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Superhydrophobic Coatings
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Facile Fabrication of Superhydrophobic Nanocomposite

Coatings Based on Water-Based Emulsion Latex
Jixiang Yang, Huiyun Liang, Liheng Zeng, Shuai Liu, and Tianying Guo*

become an outstanding strategy to fabri-

To prepare water-based superhydrophobic coatings with excellent properties cate superhydrophobic coatings.
would be of great significance, but it remains difficult to solve the problems Generally, polymer/inorganic super-
hydrophobic composite coatings are pre-
of uneven dispersion of hydrophobic modified inorganic nanofillers in water
pared by incorporating modified inorganic
and poor interfacial compatibility between hydrophilic inorganic nanofillers nanofillers into polymer resin. Inorganic
and polymer matrix in the film. Herein a novel and green technology is nanofillers modification is a good way
reported to disperse dodecyltriethoxysilane in water-based polymer system for evenly dispersing inorganic–organic
uniformly by adsorbing it on the surface of emulsion latex particles first. Then phase due to the improved interfacial
compatibility. As it has been demonstrated
after silica nanoparticles being introduced into the system, the hydrophobic
that surface chemical composition and
modification is realized by the coupling reaction between silica nanoparti- surface topography act synergistically to
cles and the alkylsilane in the film-forming process. Furthermore, various construct superhydrophobic surface.[13]
common water-based emulsion latexes are able to be applied as the binder The inorganic nanofillers used here are
between the modified nanoparticles and substrates. The resulting coatings normally modified with hydrophobization
exhibit excellent superhydrophobicity and show remarkable mechanical dura- reagents, which will promote the supe-
rhydrophobicity on the coating surface.
bility as well as chemical stability. In addition, these nanocomposite coatings
Recent progress has developed a myriad of
are demonstrated of high performance for oil/water separation. The findings hydrophobic inorganic nanomaterials, for
provide a valuable way to fabricate water-based and fluorine-free superhydro- example, fluorinated multiwalled carbon
phobic coatings with excellent properties for potential industrial applications. nanotubes,[14] oligodimethylsiloxane modi-
fied fumed silica nano­ particles,[15] and
fluorinated silica nanoparticles.[16]
1. Introduction Poly­mer/inorganic superhydrophobic coatings possessing
excellent water-repellent properties could be obtained after
On account of the significant potential applications in self- the hydrophobic inorganic nanofillers being introduced into
cleaning,[1] anti-icing,[2] oil/water separation,[3] corrosion poly­mer resin. However, to dissolve the polymer resin and dis-
resistance,[4] drag reduction,[5] and so forth, superhydrophobic perse hydrophobic inorganic nanofillers evenly, VOCs such as
coatings, which generally demonstrate static water contact acetone, tetrahydrofuran, and toluene were required to prepare
angles (CAs) over 150° and sliding angles (SAs) below 10°,[6] the dispersion, which would lead to severe environment prob-
have gathered enormous attractions. Through years of persis- lems. Thus, these drawbacks remarkably hold up the practical
tent efforts, various successful methods have been developed applications of the superhydrophobic composite coatings.
to fabricate superhydrophobic surfaces such as lithography,[7] In recent decades, water-based coatings have been more and
phase separation method,[8] sol–gel processing,[9] chemical/ more popular in coatings industry due to the environmental
electrochemical etching,[10] layer-by-layer assembly,[11] and pollution, resource waste, and high costs of solvent-based coat-
polymer/inorganic composites.[12] Among these approaches, ings.[17] And commercial water-based emulsion latex could be
with the advantages of simple fabrication process and excellent widely accessed in preparing water-based coatings nowadays.
coating performance, polymer/inorganic composites have However, low surface energy materials especially hydrophobic
modified inorganic materials are difficult to disperse in water,
thus only limited studies of water-based superhydrophobic
Dr. J. X. Yang, H. Y. Liang, L. H. Zeng, Dr. S. Liu, Prof. T. Y. Guo coating systems have been reported.[18] For instance, Zhou et al.
Key Laboratory of Functional Polymer Materials
Ministry of Education
reported using a stable dispersion of polytetrafluoroethylene
Institute of Polymer Chemistry (PTFE) nanoparticles, fluorinated alkylsilane and fluorocarbon
College of Chemistry surfactant to prepare superamphiphobic surface, in which the
Nankai University similar fluoroalkyl chain in abovementioned ingredients syn-
Tianjin 300071, China ergistically played an important role.[18a] The other methods
E-mail: [email protected]
mostly introduced hydrophilic nanofillers in water-based sys-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/admi.201800207.
tems. For example, Schutzius et al. developed a superhydro-
phobic coating via polyolefin blend dispersion and exfoliated
DOI: 10.1002/admi.201800207 graphite nanoplatelets under alkaline conditions.[18b] Mates

