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A novel superhydrophobic hybrid nanocomposite

material prepared by surface-initiated AGET ATRP
Cite this: J. Mater. Chem. A, 2014, 2,
9390 and its anti-icing properties
Xiaoli Zhan,† Yingdi Yan,† Qinghua Zhang* and Fengqiu Chen

Ice aggregation is a global challenge, especially for cold regions. In this article, a novel anti-icing hybrid
material synthesized by grafting fluorinated polymer chains to silica nanoparticles via surface-initiated
activators generated by electron transfer atom transfer radical polymerization (SI-AGET ATRP) was
proposed. It showed such properties as controllable molecular design, wonderful thermal stability and
high superhydrophobicity. Most importantly, it exhibited excellent anti-icing properties by using coatings
with different wettabilities that varied from hydrophilic to superhydrophobic. Its large static water
contact angle (WCA, 170.3
) and small contact angle hysteresis (CAH, <3
) can promote the removal of
droplets efficiently. A new characterization method, DSC, was used to test the crystallization point of
water and its results demonstrated that the crystallization point can be depressed to a large extent
(6.82
C). The low temperature WCA showed that it can postpone the freezing time from 196 s to
10 054 s which indicates the surface can prevent ice formation well, especially with the help of external
Received 6th February 2014
Accepted 21st March 2014
forces. The mechanisms were discussed based on physicochemical properties, heterogeneous
nucleation theory and heat transfer theory. According to the present study, it is reasonable to predict
DOI: 10.1039/c4ta00634h
that the organic–inorganic hybrid superhydrophobic coating will be a prospective anti-icing candidate
www.rsc.org/MaterialsA for various applications such as wind turbine blades, power lines and aircraft.

as propylene glycol and ethylene glycol was once used to delay

Introduction crystallization because they can lower the freezing point of
As we all know, ice adhesion and accumulation can lead to water. However, due to their hydrophilicity, the adhesion
major inconvenience to individual daily life, such as traffic strength between water and the substrate is large and it hinders
interruption, communicating destruction, loss of power and the the removal of condensed water. Then, hydrophobic coatings
damage of equipment related to aviation, telecommunications, with low surface energies aroused interests because the large
electricity and transportation.1 In fact, it can also lead to major contact angle makes the rolling process easier. This kind of
economic losses to countries. The snowstorms of southern coating mainly consists of uorinated polymers,3,4 organo-
China caused huge economic losses of up to several billion silicones,5 uoroalkylsilanes6,7 and fatty acids.8 Although this
dollars during the Spring Festival of 2008. Thus, research on type of coating has an anti-icing effect, it is not ideal. In 1997,
anti-icing coatings is of great signicance for the whole world. Barthlott et al.9 revealed the famous lotus effect and then
Recently, based on preventing ice formation and reducing ice superhydrophobic materials began to be used as anti-icing
adhesion strength, anti-icing coatings and icephobic coatings coating and exhibited excellent performance thanks to their low
have been developed.2 However, anti-icing coatings are better surface energy and enhanced surface morphology. Up to now, it
when compared with icephobic coatings as the latter consume is still a research focus.10–14
more energy. Methods to create superhydrophobic surfaces are mainly
Preventing ice formation means retarding freezing time and attributed to two categories. One is physically mixing nano-
reducing freezing temperature so that condensed water can roll particles with a low surface energy polymer.15 However, for this
off the substrates due to external forces – such as gravity, wind kind of coating, it has been proved that aer several ice–de-ice
power and centrifugal forces – before it freezes. The classica- cycles, the particle sheds the surface16,17 because of the volume
tion of anti-icing coatings can be described as hydrophilic, expansion during the process of icing or mechanical destruc-
hydrophobic, and superhydrophobic. Spraying chemicals such tion during the process of de-icing, resulting in weakened
superhydrophobicity. The other method is to fabricate, by
chemical modication, low surface energy materials on a
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou,
310027, China. E-mail: [email protected] textured surface.18–20 To obtain a surface with hierarchical
† These authors contributed equally. roughness pretreatment of substrates is necessary by methods

