Applied Surface Science 346 (2015) 68–76

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Applied Surface Science

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

Durability of a lubricant-infused Electrospray Silicon Rubber surface

as an anti-icing coating
Qi Liu, Ying Yang ∗ , Meng Huang, Yuanxiang Zhou, Yingyan Liu, Xidong Liang
State Key Lab. of Power System, Dept. of Electrical Engineering, Tsinghua University, Beijing 100084, China

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

Article history: Slippery liquid-infused porous surfaces (SLIPS) are attracting great interest as anti-icing coatings.
Received 10 December 2014 However, the most challenging point for SLIPS is their durability. A heptadecafluorodecyl
Received in revised form 6 February 2015 trimethoxysilane-fluorinated hierarchically micro-structured silicone rubber surface was prepared by
Accepted 8 February 2015
electrospray method coupled with phase separation which had a contact angle of the lubricant  ls(a) = 0◦ .
Available online 16 February 2015
This study investigated the effects of the surface chemistry, length scale and hierarchy of the sur-
face topography of the underlying substrates on their ability to retain the lubricant during repetitive
Keywords:
icing/deicing, water washout and ice-shedding treatments. This study compares the lubricant retention
Durability
Lubricant-infused electrospray silicon rate, ice formation time and ice adhesion strength. The result demonstrated that SLIPS with a fluori-
rubber surface nated hierarchical micro/nano scale substrate maintains the best anti-icing capability. Lubricant in the
Anti-icing microscale pores can easily creep up to the surface with nano-scale pores providing stronger capillary
forces to hold the lubricant in the pores only if  ls(a) = 0◦ with a rolling hill pattern lubricant surface
morphology formed during the loss of lubricant. Such fluorinated hierarchically nano/micro structured
substrate will enable the lubricant to completely cover the surface which reduces heterogeneous nuclea-
tion and frost propagation velocity.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
The problems caused by ice formation impact many aspects of
our lives including power generation (wind turbines) and trans-
mission (overhead transmission lines and towers), aircraft, oil
platforms, and building roofs [1–5]. Studies on designing an anti-
icing surface have been taken for years by using low surface energy
coatings and designing nano/micro topography (i.e. lotus leaf struc-
ture) to delay icing and reduce ice adhesion [6–13]. However, recent
research has shown that superhydrophobic is not equal to super-
icephobic [14]. In high humidity atmospheres, superhydrophobic
surfaces significantly accelerate ice formation with larger ice adhe-
sion strengths since the water condensation takes place both on top
of and between surface asperities [14–16]. This problem could be
solved if water condensation was prevented in the porous struc-
ture, that is, if the superhydrophobic effect could be limited to a
solid smooth surface. Such surfaces can be made by physical or
chemical functionalization. Although the chemical functionaliza-
tion method is promising, formation of such textured surfaces is
∗ Corresponding author.
E-mail addresses: yingyang@tsinghua.edu.cn, winifred.yang@gmail.com,
yingyang@mail.tsinghua.edu.cn (Y. Yang).
rather complicated and expensive to scale up. Wong et al. described
a simple, cost-effective way to design anti-icing surfaces using self-
repairing slippery surfaces with pressure-stable omniphobicity
(including hydrophobicity and icephobicity) called slippery liquid-
infused porous surfaces (SLIPS) [17]. The key to achieving this
property is to create a substrate which stabilizes and wick the lubri-
cant into pores. Such surfaces provide an ultra-smooth, chemically
homogeneous interface that can presumably eliminate the nuclea-
tion sites [18,19]. The high lubricant mobility and the substrate
properties (the morphology and surface chemistry) play important
roles in the ice-phobic property [20]. Most previous studies have
focused on the ability to repel low surface energy liquids [21–24].
Only a few publications have focused on SLIPS anti-icing proper-
ties [18,19,25–27]. Kim et al. investigated the effect of the length
scale and the hierarchy of the surface topography of the underly-
ing substrates on their ability to retain the lubricant for high shear
conditions [28]. The results showed that uniform nano-features
provide the most shear-tolerant liquid-repellent behavior. How-
ever, the most practical applications of anti-icing surfaces have to
tolerate not only larger shear forces but also repeating icing/deicing
and rain washout. The anti-icing mechanism of such surfaces is still
not fully understood. Recently, Smith et al. reported that the lubri-
cant film encapsulating the texture was stable only if the oil contact
angle on the textured surface was 0◦ [20]. Moreover, Anand, S. et al.

http://dx.doi.org/10.1016/j.apsusc.2015.02.051
0169-4332/© 2015 Elsevier B.V. All rights reserved.