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et al. fabricated superhydrophobic coatings on nonwoven the emulsion latex particles via hydrophobic interaction and
and cellulosic substrates consisting of aqueous fluoroacrylic compatibility of similar structure. Subsequently, silica nano-
copolymer dispersion and hydrophilic bentonite nanoclay particles added in the system could be modified by coupling
particles.[18e] In these attempts to fabricate water-based super- reaction via the contact with alkylsilane after water evaporated
hydrophobic coatings, though hydrophilic inorganic nanofillers in the film-formation process. The resulting superhydrophobic
can be dispersed in water simply and homogeneously to form nanocomposite coatings were proved to be highly stable under
coating suspension, phase separation and nanofillers deposi- mechanical damage and chemical attack. This strategy pro-
tion would emerge in the nanocomposite coating matrix due vides a practical and universal platform to prepare water-based
to the poor interfacial compatibility between inorganic and and fluorine-free superhydrophobic nanocomposite coatings.
organic components, which leads to the poor mechanical sta- More importantly, the components in the coating suspension
bility or insufficient surface roughness. Besides, although be are changeable, and taking into consideration of the massive
frequently used to fabricate superhydrophobic surfaces with its emulsion latexes, numerous nanofillers, and diverse modifica-
excellent performance to reduce surface tension,[19] fluorinated tion reactions, this system proposed here demonstrates great
chemicals including fluoropolymer compound and perfluoro- promise for the development of water-based superhydrophobic
alkylsilanes have potential adverse impact on human health and coatings for real-life application.
environment, which calls for the development of fluorine-free
superhydrophobic coatings.[20] Hence, despite many advances
have been achieved, it is still challenging to develop water-based 2. Results and Discussion
and fluorine-free nanocomposite coatings with modified inor-
ganic components possessing excellent superhydrophobicity 2.1. Preparation of Superhydrophobic Nanocomposite Coatings
for practical application.
In this work, we introduced a novel approach to fabricate The preparation of superhydrophobic nanocomposite coating
water-based and fluorine-free superhydrophobic nanocom- is illustrated in Figure 1a. As dodecyltriethoxysilane is soluble
posite coatings. First, dodecyltriethoxysilane was dispersed in in ethanol but insoluble in water, ethanol was introduced to
the water-based polymer system uniformly by adsorbing on help the dispersion of alkylsilane in water-based emulsion

Figure 1.  a) The schematic illustration of the preparation of superhydrophobic nanocomposite coatings. b,c) The histogram of size distribution pre-
sented the sizes of silicone-acrylic emulsion latex particles in the dispersion of emulsion latex before and after the alkylsilane added.

