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Multiple Levels Hydrophobic Modification of Polymeric Substrates

by UV-Grafting Polymerization with TFEMA as Monomer
Yanning Chen,1 Dong Chen,1 Yuhong Ma,2 Wantai Yang1,2
1

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology,
Beijing 100029, China
Correspondence to: W. Yang (E - mail: [email protected])

Received 10 November 2013; accepted 6 January 2014; published online 30 January 2014
DOI: 10.1002/pola.27099

ABSTRACT: The hydrophobic solid surface modification with

fluorine-containing monomers has received tremendous attention because of its unique structure and excellent property.
However, these hydrophobic films normally suffer from two
major problems: one is weak interface interaction between fluoropolymers and substrates, and the other is the high cost of
fluorine-containing monomers. Herein, with the aim of feasible
industrial application, a facile in situ UV photo-grafting method
is reported, which could ensure the formation of chemical
bonds between fluoropolymer-grafted layer and substrate with
a low cost commercial 2,2,2-trifluoroethyl methacrylate
(TFEMA) as monomer. With low-density polyethylene (LDPE)
film as a model substrate, four kinds of poly-TFEMA-grafted
layer are fabricated on LDPE films with different surface mor-

phologies: polymer brush, polymer network, crosslinked nanoparticles, and a micro- and nanoscale hierarchical structure.
The experimental results showed that the water contact angles
(CAs) of the LDPE films grafted with polymer brush, polymer
network, and crosslinked nanoparticles were (103 6 2) ,
(95 6 2) , and (122 6 2) , respectively, which were much higher
than that of LDPE film. The introduction of micro- and nanoscale hierarchical structures can dramatically improve the surface roughness, which will further enhance the film
hydrophobicity, and the water CA can reach as high as
C 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A:
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INTRODUCTION The

on a hydrophobic surface (CA >90 ), and the other is to

modify a rough surface with compounds having low surface
energy, such as fluorinated compounds.9 As known, fluoropolymers have excellent weather resistant, good thermal stability, outstanding chemical inertness, low friction coefficient,
extremely low surface energy, and so forth.10,11 Therefore
the fluoropolymers have attracted great attention due to
their unique property since Plonkett first discovered a slippery white powder inside a canister of tetrafluoroethylene
(TFE) gas in 1938.12 Since then, the fluoropolymers have
found various applications in high-tech and modern technologies, for example, biomaterials, insulators and paints,
due to their excellent property.1316 Because they are very
effective in reducing surface energy of materials, the fluorinated polymers have more applications in the field of functional coatings, namely, water and oil repellents for the
textile, conservation of culture relics, and surface protection
of polymer films.17,18 However, two issues are faced in practical applications: one is unstable interface between fluoropolymers and substrates because of their difference in
surface energy, and the other is high price of fluorinecontaining monomers or polymers. Commercial monomer,

hydrophobic solid surfaces have

received tremendous attention from both theoretical and
practical aspects because of their unique structure, excellent
property, and numerous potential applications in many
fields, for instance, avoiding corona discharge under rainy
condition by conductor coated with super-hydrophobic film,
preventing the adhesion of dust onto traffic indicators, and
constructing self-cleaning surfaces which simulate the skin
of insects and plants.13 Besides the above mentioned fields,
the hydrophobic surfaces also have many other applications.
For example, Yamauchi et al. succeeded in reducing the
adherence of snowflake on the antenna by the use of waterrepellent coatings.4 Fukuda et al. reported that the frictional
drag could be dramatically reduced by using a waterrepellent surface and air-injection, indicating that hydrophobic films are effective for the ship hull, tubes, and pipes.5
Intensive investigations have demonstrated that the surface
hydrophobicity (wettability) can be controlled by both the
surface energy and surface roughness.68 Generally, there are
mainly two ways to construct hydrophobic surface. One is to
create a rough structure (e.g., with a hierarchical structure)

KEYWORDS: films; fluoropolymers; nanoparticles; photopolymerization

C 2014 Wiley Periodicals, Inc.

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SCHEME 1 The fabrication strategies of four kinds of PTFEMA grafted layer with different surface morphologies on LDPE film. (A)
PTFEMA brush; (B) PTFEMA network with TMPTA as crosslinker; (C) PTFEMA/TMPTA crosslinked nanoparticles with TMPTA as
crosslinker; (D) Micro- and nanoscale hierarchical structure based on TFEMA and TMPTA.