 Q. Liu et al. / Applied Surface Science 346 (2015) 68–76
reported that ice formation and water droplets can accelerate lubri-
cant depletion [29]. Thus, the most challenging point for SLIPS as
an anti-icing material is durability. The water-tolerant behavior of
SLIPS has not been reported previously to our knowledge. Thus a
systematic study of the water-tolerance of SLIPS is needed. Wang
et al. reported on silicon-oil-infused polydimethylsiloxane (PDMS)
coatings instead of lubricants. The surface had a low surface energy
and a very low ice adhesion strength of 50 kPa, only about 3% of the
strength on a bare aluminum (Al) surface [30].
The electrospray technique is a straightforward way to prepare
nano/micro structured coating materials [31–33]. Polymer solu-
tions are commonly used electrospray solution. Meanwhile,
polymer coatings remain unbeatable in terms of price, flexibility,
light weight and compatibility among the coating material candi-
dates. Although more than 100 kinds of polymer solutions can be
electrosprayed, few of studies have used silicon rubber, one of the
most important and cost-effective materials in power transmission
and roofing [34,35].
This paper presents a one-step electrospray method cou-
pled with phase separation to prepare heptadecafluorode-
cyl trimethoxysilane (FAS-17) fluorinated hierarchically micro-
structured high temperature vulcanized silicone rubber (HTV)
substrates infiltrated with a perfluoropolyether lubricant to form
the SLIPS. DuPont Krytox GPL103 (density = 1.92 g/ml, kinematic
viscosity = 82 cSt, surface tension = 17 mN/m), a perfluoropolyether
(PFPE), was used as the model lubricant in this paper. The effects of
the hierarchy topography and surface chemistry of the underlying
substrates on their lubricant retention ability and anti-icing perfor-
mance were investigated for many icing/deicing cycles as well as for
rain washout with different intensities. The performance of SLIPS
icephobicity was characterized based on the lubricant retention
behavior, the contact angle hysteresis, the frost formation process,
and the ice adhesion characteristics of samples with various mor-
phologies and surface chemistries.
2. Methods
2.1. Preparation of HTV substrates
A 25 wt% silicon rubber solution (R-6040, two part system
A:B = 1:1, Blue Star New Materials Co., Ltd. Cheng Du, China) was
used as the “Mother solution” (labeled “MS”) by mixing compo-
nents A and B of the HTV with a 1:1 mass ratio (reaction formula was
shown in SI), using petroleum ether as the solvent with mild stirring
for ∼4 h at room temperature. The porous silicon rubber substrates
used different additives added into the MS with 2 ml DMF, 2 ml
DMF + 0.25 g SiO2 (Particle size 50 ± 5 nm, West Asia Chemical Co.,
Ltd. China), or 2 ml DMF + 0.25 g SiO2 + 0.6 ml heptadecafluorodecyl
trimethoxysilane (FAS-17) mixed into 10 ml of MS to induce phase
separation during the electrospray process. The electrospray used a
supply rate of 1.0 ml/h, 34 kV on the spinneret, and 25 cm distance
between the spinneret and the grounded collector (the schematic
of the electrospray system has been shown in Fig. S4). The collec-
tor was heated to 200–300 ◦ C during the electrospray process to
immediately vulcanize the HTV sample when the sprayed solution
dropped onto the collector. The films were 80–100 ␮m thick. The
MS with 2 ml DMF + 0.25 g SiO2 + 0.6 ml FAS-17 additives was also
used as the solution to cast a film on an Al substrate for comparison.
The film was vulcanized at 120 ◦ C for 20 min.
2.2. HTV film characterization
The substrates were prepared on aluminum foil where the sam-
ple shape and size could be easily controlled. A LEO-1530 scan
electron microscope (LEO Corp. Germany) was used to observe
69
the sample microstructures. Mercury injection (AutoPore IV 9510,
Micromeritics Instrument Corp, America) was used to measure
the porosity and pore diameter distributions. X-ray Photoelec-
tron Spectroscopy (ESCALAB 250Xi, Thermo Fisher Scientific Corp.
America) and ATR-FTIR (Nicolet NEXUS 6700, Thermo Fisher Sci-
entific Corp. America) were used to analyze the surface chemistry
of the substrates. Since the HTV films could not be easily peeled
off the foil, reflection ATR-FTIR was used for the measurement. The
samples used in these tests were all on Al foil and the weight of
silicon rubber substrates were obtained by subtract the weight of
foil.
2.3. Icing/de-icing cycles with SLIPS.
The icing/de-icing cycles used a cooling stage with a stage sur-
face temperature controlled to −14 ± 1 ◦ C. The experimental cell
was enclosed with a surrounding air temperature of 18 ± 2 ◦ C with-
out any flow of the surrounding air. The relative humidity was
80–90%. The freezing time was recorded when the whole substrate
was completely covered by ice with none of the original surface
directly exposed to the air. The homogeneous frost layer thick-
nesses ranged from 100 ␮m to 3 mm. After each de-icing cycle, the
substrate was placed at a tilt angle of 30◦ at room temperature for
1 h to remove the melt water from the surfaces. The lubricant mass
loss was then measured. Each measurement was carried out on 10
paralleled samples at the same time to get the average value.