9390 | J. Mater. Chem. A, 2014, 2, 9390–9399 This journal is © The Royal Society of Chemistry 2014
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Paper Journal of Materials Chemistry A

such as chemical etching,21,22 crystal growth23,24 and lithog- N,N,N0 ,N00 ,N00 -pentamethyldiethylenetriamine (PMDETA, 99%)
raphy.25,26 So, this method requires multiple steps and is not and g-aminopropyltriethoxysilane (APTES, >98%) were
suitable for large area application.27,28 Taking these shortcom- purchased from Aldrich Chemical Co. and used as received.
ings into consideration, a coating which is suitable for large Toluene was purchased from Sinopharm Chemical Reagent Co.
area application and with excellent durability was synthesized and was puried by distillation from CaH2. 2-(N-Ethyl-
by initiating polymerization from the surfaces of the silica peruorooctanesulphamido) acrylate (EFOA, >95%) was
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nanoparticles. Since the uorinated polymer chains were graf- synthesized according to the literature39 and puried in
ted onto particles, the covalent bond between surface and the acetone. Butyl acrylate (BA) was purchased from Aldrich
polymer was strong enough to prevent separation. The abrasive Chemical Co. and polymerization inhibitors were removed by
resistance was improved largely. Furthermore, the coating was chromatography, it was then stored in a refrigerator at lower
very rigid. Though water expands while freezing, it is likely that than 4
C. Other reagents and organic solvents, unless
the pressure created by trapped air led to crack initiation and otherwise specied, were purchased from Sinopharm Chemical
propagation as well as ice-bonding.29 Regent Co. and used without any further purication.
Besides, this kind of organic–inorganic hybrid material has
other fascinating properties which cannot be obtained just by Sample preparation
mixing inorganic nanoparticles with polymers. These
The approaches to prepare amino-functionalized, 2-bromoiso-
composite materials have the advantages of both organic poly-
butyrate-functionalized and poly(BA-co-EFOA) graed silica
mers and inorganic materials. The organic parts provide
particles are shown in Fig. 1.
controlled molecular structure and weight and good process-
Synthesis of amino-functionalized silica nanoparticles SiO2–
ability, while the inorganic parts offer a high modulus and
NH2. Typically, 15 g of silica nanoparticles, 300 mL of anhy-
wonderful thermal and mechanical stability. Due to these
drous toluene and 21 mL of APTES were placed in a 500 mL
remarkable physicochemical properties, organic–inorganic
round bottom ask equipped with a Graham condenser. The
hybrid materials are applied in diverse elds such as nano-
reaction mixture was stirred by PTFE magnetic stir bar at 110
C
materials, optoelectronic devices, catalysts, biology and so
under nitrogen atmosphere overnight and then cooled to
on.30–32 However, their application in the anti-icing eld has, to
ambient temperature. The nanoparticles were isolated by high-
the best of our knowledge, few reports.
speed centrifugation and vacuum ltration. Then the sediments
It is widely known that graing well-dened polymers on
were redispersed in acetone and centrifuged again. The puri-
particles needs two steps. Firstly, the introduction of one or two
cation cycle mentioned above was repeated several times to
initiators to the surface of the particles and then gradual growth
remove excess reagents. The product, named as SiO2–NH2, was
of the polymer chains away from the interface. This graing-
dried in a vacuum oven at 50
C for 6 h.
from approach can be carried out by living/controlled poly-
Synthesis of amino-functionalized silica nanoparticles SiO2–
merizations,33–36 among which atom transfer radical polymeri-
NH–Br. 1.5 g of SiO2–NH2 nanoparticles, 50 mL of dichloro-
zation (ATRP) is especially attractive for its tolerance of
methane and 0.5 mL of triethylamine were mixed in a round
impurities, mild polymerization conditions and compatibility
bottom ask immersed in an ice–water bath. Aer cooling to
with a wide range of monomers. To overcome the drawbacks of
0
C, the mixture of 2 mL of BiBB and 20 mL of
normal ATRP such as challenging inert atmosphere, ATRP
using activators generated by electron transfer (AGET) was
developed.37,38
In this work, we synthesized a kind of organic–inorganic
hybrid material by graing poly(butylacrylate-co-2-(N-ethyl-
peruorooctanesulphamido) acrylate) to silica nanoparticles via
SI-AGET ATRP. By spin-coating the solution of this material,
superhydrophobic surfaces were obtained. Its controllable
polymerization, chemical composition and surface morphology
were characterized by corresponding analysis methods. Its anti-
icing properties were tested by, besides traditional contact angle
hysteresis and water contact angle analysis, differential scan-
ning calorimetry (DSC) comparing hydrophilic, hydrophobic
and uncoated surfaces. Furthermore, the mechanisms were
explored on the basis of physicochemical properties, heteroge-
neous nucleation theory and heat transfer theory.

Experimental
Materials
Fig. 1 General approaches to prepare the amino-functionalized, 2-
Fumed silica (SiO2, >99.8%, 14 nm) was purchased from bromoisobutyrate-functionalized and poly(BA-co-EFOA) grafted silica
Ximeng Chemical Co. 2-Bromoisobutyryl bromide (BiBB, 98%), particles.