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latex. With the increase in the ethanol content, the alkylsilane latex particles. Finally, the coating suspension was directly
could be evenly dispersed in ethanol/emulsion latex dispersion. applied on substrates by spraying to get superhydrophobic sur-
Because of the low surface tension of emulsion latex particles, faces. With the suitable weight ratio of polymer content, alkyl-
when alkylsilane was added in ethanol/emulsion latex disper- silane, and silica nanoparticles of 10:6:9 in the nanocomposite
sion, it would be adsorbed on the surface of emulsion latex coating suspension, the CA reached the highest of 155.6°, and
particles by hydrophobic interaction and van der Waals force the SA was lowest of 4.7° for silicone-acrylic nanocomposite
(Figure S1, Supporting Information). Therefore, by measuring coatings (Figures S5 and S6 and Table S1, Supporting Informa-
the particle sizes of latex particles after alkylsilane added to the tion). Similarly, superhydrophobicity was achieved on styrene-
ethanol/emulsion latex dispersion with different ethanol con- acrylic and pure-acrylic nanocomposite coatings, which the
tent, it was observed that the alkylsilane could be completely CAs reached 154.1° and 151.4°, the SAs reached 6.8° and 9.7°,
dispersed when the weight ratio of ethanol to emulsion latex is respectively, also with the weight ratio of the three components
2:5 (Figure S2, Supporting Information). Furthermore, without as 10:6:9.
emulsion latex, the alkylsilane would be separated from the eth- Because of the nanosize diameter and high specific surface
anol/water dispersion when it was diluted with water, and the area, the dispersion and the agglomeration of silica nanoparti-
alkylsilane also cannot be well dispersed in alkylsilane/silica cles will provide coating surface with micro/nanoscale rough
nanoparticles dispersion (Figure S3, Supporting Information). structure (Figure S7, Supporting Information). As shown in
As shown in Figure 1b, c, after alkylsilane being incorporated Figure 2a, b, the representative surface morphologies on the
to the ethanol/emulsion latex dispersion, the sizes of emulsion silicone-acrylic nanocomposite coating were obtained by the
latex particles changed from about 103.2 to 129.7 nm, which scanning electron microscopy (SEM) measurement. The micro-
confirmed that alkylsilane molecules were adsorbed on the sur- scale roughness and nanoscale aggregation constituted by silica
face of the particles. And due to the homogeneously dispersion nanoparticles are apparently presented on the coating surface.
of emulsion latex particles in the water-based system, alkylsilane And there are plenty of irregular cavities among nanopar-
molecules were also homodisperse. Subsequently, the disper- ticle clusters. On the basis of Wenzel and Cassie's theories, air
sion was mixed with silica nanoparticles aqueous dispersion to trapped in the void spaces on the rough surface bring about the
prepare water-based and fluorine-free superhydrophobic nano- antiwetting properties. However, the phase separation of nano-
composite coating suspension. The sizes of particles in silica particles and polymer content presented on the coatings in the
nanoparticles dispersion and alkylsilane/emulsion latex/ silica absence of alkylsilane, but the homodispersion of nanoparticles
nanoparticles dispersion were investigated as well (Figure S4, and polymer content appeared in the exist of alkylsilane, due to
Supporting Information), though the sizes changed to 138.6 nm the different compatibility of nanoparticles and polymer content
in the final coatings suspension, that is mainly because of with or without modification by alkylsilane (Figure S8a, b, Sup-
the addition of silica nanoparticles which showed the particle porting Information). The surface roughness was also meas-
sizes as 323.4 nm in aqueous dispersion due to agglomeration ured by atomic force microscope and characterized by the root
of nanoparticles. The resulting size distribution of the parti- mean square of roughness (Rq) on the nanocomposite coating.
cles indicates that the addition of silica nanoparticles have no As can be seen from Figure 2d, e, the micro/nanoscale struc-
obvious influence to the adsorption of alkylsilane on emulsion ture was further confirmed and the Rq are 153.0 nm. However,

Figure 2.  a,b) SEM images of the silicone-acrylic superhydrophobic nanocomposite coating. c) EDX measurements of the nanocomposite coating,
the insets are snapshot of measured CAs. d,e) The atomic force microscopy (AFM) image of the nanocomposite coating and pristine silicone-acrylic
coating. f) The CAs and SAs on the surfaces of different substrates.

