Colloids and Surfaces A 561 (2019) 101–108

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Colloids and Surfaces A

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

Superhydrophobic and photocatalytic PDMS/TiO2 coatings with T

environmental stability and multifunctionality
Yaling Wang1, Zhiwei Huang1, Robert S Gurney, Dan Liu
⁎

School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, China

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Maintaining the long-term stability of TiO2-based superhydrophobic (SH) coatings remains a considerable
Superhydrophobic challenge because of the strong photocatalytic properties of TiO2. The organic SH components that surround the
Photocatalytic TiO2 particles are often degraded when the coating is exposed to UV light, thus destroying the anti-wettability
Multifunctional properties. In our work, we fabricated a UV-stable SH coating from dispersions of polydimethylsiloxane (PDMS)
Self-cleaning
and TiO2 nanoparticles, which can be easily applied to a wide range of substrates by spray coating. The resulting
Environmental stability
films possess SH properties due to the combination of the low surface energy of PDMS, and the hierarchical
structure resulting from the different aggregation sizes of TiO2 nanoparticles. The coating can recover its SH
properties after exposure to organic pollutants, which can be photo-degraded and removed by TiO2. The coating
is highly durable due to the crosslinked PDMS, and SH properties are retained after 7 days under UV light, or 3
months exposure to sunlight in outdoor conditions. We also demonstrate the coating’s good resistance to cor-
rosion, water impact, and high temperature, all while maintaining superhydrophobicity. This multifunctional SH
coating represents a very promising material for commercial and industrial coatings applications.

1. Introduction (WCA) higher than 150°, and a sliding angle (SA) lower than 10°. Water
droplets can thus easily roll across these surfaces and carry away sur-
SH surfaces can be prepared through a variety of methodologies and face contaminants, hence SH films often display good self-cleaning
technologies [1–5] and are defined as having a water contact angle properties. In recent years, SH surfaces have showed wide industrial

⁎
Corresponding author.
E-mail address: dliu@whut.edu.cn (D. Liu).
1
These authors contributed equally.