2.4. Simulated rainfall tests
The rainfall was simulated by a pressurized water spray. The
drop size distribution on the surface was determined by measur-
ing the drop size on an aluminum plate with the drops found to
have diameters of 300 ␮m–3 mm after contact the plate. The falling
heights were from 0.5 m to 2 m. Water evaporation was not taken
into consideration since the drop size was measured after contact.
All the tested substrates were placed at a 30◦ tilt angle and washed
for different periods. The lubricant loss and contact hysteresis angle
were measured after each test. The advancing and receding con-
tact angles were measured using a contact angle goniometer (JCY-2,
Shanghai Fang Rui instrument Co., LTD) with a 5 ␮L DI water droplet
gently deposited on the substrate. Digital microphotographs of
the deionized water drops were taken in the horizontal direction
within 1 s using a digital microscopic camera. The contact angle
of each sample was directly measured from the microphotographs
using a protractor to get the average of the contact angles of the
drop at both three-phase contact points.
2.5. Ice adhesion strength measurements
The ice adhesion strength was measured using a custom-built
ice adhesion apparatus [26,27]. The samples were clamped to a
base plate with a cubic aluminum box with a 6 cm × 6 cm cross sec-
tion filled with 40 ml of water inverted on top. The entire sample
was cooled at a rate of 2 ◦ C per second from room temperature to
−20 ◦ C and maintained at this temperature for about 1 h to freeze
the water. A tensile tester (PN-TT300, HANGZHOU PNSHAR THCH-
NOLOGY CO., LTD.) was then used to apply a shear force to the Al box
with the strength required to fracture the ice-substrate interface
then recorded. Each measurement was carried out on 10 paralleled
samples at the same time to get the average value.
3. Results
The fluorinated hierarchically micro-structured HTV coatings
were prepared on aluminum (Al) substrates. The hierarchy of the
surface topography was adjusted by adding different additives
70 Q. Liu et al. / Applied Surface Science 346 (2015) 68–76
Table 1
Contact angles of a 5 ␮l water droplet and the lubricant on each type of silicon rubber
substrate before being infiltrated.
Substrate S-FNM S-NM S-M S-F
 ws(a) (◦ ) 162.6 ± 5.8 141.3 ± 4.6 126.8 ± 3.5 81.8 ± 4.3
 ls(a) (◦ ) ∼0a 11.2 ± 5.1 24.1 ± 3.9 25.8 ± 3.7
a
The lubricant can infiltrate completely into the substrate S-FNM.
and non-solvents in the solution preparation step to induce phase
separation during the electrospray process. Cast films were also
prepared for comparison.
Fig. 1 shows SEM images of different HTV samples. The addi-
tion of the non-solvent DMF into the electrospray HTV solution
created a micro-mastoids structured HTV coating on the Al sub-
strate. The micro-mastoids were 10–30 ␮m in diameter (labeled
“S-M”, Fig. 1a). The hierarchical topographies had SiO2 nanopar-
ticles mixed into the DMF-added HTV solution with the mastoid
diameters decreasing to 1–6 ␮m with nano-scale features seen on
the mastoids (labeled “S-NM”, Fig. 1b). Furthermore, FAS-17 was
mixed into the SiO2 and DMF-added HTV solution to improve the
affinity with the infiltrated fluorinated liquid lubricant to form
the SLIPS [28,36]. The result was a hierarchically micro-structured
coating produced by the electrospray and vulcanization (labeled
“S-FNM”, Fig. 1c). For comparison, a cast film was prepared using S-
FNM solution with no obvious micro-structure found (labeled “S-F”,
Fig. 1d).
Since the FAS-17 was pre-mixed into the HTV solution as an
additive instead of being directly functionalized on the surface, XPS
and FTIR spectroscopies were used to demonstrate the presence
of fluorine groups on the top-layer of the surface after high tem-
perature vulcanization. The XPS spectra for the substrate S-FNM is
shown in Fig. 2a. The S-FNM spectra contain F, Si, C and O peaks.
The high resolution C1s spectrum from 291 eV to 293 eV confirms
the presence of the fluorine group –CF3 on the surface [37]. The
IR spectrum in Fig. 2b shows stretching bands around 1200 cm−1
and 1148 cm−1 which are reported to be attributed to –CF2 and –CF
groups on different sites [38].