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the pristine silicone-acrylic copolymer coating had smooth sur- common water-based emulsion latex, alkylsilane, and unmodi-
face with Rq of 12.3 nm. Energy dispersive X-ray (EDX) analysis fied silica nanoparticles in water with the assistance of small
further confirmed the surface chemical composition on the amount of ethanol to form homogenously nanocomposite
nanocomposite coating. As depicted in Figure 2c, the content of coating suspension was used. In the nanocomposite coating
carbon is 55.68% for the silicone-acrylic superhydrophobic nano- suspension, alkylsilane was dispersed in the water-based disper-
composite coating, but the content of carbon is merely 29.82% sion then adsorbed on the surface of latex particles which have
for the nanocomposite coating in the absence of alkylsilane been verified by the change of particle sizes. The surfactant on
(Figure S8c, Supporting Information), which reveals that the the surface of latex particles could stabilize the adsorbed alkyl-
long alkyl chain in alkylsilane gathered on the coating surface. silane. During the film-forming process, with the continuous
To expand these superhydrophobic nanocomposite coat- water evaporation, emulsion latex particles and silica nano-
ings into large-scale and real-life application, the adaptability particles would accumulate and contact with each other. Then
between the nanocomposite coatings and different substrates alkylsilane could migrate to the surface of silica nanoparticles
needs to be investigated. We used various substrates such as from emulsion latex particles, and coupling reaction occurs
glass, paper, steel, wood, textile, and aluminum for the coating between alkylsilane and silanol group on the surface of silica
(Figure 2f and Figure S9, Supporting Information). Because of nanoparticles (Figure 3). To confirm the reaction of alkylsilane
the good film-forming and adhesion of silicone-acrylic, styrene- with nanoparticles in the film-forming process, the attenu-
acrylic, and pure-acrylic emulsion latex on these substrates, the ated total reflectance Fourier transform infrared spectroscopy
superhydrophobic nanocomposite coatings can be coated on (ATR-FTIR) spectrum of the nanocomposite coatings was
different substrates suitably. With sphere-like water droplets applied (Figure 4 and Figure S10, Supporting Information),
formed on the coating surface, it reveals the excellent water the peak at 1061 cm−1 represents the SiOSi structure. The
repellency of the coating on different substrates. absorption band at 2923 cm−1 can be attributed to the vibration
of the CH bond and the peak appeared at 722 cm−1 represents
the wagging stretching of CH2 structure in the alkyl chains
2.2. Validation of the Film-Forming Process of alkylsilane. Compared to the ATR-FTIR spectrum of silica
nanoparticles and pristine polymer coatings, the characteristic
It is well known that the hierarchical micro/nanoscale struc- peaks of CH and CH2 obviously strengthened in the spec-
ture and low surface energy materials lead to extreme water trum of superhydrophobic nanocomposite coatings (Figure 4a
repellency properties on the coating surface. Different from and Figure S10a, d, Supporting Information). It indicates that a
the methods that synergistically stable dispersing PTFE nano- lot of alkyl groups in the superhydrophobic nanocomposite coat-
particles in water with fluorinated alkylsilane and fluoro- ings, which provides low surface energy on the coating surfaces.
carbon surfactant, or codispersing hydrophilic nanofillers with Furthermore, the three kinds of superhydrophobic nanocom-
hydrophobic emulsion latex,[18] here the strategy of dispersing posite films were dissolved in tetrahydrofuran. Subsequently

Figure 3.  The schematic illustration of the film-forming process occurred in the superhydrophobic nanocomposite coatings.