https://doi.org/10.1016/j.colsurfa.2018.10.054
Received 3 September 2018; Received in revised form 19 October 2018; Accepted 21 October 2018
Available online 28 October 2018
0927-7757/ © 2018 Elsevier B.V. All rights reserved.
Y. Wang et al.
and biological applications such as de-icing [6], self-cleaning outdoor
windows [7], oil-water separation [8], and antibacterial surfaces for the
medical industry [9]. The two key factors for SH wetting behavior are
considered to be low surface energy and multiscale structure (rough-
ness) [10,11]. It follows that two methodologies can be employed to
fabricate SH surfaces: optimizing roughness on a low surface energy
material; or modifying a rough surface using low surface energy ma-
terials.
Fabrication of TiO2 hybrid SH surfaces has attracted increasing at-
tention in recent years [12–14], as the photocatalytic properties of TiO2
makes them possible to work in harsh environmental conditions. When
semiconductor metal oxides like TiO2 are excited by high-energy ul-
traviolet light, photogenerated holes and electrons can be produced and
provide the metal oxides excellent photocatalytic properties. The strong
oxidizing agents (O2− and OH% radicals) on the coating surface gen-
erated by the charge carriers can decompose absorbed organic mole-
cules [15]. For instance, when a TiO2-based SH surface is polluted by
oily dirt or organic matter, the TiO2 can degrade the pollutants, and this
self-cleaning recovers the SH properties [16,17]. However, TiO2 will
also degrade those low surface energy materials that constitute the SH
films, resulting in extremely poor durability of the SH properties which
represents a hurdle to be overcome if such materials are to be used in
real applications.
Polymeric materials like PDMS are used in many everyday ma-
terials due to their excellent durability and mechanical properties
because of their stable crosslinked structure. PDMS has hydrophobic
properties, chemical inertness, high elasticity, easy processing as
well as being environmentally-friendly [18,19]. For example, Zhou
et al. added 1 wt.% PDMS into fluoroalkyl silane modified silica
nanoparticles, which significantly improved the mechanical proper-
ties of the SH film [20]. Researchers have also shown that using
PDMS with TiO2 does not inhibit the photocatalytic properties of
TiO2. Wooh et al. [21] fabricated a photocatalytic SH surface via
grafting PDMS brush onto the surface of MOPCs, and Zhao et al. [22]
prepared SH surfaces by embedding TiO2 nanoparticles into printed
arrays of PDMS posts, which exhibit good photocatalytic and self-
cleaning properties. Shuai et al. [23] made a superhydrophobic and
superoleophilic PDMS-TiO2 coated PU sponge by immersing a PU
sponge in TiO2 sol-gel, followed by in situ polymerization of PDMS.
PDMS also acts as a bonding agent to hold the SH nanoparticles to-
gether and adhere them to the substrate. Huang et al. [24] reported
an approach to fabricate durable multifunctional SH surfaces by
using a TiO2/PDMS/Cu coating system in which PDMS imparts good
mechanical properties and serves as both the adhesive and hydro-
phobic material.
These strategies demonstrate the benefits and feasibility of PDMS
for use in SH materials. However, some approaches such as etching
[25], sol-gel synthesis [26,27], chemical polymerization [23], and
chemical vapor deposition [28] are time-consuming and require com-
plicated procedures, specific equipment, or harsh conditions, which
limit their applications in large scale production. An economical, simple
and effective method to fabricate physical and chemical stable SH
surfaces is pursued by researchers.
Herein, inspired by the above investigations and considering the
feasibility for large-scale production, a facile, environmentally-friendly
and effective method for fabricating a multifunctional SH coating is
demonstrated by blending PDMS and TiO2 nanoparticles in good sol-
vents. After spray-coating the blend solution onto various substrates
and curing at 120 °C, SH surfaces were obtained through the combined
contributions of aggregated TiO2 nanoparticles and the low surface
energy PDMS. Water impacting tests, immersion in corrosive liquids,
high temperature calcination, and degradation of organic materials
demonstrate the excellent photocatalytic properties and high physical
and chemical stabilities of this SH coating. Such a SH surface is po-