Fig. 2c shows the mercury intrusion curves for the 4 substrates
and the mercury intrusion volumes are plotted against the pore
diameter. As the diameter decreases, the accumulated mercury vol-
ume in the pores gradually increases. The pore volume for substrate
S-F is notably different from the other three electrospray coatings
with only ∼0.11 ml/g and pore sizes in the range of ∼3 to ∼40 nm,
which indicates that the bulk is relatively solid and the surface is
flat. The pore volumes for substrates S-FNM is ∼0.73 ml/g, S-NM is
∼0.58 ml/g, S-M is ∼0.51 ml/g. The proportions of the volume with
pores above 50 ␮m increases from 41% to 53% and to 60% while
the proportions of the volume with pores below 10 ␮m decreases
from 22% to 17% and to 9% for substrates S-FNM, S-NM and S-M.
Thus, substrate with a larger porosity and smaller pore diameter
can be produced using the non-solvent DMF, SiO2 nanoparticles
and FAS-17 by the electrospray coupled phase separation method.
The hydrophobicity and oleophilicity of these substrates were
characterized by measuring the static contact angles of water
droplets  ws(a) (subscript ‘w’) and lubricant  ls(a) (subscript ‘l’) on
the textured solid (subscript ‘s’) in the presence of air (subscript ‘a’).
The results are shown in Table 1. The suffix “K103” was added to the
surface names here to indicate that the surface were infused with
Krytox GPL103 (e.g. S-FNM-K103). Only the fluorinated hierarchi-
cal substrate S-FNM shows superhydrophobicity while the other 3
samples exhibit hydrophobicity with varying degrees for static con-
tact angles less than 150◦ . Only  ls(a) on substrate S-FNM decreased
to ∼0◦ while the others were all larger than 10◦ . This indicates that
fluorinating the flat HTV surface alone or increasing the substrates
roughness alone will reduce  ls(a) to a relatively low value but not
zero.  ls(a) will decrease to zero only if both factors are combined
in one substrate.
To demonstrate the lubricant retention ability, lubricant infused
HTV samples were subjected to repetitive icing/deicing treatments
in static experiments and water washout treatments with different
intensities in dynamic experiments.
Fig. 3a shows the durability of the samples after repetitive
frosting/de-frosting treatments. The freezing time here was defined
as the time at which the specific area (10 cm × 10 cm) surface was
completely covered by frost. That freezing times of substrates S-
FNM, S-NM, S-M and S-F without lubricant infiltration were ∼7 min,
∼8 min, ∼6 min and ∼9 min, respectively (for the Method Section
experimental conditions). After being immersed in the lubricant,
the freezing times were ∼62 min, ∼59 min, ∼48 min and ∼51 min
for the first cycle which indicates that the lubricant delays the frost
formation compared to the dry substrates. The freezing time was
∼35 min after 14 cycles and dropped to ∼13 min after 18 cycles for
S-FNM-K103 which is much longer than the other three samples’.
The decreasing in the freezing times should be related to the sample
surface chemistry, pore volumes and pore structures. The ratio of
freezing time for each surface increased with decreasing substrate
pore volume.
As the number of icing/deicing cycle increased, the freezing and
thawing times accelerate which is related to the lubricant deple-
tion. Thus, the total lubricant mass in the substrates was measured
to calculate the lubricant retention rate (LRR) before and after each
cycle.
Fig. S1 shows the lubricant retention rates for the 4 samples.
As the number of cycles increased, LRR dropped to <35% at the
4th cycle for all the samples indicating a rapid loss of the lubri-
cant. Among the three electrospray substrates, the hierarchically
structured surface S-FNM best retained the lubricant. For instance,
after 4 cycles, the LRR of S-FNM-K103 was ∼37%, S-NM-K103 was
∼32% and S-M-K103 was ∼17% and they decreased to ∼20%, ∼10%
and ∼8% after 16 cycles. Substrate S-M-K103 with only the micro-
scale features showed the fastest lubricant loss. The flat surface
preserved the better lubricant retention rate than S-FNM-K103
especially after 4 cycles although the surface was quite flat. The
pores on substrate S-F-K103 are all nanoscale pores in the range
of ∼3 to nm as shown in Fig. 2c. Nano-features provide the largest
capillarity which is benefit for wicking the lubricant of SLIPS. More-
over, the fluorofunctionalized surfaces S-FNM and S-F had stronger
affinity for the PFPE which also improved the lubricant retention
rate of the substrates compared to the other 2 samples.
Sample S-FNM-K103 had the best ice-delay performance based
on the freezing time test, which indicates that the icing resistance
ability of the substrate is not only related to the lubricant retention
rate but also to the absolute mass of the lubricant. For example,
S-F-K103 had the worst icing resistance due to the smallest total
pore volume. The lubricant retention rates shown in Fig. S1 after
being held vertically for 30 min show that only ∼0.35 g lubricant
remained on S-F which is much less than that on the electrosprayed
substrates.
