different samples with WPal:VASO:VAPTES of 4 g:0 mL:0 mL (a), 4 g:0.5 mL:0 mL (b),
4 g:1.0 mL:0 mL (c), 4 g:1.0 mL:0.1 mL (d), 4 g:1.0 mL:0.3 mL (e), 4 g:1.0 mL:0.5 mL (f), 4 g:0 mL:0.5 mL (g), and 4 g:1.0 mL:0.5 mL (h) (APTES was added before ASO).
291
U.S.A.) in a KBr pellet at ambient temperature, wherein the sample con-
tent in KBr was 0.5%. For each sample, 32 scans were recorded in a 400
4000 cm1 spectral range at a resolution of 4 cm1. The thermal gravi-
metric analysis (TGA) and differential thermal analysis (DTA) were per-
formed by a thermogravimetric analyzer (Q5000IR, TA Co., U.S.A.) at a
scan rate of 10 C/min from room temperature to 800 C in nitrogen.
3. Results and discussion
3.1. Hydrophobic performance investigation of Pal-ASO-APTES composite
The modication effect of ASO and APTES on Pal was investigated
rst as shown in Fig. 1A and B. The CA of Pal varied with the amounts
of ASO and APTES, indicating that both ASO and APTES showed signi-
cant effects on the hydrophobic property of Pal. ASO alone (WPal:VASO
of 4 g:0.5 mL and 4 g:1.0 mL) could effectively increase the CA of Pal. Be-
sides, the addition of both ASO and APTES (WPal:VASO:VAPTES =
4 g:1.0 mL:0.5 mL) could further increase the CA of Pal, and CA increased
with the increasing amount of APTES. However, APTES alone was not
able to increase the CA of Pal, as shown in Fig. 1Ag and Bg. CA of the sam-
ple prepared by adding APTES before ASO (Fig. 1Ah and Bh) was rela-
tively lower compared with adding ASO before APTES (Fig. 1Af and
1Bf), indicating that ASO should be added before APTES. Considering
the modication performance and cost, WPal:VASO:VAPTES =
4 g:1.0 mL:0.5 mL was selected as the optimal modication condition.
As shown in Fig. 2a, b, and the inset in Fig. 2d, a water drop could
keep a spherical shape on the surface of SP coating or powder, but
spread rapidly on the surface of Pal. Contaminated water containing
soil or methylene blue was used to evaluate the self-cleaning perfor-
mance of SP or Pal coating. It was found that the contaminated water
tended to form spheres and roll off from the SP coating with a certain
angle between 40 and 60 (Videos S1 and S2). However, it just owed
down slowly and tended to be retained on the surface of the Pal coating,
making the surface polluted (Videos S3 and S4). Additionally, coal ash as
292 L. Zhou et al. / Applied Clay Science 132133 (2016) 290295

Fig. 2. Digital photographs of water states on (a) Pal and (b) SP coatings (inset of (b): CA of a water drop); digital photographs of (c) Pal and (d) SP powders in water (inset of (d): a water
drop on the surface of SP powder).

a contaminant was put onto the surface of SP or Pal coating to investi-
gate their anti-dust abilities. The results displayed that coal ash on the
SP coating could be easily washed off by water (Video S5). However, it
was difcult to be washed off from the Pal coating (Video S6). Clearly,
SP coating displayed a signicantly higher self-cleaning ability com-
pared with Pal coating. Interestingly, SP powder could disperse steadily
on the surface of water (Fig. 2d). However, Pal powder precipitated eas-
ily in a minute (Fig. 2c). These results indicated that SP possessed higher
hydrophobic and self-cleaning capacity compared with Pal.
3.2. Investigation of the hydrophobic property of SP
As shown in Fig. 3A, the absorption peaks at 3551 and 3390 cm1
were ascribed to the stretching vibrations of zeolitic water (OH2) and
adsorbed water (H2O) of Pal. The peaks at 984 and 1036 cm1 were as-
cribed to the stretching vibrations of SiOSi of Pal. After being modied
by APTES, these main characteristic peaks of Pal can also be seen clearly
in the spectrum of Pal-APTES. As for Pal-APTES, compared with APTES
alone, the peak ascribed to stretching vibration of CH3 became