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Figure 4.  a) ATR-FTIR spectra of the silicone-acrylic nanocomposite coating. b, c) Zoom-in the ATR-FTIR spectra of the silicone-acrylic nanocomposite
coating. Four kinds of samples were presented: silica nanoparticles, pristine polymer coating, superhydrophobic nanocomposite coating, and the
residues after dissolving. The samples named as “residues after dissolving” were prepared by dissolving the superhydrophobic nanocomposite films
in tetrahydrofuran and centrifuging to get silica nanoparticles and repeated the washing process for three times.

the suspension was centrifuged and repeated this washing polymer matrix by modification after film-forming process,
process for three times, then dried. After the washing process, which correlates to the mechanical stability of coating films.
the polymer component and the possible self-polycondensated Therefore, this is a good strategy to fabricate water-based super-
alkylsilane could be washed away, and silica nanoparticles hydrophobic nanocomposite coating.
would be residue. From the magnified ATR-FTIR spectrum
(Figure 4b,c and Figure S10b,c, e,f, Supporting Information),
the characteristic peaks of CH and CH2 retained, that 2.3. Mechanical Durability
means the reaction between alkylsilane and silica nanoparticles
occurred. Certainly, these results confirmed the aforementioned Because that micro/nanoscale structure is usually damaged by
film-forming process. As a result, alkylsilane modified silica mechanical friction easily, which leads to the loss of superhy-
nanoparticles would improve the compatibility with poly­mer drophobicity, fabrication of robust surface has been an impor-
content and reduce the surface energy on the coating surface. tant issue in the application of superhydrophobic coatings. In
For this reason, the hydrophilic nanoparticles can not only this work, different methods were used to evaluate the robust-
be well dispersed in the water-based nanocomposite coating ness of the superhydrophobic nanocomposite coatings such as
suspension but also have good interfacial compatibility with sandpaper abrasion and compression-release test (Figure 5a,b

Figure 5.  a) CAs and SAs of silicone-acrylic nanocomposite coating after different abrasion cycles. b) The CAs and SAs of the sponge coated by silicone-
acrylic nanocomposite coating after different compression-release cycles. c) The nanocomposite coatings immersed in ethanol, n-hexane, butyl acetate,
and xylene for 14 d, and water droplets on the coating surface.