In practical applications, the SLIPS surface characteristics are
not only related to the loss of lubricant in the de-icing process but
also the loss caused by water flow. Therefore, the SLIPS surfaces
with different morphologies were further evaluated after subject-
ing the substrates to pressurized water spray and comparing the
freezing times at which specific area substrates were completely
covered by ice. 1 cm × 1 cm square substrates were used to reduce
the freezing times and speed up the process of experimentation for
the edge effect of the substrates [27,39]. Fig. 3b shows the freez-
ing times for different lubricated substrates for different spray flow
rate for 10 h. The trends of these curves are similar for the different
samples at the same flow rate 0.003 ml/min cm2 with the freez-
ing times decreasing with the longer spray periods. The ratio of
 Q. Liu et al. / Applied Surface Science 346 (2015) 68–76
Fig. 1. SEM images of HTV samples. (a) 10 ml HTV solution + 2 ml DMF, S-M, electrospray; (b) 10 ml HTV solution + 2 ml DMF + 0.25 g SiO2 , S-NM, electrospray; (c) 10 ml HTV
solution + 2 ml DMF + 0.25 g SiO2 + 0.6 ml FAS-17, labeled S-FNM, electrospray; and (d) 10 ml HTV solution + 2 ml DMF + 0.25 g SiO2 + 0.6 ml FAS-17, S-F, cast film.
the freezing times at 0 h and 10 h was smallest for S-FNM-K103
and larger for S-NM-K103, S-M-K103 and S-F-K103. At the starting
point of the experiments, the freezing times of all the samples were
all in the range of 750–850 s related to the lubricant properties on
the substrate surfaces. The freezing times of the four samples are
all ∼350 s except for S-FNM-K103 after 10 h. The freezing times of
samples S-FNM-K103, S-NM-K103, S-M-K103, and S-F-K103 sub-
strates without lubricant were all 300–400 s, which is similar to the
freezing times of the SLIPS samples after being sprayed for 10 h. This
indicates that the lubricant properties were totally lost. It should be
pointed out that after 1 h of flushing, the drop ratio of freezing time
is related to the surface chemistry and pore structures. The freezing
time decreased dramatically to ∼300 s and remained at that level
for sample S-F-K103 without microstructures. The drop ratios of
the other 3 curves indicate that surface chemistry has strong effect
on lubricant infiltration while pore size and pore volume of the sub-
strate becomes a dominant parameter for lubricant retention ratio
if the surface is lubricantphilic. The results show that drop ratio of
freezing time increased with decreasing of substrate porosity and
increasing of pore size in our case. The fluorofunctionalized hier-
archical structured surface gives the best capacity retention. Thus,
the spray flow rate tests were only carried on sample S-FNM-K103.
The freezing time decreased with increasing of spray flow rate with
a freezing time of ∼500 s at 0.003 ml/min cm2 that decreased to
∼380 s at 0.02 ml/min cm2 and 0.1 ml/min cm2 after 10 h. Thus, the
lubricant capacity retention ratio is better for smaller spray flow
rate on the order of 10−3 ml/min cm2 .
The contact angle hysteresis of the water droplets was then
measured to identify the effect of the water flow on the lubricant
retention at room temperature. The hysteresis was measured on
the 4 lubricated substrates using 5 ␮l DI water droplets after flush-
ing with different spray flow rates and times. The results in Table 2
show that at a flow rate of 0.003 ml/min cm2 , the droplet still slip on
the S-FNM-K103 surface even after more than 8 h, but within only
3 h on S-NM-K103 and 1 h on S-M-K103. The drop did not slide off
after less than 1 h of flushing on S-F-K103. These results indicate
that the hierarchically structured roughness coupled with the sur-
face chemistry modification is very important for maintaining the
surface slip properties. The droplet remained on the surface after 8 h
71
of flushing at 0.003 ml/min cm2 , but the time decreased to 2 h when
the rate was increased to 0.02 ml/min cm2 . The surface prevented
the water drop from slipping after 1 h of flushing at 0.1 ml/min cm2 .
Thus, the contact angle hysteresis increased with increased flushing
time. The results indicate that both the increased intensity and the
length of the flushing period lead to rapid depletion of the lubricant.
The lubricant loss was also measured by weight to determine
the lubricant retention rate of the 4 samples in dynamic tests. The
results are shown in Fig. S2. The LRR of all samples decreased with
increasing washout time. S-F-K103 have the smallest LRR followed
by S-FNM-K103, S-NM-K103 and S-M-K103 with the largest LRR
at all the tested flow rates. The LRR also decreases with increasing
flow rate with the same sample. This may occur because most of the
lubricant mass loss in the dynamic tests happens when the capillary
force from the nano/micro-scale features is less than the water flow
pressure. Although the LRR of sample S-F-K103 is high, the capacity
(absolute mass) of lubricant is small. These results also confirm that
the durability of the substrate surface properties is not only related
to lubricant retention rate but also to the lubricant capacity for
dynamic conditions.