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Journal of Materials Chemistry A Paper

dichloromethane were added dropwise. The solution was stir- 500 MHz nuclear magnetic resonance spectrometer (Advance
red at 0
C for 0.5 h and then at room temperature for 24 h. The DMX500) and was carried out with a 5 wt% solution in CDCl3 at
method of isolation and purication of the product was similar room temperature, using tetramethylsilane (TMS) as internal
to procedures described for SiO2–NH2. The nal product, reference. The chemical composition was analyzed by XPS
named as SiO2–NH–Br was also dried under vacuum oven at 50 (Thermo Scientic, USA) with an Al Ka X-ray source. The X-ray


C for 6 h. gun was operated at 14 kV and 350 mW, and the analyzer
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Synthesis of SiO2–P(BA-co-EFOA) nano-composites via SI- chamber pressure was 109 to 1010 Pa. The morphologies of
AGET ATRP. In this step, SiO2–NH–Br (0.5 g, 0.25 mmol of the nal particles were examined by TEM with a JEOL JEM-2010
initiating sites), BA (3.2 g, 25 mmol), EFOA (1.1 g, 2.5 mmol), transmission electron microscope (Tokyo, Japan). The solution
PMDETA (0.05 mL, 0.25 mmol), DMF solution of CuBr2 (5 %wt) was dipped onto carbon-coated copper grids and dried at room
and anhydrous toluene (10 mL) were added in a round bottom temperature. TEM was done at 80 kV. SEM analysis was per-
ask equipped with a magnetic stirrer bar. In order to make the formed using a JEOL SM 840 scanning electron microscope at
SiO2–NH–Br nanoparticles disperse homogeneously, the an accelerating voltage of 20 kV. AFM was operated by Multi
mixture was treated by ultrasonication and then immersed in an Mode (Veeco, USA) in tapping mode. The scanning range was 5
ice-water bath. Aer purging the system with nitrogen for 20 min, mm  5 mm and the root-mean-square (RMS) roughness value
the toluene solution of Sn(EH)2 (5 %wt) (0.061 g, 0.15 mmol) was was calculated from the obtained image.
added through syringe injection. The ask was then Characterization of anti-icing properties. A CAM 200 optical
transferred to an oil bath at 80
C. The ratio of contact-angle goniometer (KSV Instruments, Helsinki, Finland)
BA : EFOA : CuBr : PMDETA : SiO2–NH–Br was 100 : 10 : 1 : 1 : 1 was used for CA measurements at both the ambient tempera-
in this study. Aer polymerization, the resulting solution was ture and 18
C. The CAH was measured by tilting the sample
opened to the air to terminate the polymerization, and then stage from zero to higher angles until the droplet rolled off the
added into methanol and the nanoparticles were isolated via surface, then the advancing angle and the receding angle can be
high-speed centrifugation. Redispersed in THF, the precipitation calculated. The volume of the tested water droplet is 2 mm. The
was isolated via centrifugation again. This purication cycle was inuence on crystallization point of water was observed from
repeated three times. The nal nanoparticles were dried at room the DSC with a DSC Q200 system (TA instruments). Before the
temperature under vacuum overnight. DSC measurements, the sample pan was coated by the products
Spin coating of SiO2–P(BA-co-EFOA) nano-composites. SiO2– with different wettability. The temperature ranged from room
P(BA-co-EFOA) was dissolved in tetrahydrofuran (concentration temperature to 50
C with a cooling rate of 10
C min1.
5 wt%) and sonicated for 1 h prior to use. The solution was spin-
coated onto clean glass slides at room temperature using a
chemical technology KW-4A spinning coater. A rotational speed
Results and discussion
of 1200 rpm and a holding time of 30 s were chosen. Aer that Fig. 2 illustrates the whole process of preparation and applica-
the sample was allowed to evaporate slowly for a day. Then it tion of the superhydrophobic anti-icing surface. The pristine
was dried for 12 h in a vacuum oven at 80
C and annealed at silica was functionalized by triethylamine and 2-bromoisobu-
130
C for 30 min. tyrate, nally, poly(BA-co-EFOA) was graed to functionalized
silica particles. By spin-coating the solution of synthesized
Characterization
Characterization of controlled polymerization. Thermogra-
vimetric analysis (TGA) was carried out on a TGA2050-TA
Instrument (USA). The samples were analyzed under a nitrogen
atmosphere with a heating rate of 10
C min1 from room
temperature to 800
C. Molecular mass (Mn) and molecular
distributions (Mw/Mn) of the polymer were determined by gel
permeation chromatography (GPC) equipped with a Waters
1525 two-component high performance liquid chromatography
pump, a Waters 717 automatic sampler, three Styragel HT
columns and a Waters 2414 refractive index detector. A series of
low-polydispersity polystyrene standards were employed for the
Fig. 2 Schematic illustration of the preparation and application of the
GPC calibration. The eluent was tetrahydrofuran (THF) at 35
C superhydrophobic anti-icing surface, (1) pristine silica nanoparticles (2)
with a ow rate of 1.0 mL min1. The polymer was cleaved from fabrication of functionalized silica nanoparticles, (3) grafting fluori-
particles by hydrouoric acid. nated polymer chains to particles via SI-AGET ATRP, (4) formation of
Characterization of superhydrophobic surfaces. Fourier micro-/nano-hierarchical structures, (5) micro water droplets are
formed in the valley, (6) converged microdroplets are deformed by
transform infrared (FTIR) spectra were measured on a Nicolet
unbalanced surface tension, (7) microdroplet directionally moves to
5700 FT-IR spectrometer in the range of 4000–600 cm1. The top and finally, is suspended on the surface, (8) water roll off with
samples were dissolved in THF and cast onto KBr disks to be outside forces, and (9) magnification of dashed frame illustrating the
analyzed. 1H-NMR analysis was conducted with a Bruker unbalanced surface tension caused by the wettability gradient.