Fig. 3. A: FTIR spectra of (ac) APTES, Pal, and Pal-APTES (WPal:VAPTES = 4 g:0.5 mL); B: FTIR spectra of (df) ASO, Pal-APTES (WPal:VAPTES = 4 g:0.5 mL), and SP. (C) Schematic illustrations
of reaction between Pal and APTES (g), and hydrogen bonds formation between Pal and ASO (h).
 L. Zhou et al. / Applied Clay Science 132133 (2016) 290295 293

Fig. 4. X-ray diffraction of SP (a) and Pal (b). Fig. 6. TGA (black) and DTA (red) curves of SP.

weakened and blue shifted from 2972 to 2933 cm1, the peak ascribed
to bending vibration of NH2 was weakened and red shifted from 1599
to 1489 cm1, and the peak at 1101 cm1 ascribed to the bending vi-
bration of CO disappeared. These results indicated that Pal probably
reacted with APTES through dealcoholization effect (Fig. 3g). As seen
in Fig. 3B, compared with Pal-APTES, the peaks (stretching vibrations
of OH2 and H2O, and swing vibration of OH) of SP red shifted from
1657 to 1655, 3390 to 3386, and 640 to 636 cm1 respectively. In addi-
tion, the peak (SiC stretching vibration) of ASO was weakened and red
shifted from 803 to 800 cm1, the peak ascribed to CH3 stretching vi-
bration was weakened and blue shifted from 2961 to 2964 cm1, and
the peaks at 1559 and 3700 cm 1 (NH2 vibration) disappeared.
These results demonstrated that hydrogen bonds (H-bonds) probably
existed between ASO (NH2, CO and CH3) and Pal (OH2, H2O, and
OH) (Fig. 3h). These FTIR analyses suggested that Pal could be effec-
tively modied by APTES and ASO through dealcoholization effect and
H-bonds respectively.
In order to study the crystal structure information of SP, XRD mea-
surements were performed as shown in Fig. 4. Several reections
(d = 3.34, 2.54, and 1.67 ) of SP were intensied compared with Pal,
which was probably because Pal could form large bunches via the H-
bonds between ASO and Pal so that the amount of rods in the same di-
rections increased. However, some reections (d = 4.25, 1.67, and
1.54 ) of SP were weakened compared with Pal. This might be because
APTES could increase the dispersion of Pal through the dealcoholization
effect as mentioned above.
Besides, the morphologies of SP system were observed. From Fig. 5a,
d, and g, it could be seen clearly that Pal was made up of a great many of