In addition to the ability to delay ice accretion, the ability of
the SLIPS to reduce the ice adhesion strength should also be eval-
uated. The ice adhesion strength was measured every 3 frosting
cycles for a total of 20 cycles. Fig. 3c shows the variation of the
ice adhesion strength with the repetitive frosting/defrosting cycles.
The ice adhesion strength on the SLIPS was 1–2 orders of magnitude
less than on the dry surfaces (the average for the dry S-FNM was
2900 kPa, for S-NM was 2500 kPa, for S-M was 1500 kPa, and for S-
F was 1500 kPa). For instance, the average ice adhesion strength
on the SLIPS were measured to be ∼60 kPa before the frosting
cycles, which is nearly 2 orders of magnitude lower than on the
bare substrate S-FNM which has a superhydrophobic surface. Such
a low ice adhesion strength might be attributed to the ultrasmooth
solid-liquid (ice-lubricant) interface provided by the lubricant on
top of the substrate. For dry substrates, the ice adhesion strength
on the superhydrophobic surface (S-FNM) was much larger than
that on the hydrophobic surfaces (S-NM, S-M and S-F) which is
in agreement with studies with literature [15,40,41]. In addition,
the adhesion strength on SLIPS for all the different substrates
72 Q. Liu et al. / Applied Surface Science 346 (2015) 68–76

Fig. 2. Characterization of substrates. (a) XPS spectrum of S-FNM coating. The high-resolution inset is the C1s spectrum. (b) FTIR spectra of S-FNM coating. (c) Mercury
porosimetry curves for the 4 samples.

increased with gradually increasing difference with the increas-
ing of frosting/de-frosting cycles. After 20 cycles, the ice adhesion
strength reached 1500 kPa for the oil-infiltrated S-M and 1400 kPa
for the oil-infiltrated S-F which is consistent with the dry sub-
strates, indicating that the lubricant has already been depleted. The
ice adhesion strength on S-FNM-K103 increased to 700 kPa which
is much lower than that on the other three surfaces.
4. Discussion
easily coalesces and the droplets easily slid off because of the ultra-
smooth surface rather than becoming attached to the surface which
would promote icing (Fig. S3). This is one of the advantages that
make SLIPS surface as an excellent icephobic surface.
The nucleation barrier between homogeneous and heteroge-
neous nucleation can also account for the better anti-icing property
[44]. Nucleation on a lubricant surface is normally homogeneous
nucleation since the liquid lubricant has few solid impurities. The
nucleation barrier is calculated as:

With a fresh SLIPS sample, the substrate is covered completely

by a thin layer of lubricant. Condensation on the fluid surface is then 4
Ghomo = − r 3 GV + 4r 2 IL (1)
much easier than on the dry solid surface [42,43]. The condensate 3

Table 2
Contact Angle Hysteresis of SLIPS on different substrates with 5 ␮l DI water droplets for different simulated rainfall intensities and periods.

Substrate Flow rate (ml/min cm2 ) 1h 2h 3h 4h 8h 10 h

S-FNM-K103 0.003 4.4 ± 2.8 10 ± 3.7 15.8 ± 4.8 19.7 ± 4.2 23.5 ± 5.6 –
S-FNM-K103 0.02 20.6 ± 5.5 24.8 ± 5.2 – – – –
S-FNM-K103 0.1 – – – – – –
S-NM-K103 0.003 18.2 ± 3.5 23.6 ± 5.0 25.2 ± 3.9 – – –
S-M-K103 0.003 22.3 ± 4.7 – – – – –
S-F-K103 0.003 – – – – – –
 Q. Liu et al. / Applied Surface Science 346 (2015) 68–76
Fig. 3. Anti-frosting/icing ability of the SLIPS. (a) Freezing times on four types of
lubricated substrates (10 cm × 10 cm) for 20 cycles. The frosting process used a
cooled stage at −14 ◦ C in high humidity (80–90%) air at 18 ◦ C. After the surface
was completely covered by frost, the cooling stage temperature was raised to room
temperature at ∼13 ◦ C/min for de-frosting. (b) Freezing times of the 4 1 cm × 1 cm
samples when sprayed with pressurized water for different flow rates and durations.
(c) Adhesion force on the surfaces after icing/de-icing.