9392 | J. Mater. Chem. A, 2014, 2, 9390–9399 This journal is © The Royal Society of Chemistry 2014
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Paper Journal of Materials Chemistry A

organic–inorganic hybrid material, we obtained micro-/nano- cleaved from the nanoparticles and GPC was tested. Its result is
hierarchical structures due to surplus OH groups on the silica shown in Fig. 3(b). We can clearly observe that there is a single
nanoparticles facilitating moderate aggregation. The annealing peak curve and its polydispersity index (PDI) is 1.27. In other
process made the uorocarbon chains orientate to the surface words, the characteristics of the resulting product are quite in
which, combined with its roughness, lead to a super- line with an AGET ATRP polymerization mechanism.
hydrophobic surface. Just like the lotus leaf,40 in a humid
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environment, the micro water droplets are formed in the valley. Characterization of the superhydrophobic surface
Then, converged microdroplets form a thin liquid layer on the
Superhydrophobic coatings are coatings that are simulta-
raised areas. Due to the wettability gradient, the contact angle of
neously characterized by a water contact angle greater than 150

upper edge (qg) is less than the lower one (qs). Driven by
and contact angle hysteresis smaller than 10
. The local contact
unbalanced surface tension, the microdroplet is deformed and
angle, known as the Young contact angle q, can reach no more
directionally moves to the top and nally, suspend on it. Since
than 120
on planar surfaces even if the most efficient uorine
the adhesion between the droplet and surface is very low and
containing agents form a dense monolayer on a surface of
both the crystallization point and time are changed to a large
textured elements.42 By mimicking natural superhydrophobic
extent, the droplet can remain liquid for a long time and it can
surfaces such as lotus leaves and insects' legs, super-
be removed by outside forces easily before it freezes. The
hydrophobic phenomena are formed by combining surface
detailed characterization results concerning the controlled
chemical composition with surface roughness. As Fig. 4 shows,
polymerization, chemical composition, surface morphology
two different models are proposed to explain this phenomenon:
and anti-icing properties are as follows.
the Wenzel model43 and the Cassie model.44 Both of them dis-
played the real contact angle in function of the Young contact
Characterization of the controlled polymerization angle q which was measured for a at surface. Detailed infor-
The TGA curves of pristine SiO2, SiO2–NH–Br and SiO2–P(BA-co- mation including equations and annotations for the Young,
EFOA) are shown in Fig. 3(a). TGA has been proved to give good Wenzel and Cassie models are displayed in Fig. 4.
quantitative results relative to the Br content of the samples in Characterization of chemical composition. The chemical
previous publications on similar systems because specic composition was tested by Fourier transform infrared (FT-IR),
organic molecules pyrolyze at a specic temperature.41 Using Nuclear magnetic resonance spectroscopy (1H-NMR) and X-ray
the assumption that under 200
C the weight loss was caused by photoelectron spectroscopy (XPS).
the removal of water absorbed physically, the additional weight Fig. 5 shows the FT-IR spectra of pristine SiO2, SiO2–NH2,
losses from SiO2 and SiO2–NH–Br were attributed to pyrolysis of SiO2–NH–Br and SiO2–P(BA-co-EFOA). The broad absorption
hydroxyl groups and the introduced APTES respectively. On the brands at about 1000–1250 cm1 corresponding to Si–O–Si
basis of the data, it is feasible to quantify the yields of the stretching vibrations that appear in all of the SiO2 related the
synthesis using TGA. In order to circumvent any possible samples. The band observed at about 3446 cm1 indicates the
inuence of physically absorbed water, the results were calcu- presence of a hydroxyl group on the surface of SiO2 and the peak
lated by subtracting the weight loss under 200
C, 98.26% and at 961 cm1 is attributed to a Si–OH vibration. Compared with
97.70% for SiO2 and SiO2–NH–Br respectively. With this the FT-IR spectrum of pristine SiO2, there was a –CH2 stretching
method, the hydroxyl content of the SiO2 is found to be 3.34 vibration at 2933 cm1. The absence of a Si–OH vibration at
mmol g1. From the TGA curve of SiO2–NH–Br, the Br content of 961 cm1 shows that the hydroxyl group on the surface of silica
the SiO2–NH–Br is found to be 0.495 mmol g1, which deter- was substituted. The SiO2–NH–Br macroinitiator was synthe-
mines the dosage of reagents used in the next step. The TGA sized by the reaction of SiO2–NH2 with 2-bromoisobutyryl
curve of SiO2–P(BA-co-EFOA), besides the slight weight loss at bromide. For SiO2–NH–Br, C]O stretching vibrations of the
about 200
C due to dehydration, exhibits a large mass loss only ester at 1629 cm1 occur, which indicate that the initiator group
between 300–450
C, indicating that the polymer chain struc-
ture of the SiO2 is homogeneous. To see whether the polymer-
ization was living and controlled, the graed polymers were