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and Figure S11, Supporting Information). After 30 abrasion industrial organic pollutants. Recently, superhydrophobic
cycles in sandpaper abrasion test, little change of CAs and SAs materials provide an attractive solution. Owing to the
has been observed on the surface of the silicone-acrylic supe- good mechanical durability and chemical stability of these
rhydrophobic nanocomposite coating, the CAs retained larger superhydrophobic nanocomposite coatings, here, com-
than 150°, and SAs retained smaller than 10°. Therefore the mercial sponges coated with these superhydrophobic nano-
coating still remained superhydrophobicity after mechanical composite coatings were used in oil/water separation. Due
damage, which reveals that these superhydrophobic nano­ to the superhydrophobicity and oleophilicity on the surface
composite coatings are mechanical durability. Since alkylsilane of the sponge, oils will be absorbed into the sponge quickly
modified silica nanoparticles could be dispersed more evenly as well as the water will be repelled. So removing oil from
in the polymer matrix, and the modification improved the water could be realized. With the help of pump to extract oil
interfacial interaction between hydrophobic nanoparticles and inside the sponge, the oil outside the sponge will continu-
polymer as well as the adhesion of nanoparticles to substrates, ously enter inside spontaneously by capillary force, which
the abrasion resistance of the superhydrophobic nanocomposite results in a continuous oil/water separation (Figure 6a).
coatings was enhanced. Moreover, by spray casting the nano- Since there are various oils and organic pollutants in reality,
composite coating on sponge, the superhydrophobic sponge oils and organic solvents with different density and viscosity
still keeps superhydrophobicity after 300 times of compression- were selected to investigate the oil/water separation capacity
release cycles. That indicates the nanocomposite coating could of as-prepared sponges. As shown in Figure 6b, c, the supe-
be stably applied on flexible substrates. All above results demo­ rhydrophobic sponges can uptake many kinds of oils and
nstrate that these superhydrophobic nanocomposite coatings organic solvents with 20–40 times its own weight. And the
possess good mechanical durability. separating efficiencies are larger than 95% for various oils
and organic solvents. Furthermore, good recyclability of the
superhydrophobic sponges is a key point for utilization so
2.4. Chemical Stability that the sponge can be reused or collect different oils. From
Figure 6d, the separating efficiency is almost steady after
The chemical stability of these superhydrophobic nanocom- 12 cycles, which means the high recyclability besides the
posite coatings is necessary for the usage in practical applica- high separating efficiency. Thus, the results indicate that
tion. In this work, the chemical stability was verified by organic these superhydrophobic nanocomposite coatings have out-
solution immersion, UV irradiation test and acid/base solution standing potential application in oil/water application owing
test. The solvents including ethanol, n-hexane, butyl acetate, to the good absorption amount, separating efficiency, and
and xylene with different polarity and solubility were applied to recyclability.
research the solvent resistance of the silicone-acrylic superhy-
drophobic nanocomposite coating (Figure 5c and Figure S12,
Supporting Information). After immersion for 14 d, there are no 3. Conclusion
remarkable change of the CAs and SAs. And sphere-like droplet
can be observed on the coating surface after water dropped on In summary, we proposed a novel and green strategy to
the coatings after the solvents evaporated. Considering the out- modify silica nanoparticles with alkylsilane in water-based
door usage of the superhydrophobic nanocomposite coatings, polymer systems to fabricate water-based and fluorine-free
UV resistance is another important concerning issue. Due to superhydrophobic nanocomposite coatings and clarified
the impact of UV light to chemical bond of organic component, the modification mechanism. Hydrophobic alkylsilane was
the low surface energy on the coating surface could be changed, homogenously dispersed in water-based polymer systems
so the superhydrophobicity of the coating will be affected. It has by adsorbing on the surface of emulsion latex particles via
been implied in Figure S13a in the Supporting Information, hydrophobic interaction and van der Waals force. In the film-
the superhydrophobic nanocomposite coating is UV resistance. forming process, hydrophobic modification occurred by the
In addition, corrosive solution such as acid/base solution was contact between alkylsilane and silica nanoparticles which are
dropped on the coatings surface. These nanocomposite coatings also evenly dispersed in the coating suspension. In this way,
retain superhydrophobicity to different aqueous liquids with pH various common emulsion latexes are able to be applied in
ranging from 1 to 13 (Figure S13b, Supporting Information). this system. As the weight ratio of polymer content, alkylsi-
For further study, the nanocomposite coatings were immersed lane and silica nanoparticles to be 10:6:9, the silicone-acrylic
in 1 m HCl solution, saturated NaCl solution and water for 24 h nanocomposite coatings present the best water repellency
(Figure S14, Supporting Information). It reveals the good dura- with CA of 155.6° and SA of 4.7°. Furthermore, the coat-
bility and stability of surface superhydrophobic character for ings exhibited stable superhydrophobicity against mechanical
these superhydrophobic nanocomposite coatings to corrosive abrasion, compression-release test, organic solution immer-
solution while there is no visible change of the CAs and SAs. sion, UV irradiation, and acid/base corrosion, which showed
the durability and stability in harsh conditions. In addi-
tion, good performance was achieved in high oil absorption
2.5. Oil/Water Separation amount, oil/water separating efficiency as well as excellent
separating recyclability. It is believed this facile and environ-
An effect method of oil/water separation has been an emer- mental-friendly approach possesses prominent practicability
gency demand for the growing problem of oil spillage and in industrial applications.

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Figure 6.  a) Photograph of the separation test of oil (dyed red) from water. b) The oil absorption amount of the nanocomposite coating coated
sponges. c) Separating efficiency of the as-prepared sponges for various oils. d) Separating efficiency with different cycles for kerosene, silicone-acrylic
nanocomposite coating coated sponge used as representative.