tentially highly useful for industrial production and commercial appli-
cations.
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Colloids and Surfaces A 561 (2019) 101–108
2. Experimental
2.1. Materials
TiO2 (Degussa P25, particle size 25 nm, anatase and rutile with
80:20 wt ratio) was purchased from Xijia Chemical Company (China).
PDMS (Sylgard 184A) and curing agent (Sylgard 184B) were purchased
from Dow Corning Company (U.S.A.). The solvents, anhydrous ethanol
and hexane were obtained from Shenshi Chemical (China). All chemi-
cals were analytical grade and used as received.
2.2. Methods
PDMS precursor Part-A (Sylgard184 elastomer base) and PDMS
precursor Part-B (Sylgard184 curing agent) were mixed with propor-
tions of 10:1, then 0.8 g of the mixture was dissolved in a mixed sol-
vents of hexane (2.4 g) and anhydrous ethanol (4.8 g). The solution was
then ultrasonicated for 10 min, at which point TiO2 nanoparticles were
added to the solution and stirred then ultrasonicated for 10 min.
In order to investigate the weight ratio influence of TiO2 and PDMS
in the solution on the SH properties of the final film surfaces, a variety
of weight ratios of PDMS and TiO2 were selected. Ratios of 4:1 (0.2 g
TiO2), 4:2 (0.4 g TiO2), 4:3 (0.6 g TiO2), 4:4 (0.8 g TiO2) and 4:5 (1.0 g
TiO2), were chosen to dissolve in the aforementioned solvents. The
prepared solutions were directly sprayed on various substrates in-
cluding glass slide, rubber, cotton, silicon wafer and paper, before
curing at 120 °C for 40 min in air. The spraying process consists of using
a spray gun with a nozzle diameter of 0.5 mm and spraying distance of
approximately 20 cm with a gas pressure of 18 psi, and can completely
cover a 75 mm × 25 mm glass substrate after about 10 s.
2.3. Characterization
The surface morphology was examined by scanning electron mi-
croscope (SEM) (Hitachi S4800, Japan) at 5.0 kV. The chemical com-
positions of the coatings were analyzed by a Fourier transform infrared
spectrometer (FT-IR) (Nicolet 6700, U.S.A.) in the wave number range
of 4000–400 cm−1. UV light illumination was carried out using a 48 W
mercury xenon lamp (wavelength = 365 nm). An ultraviolet-visible
spectrophotometer (UV–Vis) (Lambda 750 S, America) was employed
for the diffuse reflectance spectra, from which CIELab colorimetric
coordinates were calculated. Stylus Profilometry (Dektak XT, America)
was used to evaluate the surface roughness of the SH coatings.
Thermogravimetric analysis (TGA) (Netzsch STA 449 F3, Germany) was
performed on the PDMS/TiO2 composite coatings, and samples were
heated at a rate of 10 °C/min. Water contact angles (WCAs) were
measured by a surface analysis instrument (Theta Attension, Biolin
Scientific, Finland) at room temperature and recorded by OneAttension
software. The average WCA values of the samples were obtained from 5
measurements at different positions of each sample using 5 μl water
droplets. The average values of sliding angles (SAs) were also gathered
from 5 drops. Every WCA experiment was repeated multiple times to
ensure a reproducible result.
3. Results and discussion
3.1. Surface characteristics
Fig. 1 shows the preparation procedure for this SH coating. The TiO2
forms aggregates in solution, and the PDMS coats the surface of these
aggregates as the film forms. Adjusting the ratio of TiO2 nanoparticles
in the blend solution results in different aggregation states in solvents,
modifying the hierarchical roughness on the surface (and hence the SH
properties) after the spray-coating operation. As seen in Fig. 2a, a pure
PDMS-coated glass substrate is hydrophobic with a WCA of 110°. When
the TiO2 content is gradually increased (with fixed PDMS content), the
Y. Wang et al.
Fig. 1. Schematic illustration of the SH coating fabrication.
WCAs quickly increased and became superhydrophobic (above 150°) at
a ratio of 4:3, and the highest WCA value of 162° is obtained when the
ratio of PDMS:TiO2 is 4:4. When the TiO2 content is furthur increased,
the WCA decreased slightly and the film became uneven. This suggests
that the PDMS is unable to fully coat the TiO2 due to too many large
TiO2 aggregates. The same tendancy is also seen for the sliding angle,
achieving an optimum SA of 1° for the 4:4 blend as shown in Fig. 2a.
Fig. 2b shows a water-rolling experiment to demonstrate the low sliding
angle, and we observed that water droplets were able to roll across the