73
Fig. 4. Schematic diagram of heterogeneous nucleation on a solid surface.
while the heterogeneous nucleation barrier on a solid surface
is:
 4 
Ghete = − r 3 GV + 4r 2 IL S() = Ghomo S() (2)
3
1 2
S() = (2 + cos )(1 − cos ) (3)
4
where r is the nucleation radius,  IL is the interfacial energy
between the nucleus and the liquid, GV is the solidification driving
force and  is the contact angle of the nucleus on a solid sur-
face as shown in Fig. 4.  is approximately equal to the contact
angle of the droplet on a flat surface which was about 80◦ here, so
Ghete ≈ 0.3Ghomo . Therefore, nuclei will more easily form on a
solid surface than on the lubricant.
The experiments showed two nucleation modes. In the first few
cycles, the ice grew only by bridging from the surrounding non-
SLIPS areas where drops nucleation formed and the freezing wave
propagated to the intermediate zone (Fig. 5 a and b), which is called
“edge mode nucleation” [39,45,46]. The propagation velocity of the
frost front in one direction was ∼0.7 mm/min. After depletion of
the lubricant, nuclei randomly formed on the surface and expanded
radially (Fig. 5c and d) which is called “random–point mode nuclea-
tion”. All these local freezing areas quickly connected together. In
this test, the propagation velocity was ∼3 mm/min during the 14th
cycle, which is 4 times faster than that during the first cycle. Thus,
the “random–point mode nucleation” and the faster propagated
velocity both shortened the icing delay time.
The mechanism for the lubricant retention in the micro-
structures needs to be understood to explain the ice build-up
characteristics of the SLIPS surface on different substrates. After
these substrates are placed vertically for 30 min, a thin lubricant
layer will be retained on the surfaces as shown in Fig. 6a. How-
ever, this coating can be easily washed away which will change
lubricant-solid contact pattern as described by Smith et al. [20].
They demonstrated that for  ls(a) = 0, the entire surface texture is
covered with a thin layer of lubricant as shown in Fig. 6b. If the
contact angle is greater than zero, part of the surface will be left
uncovered as shown in Fig. 6c.
The contact angle  ls(a) on S-FNM is 0◦ which is smaller than the
others as shown in Table 1. This indicates that S-FNM is completely
covered by lubricant as shown in Fig. 6b. In addition, for  ls(a) = 0,
the low surface tension lubricant inside the pores will creep to the
surface so there will be no solid-air contact line as shown in Fig. 6b
and d. In this case, only homogeneous nucleation will occur and
the frost build-up on the surface will be induced by “edge mode
nucleation”. The anti-icing ability will continue until the amount of
lubricant in the micro-pores can no longer cover the entire textured
surface area. Although S-F-K103 has the best lubricant retention
rate, the ability to resist icing is much poorer than S-FNM-K103
due to the limitation of lubricant capacitance. The S-NM-K103, S-
M-K103 and S-F-K103 surfaces seemed to have uncovered area on
the surfaces lubricant-air contact lines as shown in Fig. 6c, so the
74 Q. Liu et al. / Applied Surface Science 346 (2015) 68–76
Fig. 5. Ice build-up on the lubricated S-FNM surface. (a) Morphology of the freezing process at 738 s in the first cycle showing “edge mode nucleation”, (b) 1521 s in the first
cycle; (c) 183 s in the 14th cycle showing “random–point mode nucleation”, and (d) 256 s in the 14th cycle.
nucleation process began as “random–point mode nucleation” with
heterogeneous nucleation on the exposed solid. Therefore, these
had worse anti-icing abilities. The experiments showed that the
“edge mode nucleation” was sustained for 15th cycles for the S-
FNM-K103 surface while the other surfaces lasted only 2–5 cycles.
The results suggest that lubricant loss is first lost from the larger
pores and then smaller pores since the capillary force to hold the
lubricant is in proportion to the micro/nano length scales of the
pores. The remaining lubricant volume in the substrate can be then
calculated based on the lubricant mass loss recorded for the differ-
ent test conditions for the four samples.
As shown in Fig. S1, the slope of the LRR curve reaches a mini-
mum after 7 icing/de-icing cycles with S-FNM-K103. At this point
the volume of residual lubricant fills ∼40% of the pores volume
in the substrate. The pore distribution in Fig. 2c shows that 45%
of pore volume has sizes below 40 ␮m, which indicates that the
lubricant is stable in these size holes during icing/deicing. For the
non-fluorine functionalized substrates, S-NM-K103 and S-M-K103,
the pore volume proportions were ∼23% and ∼12% for which LRR
would be ∼10% and ∼7%. The critical diameters of the pores to wick
the lubricant at these points are ∼20 ␮m and ∼15 ␮m as shown in
Fig. 2c which are much smaller than that for the S-FNM-K103 sur-
face. Thus the lubricant can create a stable coating only with pores
having diameters comparable to the critical size. Surface chemistry
can enlarge the critical size in icing/de-icing process.
The effective capillary size of the PFPE lubricant during water
flushing with different flow rate could be obtained in the same way.