Fig. 3 (a) TGA curves of the reference SiO2, SiO2–NH–Br and SiO2–
P(BA-co-EFOA), and (b) GPC curve of grafted P(BA-co-EFOA). Fig. 4 Young, Wenzel and Cassie's models.

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Journal of Materials Chemistry A Paper

Characterization of surface morphology. Transmission

electron microscopy (TEM) photographs of the primary silica
nanoparticles and the resultant organic–inorganic hybrid
material are shown in Fig. 7(a–c). In Fig. 7(a), the aggregation
can be observed clearly due to the high specic surface area and
high surface free energy of the silica nanoparticles, as well as
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the presence of OH groups on the nanoparticles’ surface. While

in Fig. 7(c), polymers surrounding the silica can obviously be
seen.45 TEM micrographs of the treated nanoparticles, Fig. 7(b),
show that although graed with polymers, the aggregation was
slightly prevented. It is the key to the formation of the hierar-
chical surface morphology. Surplus OH groups facilitate
aggregation but the polymer chains prevent it. The balance
between the two contrary tendencies means that the treated
particles form micro/nanoparticles with nanopolymer hair
among which the uorocarbon chains are orientated to the
surface. These contribute to the superhydrophobic properties.
According to Fig. 7, the particles assembled with a hierar-
chical roughness that makes the surface superhydrophobic.
Images of the surface morphology were obtained by SEM and
Fig. 5FT-IR spectra of pristine SiO2, SiO2–NH2, SiO2–NH–Br and AFM. The corresponding images are shown in Fig. 8. It can be
SiO2–P(BA-co-EFOA). seen that the surface asperities are inhomogeneous. In the case
of the low magnication SEM image, the protuberances are
obviously observed at the micron scale. Aer magnifying, scat-
is linked. The FT-IR spectrum of SiO2–P(BA-co-EFOA) showed a tered nanoparticles can be seen as well, such as the area marked
broad peak at 1100–1250 cm1 which is attributable to a F–C–F by the red circle in Fig. 8(b). The surface topography obtained by
stretching vibration. All of these proved that the gra poly- the AFM images agrees pretty well with that from the SEM
merization via SI-AGET ATRP was successful. images. In addition, the micro/nano composite morphology of
In Fig. 6, the results of 1H-NMR and XPS are shown together. the surfaces obtained (AFM and SEM) perfectly matches the
We can infer the chemical composition of both the bulk and contact angle result which is shown in the top right corner of
surface by analyzing them. Fig. 6(a) shows the 1H-NMR spec- Fig. 8(b), 170.3
.
trum of the cleaved polymer in which the different hydrogen Through Fig. 8(d) and (e), we can obviously observe the
groups and its corresponding peak were annotated. According scattered peaks on a relatively at the surface. That is why in
to the value of integrations, the ratio of m and n can be calcu- Fig. 8(e), the RMS is 14.325 nm while the Rmax is 97.421 nm. The
lated as 10 : 1 which is in accordance with feed ratio. So the spacing between the textural peaks of the roughness is impor-
ratio of uorine to carbon was obtained subsequently as 17 : 83 tant for the trapping of air pockets.46 Hence for the prepared
The overall XPS spectrum of the graed silica nanoparticles' hybrid material, the water droplet cannot penetrate the pitch
surface is depicted in Fig. 6(b), and the silicon, oxygen, uorine, prole which results in a high static contact angle and low
carbon and nitrogen atomic percentage are estimated to be adhesion.
about 23.78%, 30.96%, 11.59%, 30.86% and 2.81% respectively.
There is a higher ratio of uorine to carbon in the XPS data
Anti-icing properties of the superhydrophobic surface
(11.59% : 30.86% ¼ 1 : 2.66) than in the 1H-NMR data (1 : 4.88),
indicating that the uorocarbon molecule chains migrated to Anti-icing properties mainly refer to the easy removal of
the surface and this segregation makes the surface condensed water before it freezes and the delay in crystalliza-
hydrophobic. tion of condensed water, so that ice accumulation can be pre-
vented. The anti-icing properties were characterized by contact