Fig. 5. SEM images of Pal (a, d), Pal-ASO (WPal:VASO = 4 g:1.0 mL) (b, e), and SP (c, f), and the TEM images of Pal (g) and SP (h) (inset in (h) is the TEM image of a single SP rod).
294 L. Zhou et al. / Applied Clay Science 132133 (2016) 290295
Fig. 7. (a, c): SEM images of TP; (b, d) SEM images of SP modied paint (insets in (c) and (d) are digital photographs of water states on these two kinds of paint).
nano rods which joined together to form plenty of woodpile-like
bunches. Therefore, Pal alone displayed a low dispersion. However,
after modication by ASO with low surface free energy, these bunches
became loose and most of the rods in a bunch were nearly in the same
direction (Fig. 5b and e), which was in accordance with the preceding
XRD result. The transformation of Pal microstructure was probably driv-
en by the H-bonds between Pal and ASO as mentioned above. Conse-
quently, this Pal-ASO complex displayed a higher roughness, which
was favorable for the hydrophobic property (Hitoshi et al., 2011). In ad-
dition, the ASO (a highly hydrophobic agent) adsorbed on the Pal sur-
face could also signicantly increase amounts of hydrophobic groups
on the surface of Pal and then convert Pal from hydrophilicity to
hydrophobicity.
Furthermore, as seen clearly in Fig. 5c, APTES could transform
the Pal-ASO bunches to a number of small nano clusters. In each SP
bunch, the Pal rods displayed a higher dispersion compared with Pal-
ASO and Pal (Fig. 5f). Therefore, SP showed obviously higher roughness
compared with Pal-ASO and Pal, which was probably attributed to the
decreasing combination between Pal and ASO caused by the
dealcoholization effect of APTES.
Fig. 8. Schematic diagram of the fabrication process and the mechanism of hydrophobic
paint.
Additionally, more ASO molecules were exposed on the surface of
the highly dispersed Pal in SP (Fig. 5h). Undoubtedly, SP possessed
higher roughness, more hydrophobic surface groups, and thus better
hydrophobicity compared with Pal-ASO and Pal.
The stability of SP was also investigated. After being placed at room
temperature for three months, SP still displayed an outstanding super-
hydrophobicity, indicating that SP was stable for at least three months
and thus could fulll the demand of application. Besides, the thermal
stability of SP was also investigated. As shown in Fig. 6, the mass loss
(3.795%) between 24.51 C and 105.82 C was attributed to the removal
of free water and OH2. The mass loss (3.389%) between 105.82 C and
270.34 C corresponded to desorption of OH2, and the decomposition
of ASO and APTES to small molecules. Therein, the DTA peak at
229.14 C represented that ASO and APTES started to decompose. The
mass loss (about 20.835%) between 270.34 C and 678.69 C suggested
the pyrolysis of small molecules of ASO and APTES. From this thermal
analysis, a conclusion could be obtained that the SP coating was stable
below 105.82 C.
3.3. Hydrophobic performance investigation of SP modied paint
TP generally displayed an irregular and smooth piece morphology
(Fig. 7a and c) and a hydrophilic property (inset in Fig. 7c). Thus it
tended to be polluted by contaminated water. When SP was added to
TP with a weight ratio of 30%, the SP nano clusters could be easily
adsorbed on the surface of TP piece (Fig. 7b), making TP pieces possess
rough surface, hydrophobic surface groups, and thus hydrophobic prop-
erty (Fig. 7d). Therefore, contaminated water containing methylene
blue on the surface of the SP-modied TP coating could display a spher-
ical shape with a CA greater than 140 (inset in Fig. 7d), so that the con-
taminated water could easily roll off from the coating (Video S7). In
comparison, the contaminated water on the surface of Pal-modied TP
or TP coating tended to be adsorbed and retained on the surface,
resulting in a polluted coating (Video S8 and Video S9). Obviously, the
SP-modied TP exhibited higher hydrophobicity and outstanding self-
cleaning ability compared with TP.
Based on the preceding analysis, the fabrication process and the
mechanism of hydrophobic paint could be summarized as shown
in Fig. 8. ASO could make the original Pal bunches loose with higher
roughness and more hydrophobic surface groups through H-bonds.
 L. Zhou et al. / Applied Clay Science 132133 (2016) 290295
Subsequently, APTES could transform the loose Pal-ASO bunches to
plenty of nano clusters through the dealcoholization effect, so that the
resulting Pal-ASO-APTES (actually SP) displayed much higher rough-
ness, much more hydrophobic surface groups, and thus much higher
hydrophobicity. The SP nano clusters could be easily adsorbed on the
surface of TP piece, therefore, when SP was mixed with TP, TP could cer-
tainly possess rough surface, hydrophobic surface groups, hydrophobic
property, and thus high self-cleaning capacity.
4. Conclusions
In this work, a facile and low-cost method to fabricate super-hydro-
phobic paint using Pal modied by ASO and APTES was successfully de-
veloped. Therein, ASO and APTES could effectively modify the
microstructure and surface of Pal to increase the roughness and
amounts of hydrophobic surface groups through H-bonds and
dealcoholization effect, obtaining a super-hydrophobic Pal named SP.
The addition of SP could signicantly transform traditional paint from
hydrophilic to highly hydrophobic. Meanwhile, this SP modied paint
displayed ne self-cleaning properties.
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.clay.2016.06.015.
Acknowledgments
The authors acknowledge nancial support from the National Natu-
ral Science Foundation of China (No. 21407151), the Key Program of
Chinese Academy of Sciences (No. KSZD-EW-Z-022-05), the Science
and Technology Service Programs of Chinese Academy of Sciences
(Nos. KFJ-EW-STS-083 and KFJ-EW-STS-067), and the Grant of the
President Foundation of Hefei Institutes of Physical Science of Chinese
Academy of Sciences (No. YZJJ201502).
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