SH surface even with a very small SA of 1°. Hence, the optimal pre-
paration of 4:4 PDMS/TiO2 was used in further experiments. The WCA
measurements were repeated using a variety of different liquids ranging
from strong acid to strong base, and this SH surface showed no sub-
stantial difference, with WCA values of more than 158° in each case as
seen in Fig. 2c. Furthurmore, the suspension solution can be sprayed on
a variety of substrates such as glass, cotton, silicon wafer, rubber and
paper to form SH coatings, as verified by the round droplets with high
WCAs displayed in Fig. 2d.
We employed SEM to investigate the surface structure of the PDMS/
TiO2 coating on a glass substrate. The surface roughnesses gradually
rise with increasing TiO2 content from 33 wt.% to 50 wt.%, as can be
seen from surface images in Fig. 3. In the low resolution image, it can be
seen that TiO2 nanoparticles (25 nm) agglomerate together and form
spherical agrregates with sizes between 5 and 40 μm in diameter
(Fig. 3c). Fig. 3d shows a higher resolution image of one of these larger
aggregates, in which nanoscale roughness is observed, attributed to
non-aggregated individual TiO2 nanoparticles distributed on the sur-
face. Profilometry measurments were taken at increasing concentra-
tions of TiO2, as shown in Fig. 3e. The size of TiO2 aggregates became
lager as the TiO2 content increased, correlating with the increasing
roughness of the SH coating. The multiscale roughness of the micro-
nano TiO2 aggregates, covered by hydrophobic PDMS, provides the
necessary conditions for achieving SH properties. The TiO2 nano-
particles are embedded in the hydrophobic PDMS matrix, where PDMS
not only serves as a low surface energy material but also binds TiO2
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Colloids and Surfaces A 561 (2019) 101–108
particles together, improving the compactness and continuity of the
surface structure.
3.2. Self-cleaning properties
In real-life conditions, inorganic (e.g. dust) and organic (e.g. oil)
particles will inevitably contaminate surface coatings, hence the desire
for SH sufaces with self-cleaning properties which can quickly and ea-
sily clean the surface with lower cost and labor consumption. To de-
monstrate the PDMS/TiO2 coating’s ability to resist contamination from
inorganic particles, a handful of dust collected from earth was scattered
on the SH surface as shown in Fig. 4a. With a tilt angle of about 15°,
methylene blue-dyed water droplets were employed to clean the surface
drop by drop, and the film returned to its original state after about 20
water droplets. At this point the WCA was re-measured and found to be
162°, showing the self-cleaning to be very effective at restoring the
original SH properties.
To demonstrate the photocatalytic self-cleaning properties of these
PDMS/TiO2 coatings, we show the ability of the film to degrade organic
molecules under sunlight or UV light (wavelength = 365 nm) illumi-
nation. PDMS/TiO2-coated silicon wafers were submerged into 4 ml
cuvettes containing MB solution (0.01 mmol/L methylene blue, dis-
solved in a 1:1 methanol:water mixture) as seen in Fig. 4b. One coated
film (vile 1), and a control sample of uncoated Si wafer (vile 3) were left
in natural light conditions for 6 days, after which time the MB solution
in bottle 1 had lost its color, indicating that the MB molecules were
broken down by the photocatalytic effect of TiO2 nanoparticles. There
was no change to the color of the control sample, showing that sunlight
alone will not cause degradation of MB molecules. A third vile con-
taining a coated Si wafer (vile 2) was left in a dark room for the same
time, and no color change was observed indicating that few MB mole-
cules were degraded. These results show that the photocatalytic prop-
erties of TiO2 nanoparticles in these SH coatings can be activated by
sunlight. Furthermore, the MB degradation process did not influence
the SH properties of the PDMS/TiO2 coating, and the WCA value
Fig. 2. (a) The variation of water wetting phenomena
of sprayed coatings with different TiO2 contents. (b)
Water droplets roll across a SH surface with only 1 °
SA. (c) Repelling behavior of different liquids on the
SH surface. (d) Photographs of water droplets on SH
coatings deposited on cotton, silicon wafer, rubber and
paper substrates.
Y. Wang et al. Colloids and Surfaces A 561 (2019) 101–108