Fig. 6 (a) 1H-NMR spectrum of cleaved polymer film and (b) XPS Fig. 7 TEM images of the primary silica nanoparticles and the resultant
survey spectrum of organic–inorganic hybrid silica particles. hybrid silica particles.

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Paper Journal of Materials Chemistry A

In the case of contact angle hysteresis, it determines the

force preventing the liquid rolling off the surface.48 The lower
the hysteresis, the more efficiently the drops are removed from a
horizontal surface of a coating under a wind force or air stream
pressure as shown in eqn (1)
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Dq ¼ qadv  qrec (1)

in which Dq, qadv and qrec represent the contact angle hysteresis,
the advancing contact angle and the receding contact angle
respectively. q, qadv and qrec are marked in Fig. 9.
According to the contact angle data, we nd that samples B,
C, D and E exhibited hydrophilicity, double hydrophobicity and
superhydrophobicity respectively. Compared with hydrophilic,
uncoated and hydrophobic surfaces, the superhydrophobic
Fig. 8 (a) SEM micrograph of the hybrid silica particles at 10 000 times surfaces reduced both the contact area and the force between
magnification, (b) SEM micrograph of the hybrid silica particles at
50 000 times magnification, (c) AFM 2D height image of the hybrid
the water and the surface to a large extent. We can conclude that
silica particles, (d) AFM 2D phase image of the hybrid silica particles, the condensed water can roll off the surface as long as it is tilted
and (e) AFM 3D phase image of the hybrid silica particles. slightly. On the other hand, to investigate the low adhesion
between the water and the coating, we applied a super large
droplet, 15 mm, which is 7.5 times larger than a normal one. As
angle measurements in both ambient and subzero environ- Fig. 10 shows, even if we pressed it hard, it was difficult for the
ments and by DSC measurements. In this part, ve samples droplet to adhere to the surface. So, it is rational to say that the
with different wettabilities were used. synthesized hybrid nanoparticles have good anti-icing proper-
Removal of condensed water before crystallization. The ties. Furthermore, it has been proved that the ice adhesion
crucial factor determining whether it is easy for condensed strength on rough hydrophobic surfaces has good correlation
water to roll off the surface is the force between the condensed with wetting hysteresis.49,50
water and the surface. A lower force makes the removal proce- Delay in the crystallization of condensed water. The crys-
dure easier. As for the superhydrophobic surface, the force is tallization point of a water droplet on surfaces with different
reduced by two methods, decreasing the contact area and coatings were obtained by DSC measurements at a continuously
reducing the contact angle hysteresis. lowering temperature and the whole icing process of condensed
As we all know, a large contact angle is echoed by a small water was observed using a CAM 200 optical contact-angle
contact area. What's more, when the superhydrophobic surface goniometer at a constant temperature, 18
C.
is wetted by liquid, air is trapped inside the grooves in the Through analysis of the DSC data, we found that compared
hierarchical structure. So the real contact area refers to the with the droplet dripped into an untreated crucible, the drop-
fraction of the wetted area. It has been reported that the real lets in the hydrophilic, hydrophobic and superhydrophobic
contact area is generally considerably less than 10% for super- crucibles possess lower heat ow. It is clearly caused by the heat
hydrophobic surfaces due to the presence of an air layer.47 Table insulation of both the coatings and the trapped air between the
1 shows the contact angles of the samples with different water and the substrate. The reason why the freezing point can
wettabilities. According to Table 1, we can conclude that the be inuenced is key and needs to be discussed. The sample
superhydrophobic surface decreased the contact area to a large coated with pure polymer, P(BA-co-EFOA), is the only planar
extent. surface. The reduced crystallization temperature is attributed to
adiabatic coating which actually inuences the temperature
slightly. However, for other rough samples, this phenomenon
Table 1 Contact angle (q), advancing contact angle (qadv), receding can be explained by the combination of Kelvin's law and the
contact angle (qrec) and contact angle hysteresis (Dq) for different Clapeyron relationship. Numerous nanoparticles are aggre-
surfaces achieved using a CAM 200 optical contact-angle gated on the surface, especially for the superhydrophobic
goniometera surface, forming roughness and nano-hairs scattered on the
q (
) qadv (
) qrec (
) Dq (
)