4. Experimental Section F20, FEI, USA). Morphologies of the coatings surface were characterized
by field emission scanning electron microscope (JSM-7500F, JEOL,
Materials: Hydrophilic fumed silica (average size: 14 nm) was Japan). The elemental compositions on the surface of the coatings were
purchased from Aladdin Reagent, China. Dodecyltriethoxysilane investigated by the accessory of EDX spectroscopy . Root-mean-square
(analytical grade) was provided by Heowns Reagent, China. Picassian roughness values of the coatings were carried out by atomic force
AC-122 (40% solid content, water-based, styrene-acrylic copolymer microscope (Nanoscope IV, Veeco, USA) in a tapping mode. The ATR-
emulsion) was purchased from Stahl, Netherlands. Silicone-acrylic FTIR characterization of the samples was carried out by FTIR (Tensor
copolymer emulsion (48% solid content, water-based), pure-acrylic II, Bruker, Germany) in the wave number between 4000 and 400 cm−1.
copolymer emulsion (54% solid content, water-based) were purchased The abrasion resistance test was carried out by using 600-grit
from Beijing Donglian Chemical Co. Ltd., China. Absolute ethanol sandpaper with 100 g loading on the superhydrophobic surface which
(analytical grade) was purchased from Tianjin Chemical Reagent Co. coated on glass substrates. The sample on the sandpaper was moved
Ltd., China. Polyurethane (PU) sponge was purchased from local 10 cm with one linear distance at a constant speed, and back to forth as
supermarket, China. All chemicals were used without further purification. one abrasion cycle.
Preparation of the Superhydrophobic Nanocomposite Coatings: In a Organic solvent resistance test were investigated by immersing the
typical process, silicone-acrylic emulsion latexes (10.0 g) were treated samples in ethanol, n-hexane, butyl acetate, and xylene, the CAs and
with ethanol (4.0 g) under stirring for 5 min to disperse homogenously. SAs of the nanocomposite coatings were tested every 48 h. The samples
Subsequently, dodecyltriethoxysilane (3.0 g) was introduced into the were coated on glass slide with the size as 38 mm × 26 mm.
dispersion by stirring for 10 min. Then the dispersion was mixed with UV irradiation test was carried out by a 12 W Hg lamp with a
the silica aqueous dispersion containing silica nanoparticles (4.5 g) wavelength of 254 nm (ZF-1, Shanghai Gucun Electro-optical Instrument
and water (200 mL), the final suspension was agitated for 30 min. The Factory, China), the CAs and SAs of the nanocomposite coatings were
spray coating was performed under the condition of 60 °C by a spray tested every 24 h.
gun (nozzle diameter, 0.5 mm) with the injection pressure of 25 psi, and The absorption amount and separating efficiency were determined
the spray distance between the nozzle and the substrates was 15 cm. by averages of four replicated measurements. The absorption amount
The coated substrates were dried for 12 h in room temperature and then showed the weight of solvent that can be absorbed in per gram of
further dried at 60 °C for 12 h. sponge. The separating efficiency was defined as the weight ratio of oil
Characterization: The static contact angles and sliding angles that collected by sponge to the oil in oil/water mixture before separation.
were measured using a contact angle measuring device (JC2000D, The superhydrophobic sponge was rinsed by ethanol thoroughly and
Shanghai Zhongchen Equipment Ltd., China). Deionized water was dried after every separating cycle. In the separating efficiency test, 60 g
used for the measurement, 5 µL liquid was used in the measurement oils and 120 g water were put in beaker for separation.
of contact angles and 7 µL liquid in the sliding angle measurement.
All the reported values are averages of four replicated measurements.
The surface tension was characterized by surface tension meter (JZHY-
180, Chengde Dahua Testing Machine Co., Ltd., China). The sizes of Supporting Information
nanoparticles were measured by the dynamic light scattering (Nano
ZS90, Malvern Instruments Ltd., UK). Morphologies of the particles Supporting Information is available from the Wiley Online Library or
were characterized by transmission electron microscopic (Tecnai G2 from the author.

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