Fig. 3. SEM surface images of the coating for the PDMS/TiO2 ratios (a) 4:2, (b) 4:3, and (c) 4:4. (inset) water droplet on the SH surface of the 4:4 PDMS/TiO2 coating.
(d) SEM surface image of 4:4 PDMS/TiO2 coating at higher resolution, (e) Stylus profilometry measurements compararing the surface topography for the above
samples.

Fig. 4. (a) Dust cleaning process on the SH surface by water

droplets. (b) Observation of organic degradation, with SH-coated
Si wafers immersed in MB solution. Bottle 1: SH-coated substrate
tested in sunlight; bottle 2: SH-coated substrate tested in a dark
room; bottle 3: bare Si wafer tested in sunlight (c) WCA and SA
changes against UV light illumination time when the SH surfaces
were contaminated by oleic acid. (d) WCA changes of SH surfaces
during five cycles of oleic acid contamination and UV light irra-
diation.

104
Y. Wang et al.
Fig. 6. (a) WCA and SA values of the SH coating after each cyclic water impalement. (b) FT-IR spectrum of the SH coating before and after 24 h water impact. SEM
images of the SH surface (c) before and (d) after 24 h water impacting.
remained almost unchanged before and after the MB degradation pro-
cess.
Oleic acid was used to test and verify the ability of the coating to
degradade organic materials by photocatalysis under UV light illumi-
nation. One 25 ul oleic acid droplet was dropped on the SH surface and
allowed to fully wet the surface for 5 min. The WCA decreased from
162° to 110° because of the hydrophillic groups in the oleic acid mo-
lecules. The sample was then placed under UV light (wavelength =
365 nm) and the WCA values were recorded at regular intervals to
monitor the photocatalytic self-cleaning process as shown in Fig. 4c.
After 15 min UV illumination, the WCA value began to improve, in-
dicating that the photocatalysis can degrade and remove the organic
contaminants. After 30 min, the WCA was above 150° indicating the
coating had returned to an SH state, and the SH properties were totally
recovered after about one hour. Furthurmore, even after five cycles of
the aforementioned contamination/cleaning, the oleic acid can still be
degraded successfully and the surface restores its SH properties within
1.5 h under the same irradiating conditions (Fig. 4d), indicating the
longevity of the coating.
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Colloids and Surfaces A 561 (2019) 101–108
Fig. 5. (a) WCA of SH surfaces before and after (a) UV illumina-
tion (wavelength = 365 nm) for 7 days, and (b) remaining out-
doors for 3 months (c) DRS of the SH surfaces before and after 7
days UV illumination, (inset table) variation of CIELab parameters.
(d) WCAs and SAs of SH coatings after immersing in different pH
liquids for one week.
3.3. Stability of PDMS/TiO2 SH coatings
For practical applications, the long-term stability of SH surfaces is
one of the important issues that needs to be considered. The photo-
catalytic nature of the TiO2 introduces the possibility of the degradation
of the surrounding organic material (PDMS) which would damage the
SH properties and durability of the coating. To investigate the coating’s
durability, coatings were irradiated under UV light (wavelength =
365 nm) for 7 days (∼170 h). There is almost no reduction of WCA
from 162° to 161° (Fig. 5a), and only 2° increase in SA from 2° to 4°.
When SH coated substrates were put outside for 3 months (March – May
2018 on a windowsill, temperatures from 5 °C to 30 °C, moderate hu-
midity and rainfall), WCA values of these coatings changed only slightly
from 162° to 160° and SAs changed from 2° to 4°, and the water droplets
remain spherical on both dirty (after 3 months outside) and cleaned
(same coating after rinsing with water) SH surfaces (as shown in the
photograph in Fig. 5b). The SH properties of these coatings are in-
sensitive to UV light, and impressively remain almost unchanged in
ambient outdoor conditions. The crosslinks in the PDMS contribute
Y. Wang et al.
Fig. 7. (a) TG curve of the coating material. (b) FT-IR spectra of PDMS/TiO2
surface before and after 600 °C calcination. (c) Relationship between the SH
properties of the surface and the calcination temperature.
Fig. 8. SEM images of the SH surfaces with higher (upper row) and lower (lower row) resolutions (a, e) at room temperature, and after calcination for 30 min at (b, f)
400 °C, (c, g) 500 °C, (d, h) 600 °C.
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Colloids and Surfaces A 561 (2019) 101–108
strong chemical stability, and suppress the photocatalytic degradation