A 51.5  0.5 63.7  2.1 34.7  1.7 29.9  1.2

B 40.3  0.7 73.6  1.6 22.7  1.6 50.9  0.2
C 103.0  0.2 116.9  1.8 68.6  2.1 48.3  3.9
D 113.5  0.1 129.8  1.2 99.8  1.8 29.8  2.0
E 170.3  2.4 171.5  2.1 168.7  1.9 2.7  0.2
a
Samples A, B, C, D and E represent the uncoated surface, the surface
formed by pristine SiO2, P(BA-co-EFOA), SiO2–PBA and SiO2–P(BA-co- Fig. 9 Static contact angle (q), advancing contact angle (qadv) and
EFOA) respectively. The proportion of BA and EFOA in C and E is equal. receding contact angle (qrec).

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Journal of Materials Chemistry A Paper

crystallization compared with other surfaces at a constant

temperaturewell (Fig. 11).
The photographs of individual water droplets on untreated
glass and glass coated with different coatings in the whole
Fig. 10 The process of applying a huge droplet to the surface failed as freezing process are showed in Fig. 12. It can be obviously
the droplet did not adhere to the coated surface. observed that the transparent center of the condensed water
Published on 21 March 2014. Downloaded by National Aerospace Laboratories (NAL) on 1/28/2021 12:33:11 PM.

vanished when the water began to freeze because the difference

in reectivity between water and ice.3 The recorded data
microparticles thus leading to the formation of capillaries. The demonstrate that the hydrophilic coating shortened the
formula of Kelvin's law is freezing process by 8 s, planar and rough hydrophobic coatings

 delayed it by 162 s and 236 s respectively, and most importantly,
2gVm
Pr ¼ P exp (2) the superhydrophobic coating delayed it by 9858 s which indi-
RTr
cates this kind of coating can prevent ice formation very well.
where Pr and P are the vapor pressure and saturated vapor This phenomenon can be explained thermodynamically. It is
pressure at a given temperature respectively; g is the surface well known that a water droplet must overcome the potential
energy; Vm is the molar volume of phase; R is the gas constant; T barrier to crystallize. For a superhydrophobic surface, due to its
is the temperature and r is the radius of the droplet or crystal. roughness, the crystallization can be described as heteroge-
The value of r depends on the interface. If it is concave, r is neous nucleation. Based on classic nucleation theory,51 the
positive and if it is convex, r is negative. So, it can be obviously nucleation free energy barrier (DG) can be calculated by the
observed that for a hydrophilic surface (pristine SiO2), Pr equations
decreases while r decreases. While for a SiO2–PBA and SiO2–

2pR3
P(BA-co-EFOA) coated surface, Pr increases when r decreases. DG ¼ Dg þ 2pR2 gsl fðqÞ (6)
3
Suspending on the surface with nanoscales, r is small enough to
generate a large Pr. Based on Clapeyron relationship,
ð2 þ cos qÞð1  cos qÞ2
fðqÞ ¼ (7)
dT TDba Vm 4
¼ (3)
dp Dba Hm

where T is the temperature, p is the vapour pressure, DbaVm and

DbaHm are the volume difference and enthalpy change from
phase a to b respectively. For solidication, eqn (3) is trans-
formed as
dT Dsol Vm
¼ dp (4)
T Dsol Hm
Aer integration, we get
T2 Dsol Vm
ln ¼ ðp2  p1 Þ (5)
T1 Dsol Hm

Since in the process of solidication, DVm > 0 and DHm < 0,

so, T is negatively related to P. Therefore, compared with an
uncoated surface, the hydrophilic surface with a certain
roughness possess a lower pressure, so the water droplet on it
solidies at a higher temperature (12.15
C vs. 13.37
C) and
a water droplet on a hydrophobic surface with a higher pressure
tends to be supercooled and the freezing temperature is corre-
spondingly decreased (17.44
C vs. 13.37
C). Thanks to its
smaller r, the droplet on a superhydrophobic surface froze at an
even lower temperature (20.19
C). While for the P(BA-co-
EFOA) coated surface, the pressure is similar to a smooth
surface. This is why the freezing temperature is in close prox-
imity to that on an uncoated surface. According to the DSC
observations, we can conclude that the crystallization point of
water can be reduced by optimizing the surface roughness and
chemical composition. As for the superhydrophobic surface we Fig. 11 DSC curves of supercooled water droplets dripped into an
untreated crucible and crucibles treated with pristine SiO2, P(BA-co-
made, it decreased the freezing temperature by 6.82
C. Besides
EFOA), SiO2–PBA and SiO2–P(BA-co-EFOA). The temperature was set
lowering the crystallization point, the surface can also delay to decrease at a rate of 10
C min1.