43% vt/vt (34% wt/wt as shown in Fig. S2) the lubricant was left on S-
FNM-K103 after 10 h of washing at 0.003 ml/min cm2 . The effective
diameter would be ∼36 ␮m based on the pore size distributions
shown in Fig. 2c. Accordingly, the critical sizes of the S-NM-K103
and S-M-K103 surfaces would then be ∼20 ␮m. For a flow rate of
0.02 ml/min·cm2 , the critical size of the pores on S-FNM-K103 and
S-NM-K103 is 15 ␮m while the size on S-M-K103 is ∼10 ␮m. For
a flow rate of 0.1 ml/min·cm2 , they are all ∼2 ␮m. The results also
indicate that the surface fluorination on substrates can enlarge the
critical size in water flushing dynamic process.
Moreover, it should be mentioned that positive correlation
between ice adhesion strength and lubricant retention rate was
found. Before cycling tests, ice adhesion strength on bare surfaces
is much higher than that on surfaces with excess lubricant. After
that, as shown in Fig. 3c and Fig. S1, the lubricant loss ratio was the
smallest with S-FNM-K103 while the ice adhesion strength on SLIPS
based on S-FNM which contains more micro-structures is much
lower than that on the other samples. During the lubricant disper-
sion process, the substrate becomes rougher and the surface area
becomes larger. So in our experiments, the ice adhesion strength
should depend on the exposed rubber surface area of the substrate,
which was proved and systematically studied on superhydrophobic
surface by Varanasi et al. [15].
It seems like contrary to Subramanyam’s [26] findings that the
ice-adhesion strength is dependent on texture and decreases with
increasing texture density [26]. However, both the stress con-
centrators and ice-surface contact area are determinants of ice
 Q. Liu et al. / Applied Surface Science 346 (2015) 68–76
Fig. 6. Illustrations of the air, oil and substrate contact patterns. (a) Excess oil ini-
tially on the substrate surface; (b) low surface tension lubricant inside the pores
creeps outside to completely cover the surface; (c) surface roughness increases as
the lubricant is depleted; (d) exposed surface with lubricant oil-air contact lines;
and (e) schematic of realistic contact pattern between the ice and the substrate.
adhesion strength on different kinds of surfaces [15,26]. In our case,
the microposts are spherical mastoid with which the stress con-
centration should be 1 order of magnitude smaller than that with
the edges of the cubic posts in their case. So, in our experiments,
exposed rubber surface area is the dominant factor for ice-adhesion
strength while in their experiments, the sharpness of the cubic
edges act as stress concentrators is the dominant factor for ice
adhesion strength.
5. Conclusion
In conclusion, hierarchically micro-structured silicone rubber
surfaces were prepared using the electrospray method with phase
separation. The surfaces then infused with perfluoropolyether
lubricant to form very low contact angle hysteresis SLIPS. These
substrates with different surface morphologies were then com-
pared to investigate their anti-icing characteristics and lubricant
retention abilities. The results indicate that the SLIPS based on
fluorine-functionliazed substrates with hierarchical nanoscale and
microscale features had the best suppression characteristics. The
result show that ability to delay ice accretion and the reduced
75
ice adhesion strength are both structure dependent and surface
chemistry dependent. The critical pore sizes can be enlarged in
the substrates by surface fluorination for repeated icing/deicing,
for water flushing and for ice-shedding. The lubricant retention
ability is not only related to the nano/micro surface features and
surface chemistry but also to the lubricant retention capacity of
the substrate. Lubricant in the microscale pores can easily creep up
to the surface with nano-scale pores providing stronger capillary
forces to hold the lubricant in the pores. Such fluorinated hierar-
chically nano/micro structured substrate will enable the lubricant
to completely cover the surface which reduces heterogeneous
nucleation and frost propagation velocity. Moreover, the ice adhe-
sion strengths of the SLIPS are 1–2 orders of magnitude lower
than on the conventional surfaces. Ice-adhesion strength increases
with increasing lubricant loss during the frosting/defrosting cycles.
Therefore these electrospray fluorinated hierarchical porous sili-
cone rubber surfaces could be practical low cost, simple, scalable,
and compatible icephobic surfaces.
Author contributions
Y.Y. conceived the project. Y.Y. and Q.L. designed the exper-
iments. Q.L. carried out the experiments. Q.L., Y.Y., M.H., Y.X.Z.,
Y.Y.L. and X.D.L. discussed the results. Q.L. and Y.Y. wrote the initial
manuscript which was approved by all the authors.
Conflict of interest
The authors declare no competing financial interests.
Acknowledgements
The authors would like to thank the financial support from
the National Natural Science Foundation of China (Grant No.
51102143).
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.apsusc.
2015.02.051.
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