of the C-Si chains in PDMS.
In order to be a commercially viable SH material, it is essential that
the coating retain its color integrity after ageing. To evaluate this,
colorimetric measurements were performed using CIELab tests to verify
the surface durability before and after 7 days UV aging. The color
modification (ΔE) of the films due to light exposition can be calculated
using the equation E = L2 + a2 + b2 , where L is the brightness
component (0 for black and 100 for white), a is the red-green compo-
nent (positive for red and negative for green) and b is the yellow-blue
component (positive for yellow and negative for blue). The three
chromatic coordinates were calculated from the diffuse reflectance
spectra acquired in the UV–vis spectral range from 800 to 300 nm as
shown in Fig. 5c. According to the literature, variations in E of less
than 5 are considered insignificant. [29,30] From the result in Fig. 5c,
the value of E for this coating after light exposure was calculated is
0.63, which is far less than 5, indicating a high stability of our fabri-
cated SH surface.
Long-term corrosion resistance is an important property for SH
coatings. To test the stability of the PDMS/TiO2 material, coated
glass slides were immersed in liquids ranging from pH = 1 to 13, as
well as a salt-water solution. After immersion for one-week, all WCAs
were still about 160° and all SAs remained below 5° (Fig. 5d), de-
monstrating impressive resistance to both acidic and basic solutions,
and salt.
Practical applications of SH coatings routinely involve exposure to
all kinds of environmental conditions, including the damage from the
continual impact of falling raindrops. To imitate this situation, a water
impalement test was conducted in which the water droplets hit the
coated surface once per second from a height of 50 cm, giving a 1 MPa
impact force to the surface [31]. We define one impact cycle as con-
tinuous water impalement for 3 h, and each film was tested for 8 cycles.
After each cycle, the film was put on a 60 °C heat stage for 10 min to
evaporate the water on the surface. Fig. 6a shows the super-
hydrophobicity after each cycle. After 24 h of water impacting experi-
ments the WCA values remain around 160° and the SA is between 5°–6°,
demonstrating the high durability of these coatings. After 24 h, the
impacted coating is unchanged when observed by eye, but the SEM
images before (Fig. 6c) and after (Fig. 6d) reveal some small changes.
The continuous water impacting appears to weaken the continuity of
the PDMS at the top surface. Fig. 6b shows the FT-IR spectra before and
after 24 h water impacting. A broad band centered at 3385 cm−1 cor-
responds to the stretching vibration of the eOH groups on the surface of
TiO2. The characteristic peaks at 2963 cm−1 and 1262 cm−1 corre-
spond to the symmetric bending of the eCH3 groups, and the peaks at
1097 cm−1 and 802 cm−1 belong to the Si–O asymmetric stretching
Y. Wang et al.
Fig. 9. (a) water-oil (MB dyed water and dichloromethane) separation by the SH nylon filter membrane. (b) Combustion tests of untreated and PDMS/TiO2 coated
paper. (c) Dyed water droplet on the burned paper. (d) The FT-IR spectrum of the burned PDMS/TiO2 coating.
vibration of PDMS [32,33]. After 24 h water impact, the peaks per-
taining to PDMS (2963, 1262, 1097, and 802 cm−1) have negligible
changes compared with the fresh PDMS/TiO2 coating, indicating that
most of the PDMS is not lost. It appears that the water impact can re-
move the smaller TiO2 particles and some of the PDMS on the top
surface, but this does not influence the multiscale structure of the
PDMS/TiO2 aggregates. This is a vast improvement building on pre-
vious work [28] and is attributed to the robustness of the crosslinked
PDMS in the bulk of the TiO2 spheres.
Thermal stability is another important factor in evaluating the
ability of an SH coating to resist extreme conditions. To test this,
PDMS/TiO2 powder (collected by scraping from a coated slide) were
tested by TGA up to 1000 °C as shown in Fig. 7a. The material starts
decomposing at about 340 °C, which is due to the decomposition of
PDMS – there is no decomposition of the TiO2 nanoparticles below
∼1000 °C [34]. The weight loss stabilises at about 650 °C indicating the
PDMS has decomposed, amounting to about 34% of the total weight.
This is confirmed by the PDMS characteristic peaks in the FT-IR spectra
(at 2963 cm−1 and 1262 cm−1, related to the vibration of Si−CH3)
which have almost disappeared after 600 °C calcination. To further