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Paper Journal of Materials Chemistry A

Q ¼ Qgc + Qgr  Qsc  Qsr (8)

Where Q is the net heat gain in unit time, and Q > 0 for a
superhydrophobic surface at higher temperature; Qgc and Qgr
are heat gains through heat conduction and thermal radiation
in unit time; Qsc and Qsr are heat loss through heat conduction
Published on 21 March 2014. Downloaded by National Aerospace Laboratories (NAL) on 1/28/2021 12:33:11 PM.

and thermal radiation in unit time. According to Fourier's law

ð T2
Qc ¼ KSdT (9)
T1

Where Qc is heat transfer caused by conduction; K is the heat

transfer coefficient, T1 and T2 are the temperatures of the
condensed water droplet and the surface; S is the contact area.
Thereby Qc is determined by S because K is the same for all
surfaces. For the synthesized superhydrophobic coating, its
nanohairs take up very little room and the trapped air takes up a
very high percentage. All of these increase the heat gains and
decrease the heat loss of heat conduction. Furthermore, a
Fig. 12 Photographs of individual water droplets on glass with
smaller liquid–solid contact area causes a smaller loss of
different coatings during the whole freezing process captured by a
high speed CCD camera on a CAM 200 optical contact-angle thermal radiation. To sum up, the superhydrophobic surface
goniometer. can gain much heat. According to the relationship between the
decreased temperature (DT) in the droplet and net heat gain (Q)
rw Cp ðT1  T2 Þ
Where R is the droplet radius, gsl is the solid–liquid interfacial DT ¼ (10)
Q
tension, Dg is the Gibb's energy density difference between ice
and liquid water and q is the apparent contact angle. According where rw is water density; Cp is the heat capacity of pure water at
to the equations, DG is positively proportional to f(q) which constant pressure. DT is negatively proportional to Q, that is to
means that the bigger q is, the higher DG is. The curve of f(q) is say a large Q can lead to a small DT. Thus it explains why a
shown in Fig. 13 from which we can see f(q) continuously superhydrophobic surface can delay condensed water crystalli-
increases with q. So, the growing contact angle will enlarge the zation. Without the trapped air, the P(BA-co-EFOA) coating
nucleation free energy barrier and retard the crystallization of behaved worse than the SiO2–PBA one although both of them
condensed water. For treated glass with high super- are hydrophobic.
hydrophobicity in this study, it is inevitable to delay the water
droplet freeze. Conclusions
Since trapped air exists between the condensed water and
the cold superhydrophobic substrates, we believe that the In this work, we proposed a novel anti-icing coating material
droplet on the surface is a three-phase system of interfaces. The with high superhydrophobicity which was synthesized by
process of heat transfer is changed correspondingly which is graing uorinated polymer chains from the surface of silica
also relative to the delay of crystallization. The heat transfer nanoparticles via AGET ATRP and which has not been made or
consists of the heat gains from air via contact heat conduction investigated in previous studies. This material, compared with
and thermal radiation and the heat loss to nanopolymer chains previously reported ones, exhibited fascinating advantages such
in the same way.24 The equation of heat transfer is expressed as as a high contact angle (170.3
) and abrasive resistance thanks
follows to the inorganic part and the covalent bond between organic
and inorganic materials. Its controllable polymerization,
chemical composition and morphology were characterized by
several methods and the results showed that a super-
hydrophobic coating was synthesized successfully and the
process of polymerization was living and controllable. Most
importantly, its anti-icing properties were better than the ones
reported previously. Our coating not only could promote the
removal of droplets but also showed a good ability to lower the
crystallization point and to delay the freezing time. The crys-
tallization temperature was reduced by 6.82
C and the water
droplet on a 18
C surface took 10 054 s to freeze. What's
more, the mechanisms of the anti-icing properties were dis-
cussed in detail. Finally, based on the present research, it is
Fig. 13 The curve of f(q) in the function of q. reasonable to say that the organic–inorganic hybrid

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Journal of Materials Chemistry A Paper

superhydrophobic coating is a good prospective candidate for 14 N. Miljkovic, D. J. Preston, R. Enright, et al. Electrostatic
use as an anti-icing material. charging of jumping droplets, Nat. Commun., 2013, 4, 2517.
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Acknowledgements multiresponsive and reversibly tunable wettability, J. Mater.
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This work is continuously supported by the National Natural

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