study the influence of temperature, we sintered prepared samples at
temperatures from 160 °C to 600 °C for a period of 20 min. and mea-
sured their WCAs and SAs (Fig. 7c). The films show good SH properties
up to 400 °C, with a WCA value of 155°. With increasing temperature,
the surface hydrophobicity drops very quickly and at 600 °C the surface
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Colloids and Surfaces A 561 (2019) 101–108
displays superhydrophilic properties with a WCA of 5°. As the sur-
rounding PDMS molecules degrade, and the hydrophilic TiO2 particles
are exposed.
SEM images of the SH surfaces at room temperature and after cal-
cination at 400 °C, 500 °C, and 600 °C are shown in Fig. 8 to confirm
this high temperature degradation. In the images of original film
(Fig. 8e), many micrometer-sized papillas are present, and on each
papilla (Fig. 8a) there are many nanometer-sized protuberances, in-
dicating TiO2 aggregates are encased in PDMS, with some TiO2 particles
on the sphere’s surface. This multiscale structure combined with low
surface energy of PDMS resulted in a maximum WCA of 162° and
minimum SA of 1°. When the surface was calcinated at 400 °C, the
smooth nature of the aggregates are lost and cracks appear (Fig. 8f), and
nanometer-sized protuberances from individual TiO2 nanoparticles
become more distinct as the PDMS is partly degraded (as seen in
Fig. 8b). The multiscale structure is preserved and only 6.5% PDMS is
lost, so the surface can still retain its SH properties with a WCA of 155°.
When the temperature was increased to 500 °C, many nanosized TiO2
particles were exposed (Fig. 8c) and more PDMS molecules were de-
composed, which results in the WCA decreasing to around 130°. After
heating at 600 °C, when PDMS on the SH surface was almost decom-
posed, the hydrophilic TiO2 nanoparticles were completely exposed to
the surface (as seen in Fig. 8d and 8 h). Thus the surface wetting be-
havior changed dramatically from superhydrophobic to super-
hydrophilic with a WCA of only 5°.
Y. Wang et al.
3.4. Permeability
An oil-water separation experiment was performed to study the
permeability of organic solvents through the SH film. As shown in
Fig. 9a, a nylon filter membrane treated with the PDMS/TiO2 coating
was used to separate water and dichloromethane mixture (1:1) via
pump assisted filtration. Ultimately, the 50 ml mixed solution was fully
separated in 10 s, with no water passing through the filter, and the
experiment was repeated five times with no loss of separation proper-
ties.
One reason PDMS is favorable in commercial applications is its air
permeability, which can be beneficial for breathable fabrics. To de-
monstrate that PDMS/TiO2 SH films have similar air permeability with
PDMS, combustion tests were performed on SH-treated paper. As shown
in Fig. 9b, both treated and untreated paper burnt in a similar time,
indicating that the coating doesn’t impede the contact of the oxygen to
the paper. Interestingly, the coated paper still has great SH properties
even after burning (Fig. 9c), and the characteristic peaks of the coating
are still detected by FT-IR (Fig. 9d), which demonstrates that combus-
tion only oxidized the SH coating surface without damaging the mo-
lecular structure of the cross-linked PDMS or hierarchical structure of
the coating.
4. Conclusion
A PDMS/TiO2 composite SH coating was successfully fabricated by
blending PDMS solution with TiO2 nanoparticles. The super-
hydrophobicity originates from the hierarchical structure of the dif-
ferent aggregation sizes of TiO2 nanoparticles within a robust cross-
linked PDMS network, and PDMS coats the surface of TiO2 aggregates
to offer low surface energy as well as high physical and chemmical
stability. These SH coatings possess long-term durability against UV and
sunlight, and maintain their properties after long periods of outdoor
exposure. The coating is also resistant to corrosion, high temperatures,
and has high anti-impacting ability. Alongside self-cleaning of in-
organic contaminants, TiO2 adds the ability to degrade organic mate-
rials like oleic acid and methylene blue via photocatalysis. The coating
has good air and oil permeability and can be used for oil-water se-
peration. This simple and durable multifunctional SH coating shows
good promise for future industrial and commercial applications.
Acknowledgment
The authors acknowledge the Excellent Dissertation Cultivation
Funds from Wuhan University of Technology (2017-YS-002)
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