2,2,2-trifluoroethyl methacrylate (TFEMA), is one of the most

common and cheap fluorine-containing monomers, and the
PTFEMA homopolymer is extensively used in various applications due to its excellent capacity for water repellence and
stain resistance. For this reason, TFEMA was chosen as the
fluorine-containing monomer in the present work.
Graft polymerization is known to be a useful technique for
the modification and functionalization of polymeric materials.19,20 Among various graft polymerizations, UV photografting polymerization is a bottom-up method, for which
surface radicals are formed in situ through a photo-reduction
reaction between photo-initiator and surface CAH bond of
polymeric substrates, and these surface radicals can sequentially initiate the polymerization of monomer, leading to the
formation of graft polymer chains chemically bonded onto
the substrates.21,22 During the past decade, our lab has carried out a series of researches on UV photo-grafting polymerization.2327 Polymer layer with structure of craters
could be successfully grafted onto the low-density polyethylene (LDPE) film through surface photo-grafting polymerization of trimethylolpropane triacrylate (TMPTA) with
benzophenone (BP) as photoinitiator in tetrahydrofuran/
water mixed solvent, and the mixed solvent is the key factor
leading to the formation of craters in the grafted layer.23 For
a methyl methacrylate (MMA)/divinyl benzene microemulsion
system, multilayer and monolayer crosslinked poly(methyl
methacrylate) nanoparticles with a diameter of 30 or 60 nm
have been successfully grafted onto poly(propylene) (PP) film

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by one-step and two-step photografting polymerization

method, respectively.25,26 When a N-vinylpyrrolidone/N,N0 methylene bisacrylamide inverse microemulsion was grafted
on the PP film via one-step surface photo-grafting method,
quasi-bimodal-crosslinked PVP particles (ca. 45 and 110 nm)
were formed and tethered firmly on the PP film, leading to
superhydrophilicity of the film surface [water contact angle
(CA) below 5 ].27 On the whole, the UV-initiated surface
photo-grafting polymerization provides a facile and rapid way
to construct grafted polymer layers with special nanotopography on polymer films.
In this article, with TFEMA as monomer and LDPE film as a
model polymer substrate, PTFEMA grafted layers with different morphology were obtained through an in situ UV
photo-grafting method. Under UV irradiation, hydrogen
abstraction reaction of BP took place on the surface of the
films, generating surface free radicals to initiate the graft
polymerization. Four kinds of PTFEMA grafted layers were
designed and fabricated with different recipes, including
polymer brush, polymer network, crosslinked nanoparticles,
and hierarchical structure, as shown in Scheme 1. This technology provides a new pathway to construct multilevel
structured grafted polymer layers via UV photo-grafting
polymerization, and hydrophobic or hydrophilic surface
with multilevel structured grafted layer can be designed
and fabricated by controlling the surface composition and
topography, which have potential applications in a wide
range of fields.

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FIGURE 1 (a) FTIR spectra of blank LDPE film and LDPE film grafted with PTFEMA. (b) Thickness of polymer brush and grafting
efficiency of monomer versus irradiation time. (c) Water contact angle of the PTFEMA grafted LDPE film versus polymer layer
thickness. SEM, AFM, and water contact angle images of (d) the blank LDPE film and (e) the LDPE film grafted with PTFEMA.

EXPERIMENTAL

Materials
The LDPE films (60 lm thickness, Beijing No. 7 Plastic Factory)
with a side length of 6 cm were used as substrates in all experiments. The LDPE films were extracted with acetone for 24 h
before use. TFEMA (Haerbin Xuejia Chemical Reagent Company)
was purified by distillation under reduced pressure, and stored
in a refrigerator before use. Commercial TMPTA (Tianjin Tianjiao
Chemical, China) was used as received. BP (Shanghai Chemical
Regents) was recrystallized in petroleum ether before use.
Cyclohexanone and acetone (Beijing Modern Eastern Fine Chemical Plants) were used without further purification.
LDPE Film Grafted with PTFEMA Brush
One-step surface grafting polymerization process was
employed in the present work. The reaction mixtures were
prepared by dissolving TFEMA and BP in acetone. A predetermined amount of the reaction solution (60 lL) was transferred onto the surface of LDPE film using a microsyringe.
Another LDPE film was used to cover the reaction mixture,
and the solution was spread into an even and very thin liquid layer under suitable pressure. The sandwich structure
was then fixed between two quartz plates and irradiated
under UV light (light intensity 6000 lW cm22 at k 5 254
nm) for a certain time at room temperature. After that, the
LDPE films were taken out, and the bottom films were split
off and discarded. The top LDPE films were immersed in
acetone and subjected to 40 W ultrasonic for 20 min to
remove the excess reactants and ungrafted homopolymer.
Then, the LDPE films were extracted with acetone for 8 h in
order to further remove the ungrafted polymer.

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LDPE Film Grafted with PTFEMA/TMPTA Network

The fabrication procedure of LDPE film grafted with
PTFEMA/TMPTA-crosslinked network was similar to that of
PTFEMA brush described above. The only difference was
that TMPTA was added into the reaction system to form
crosslinked structure.
LDPE Film Grafted with PTFEMA/TMPTA Nanoparticles
In this section, cyclohexanone was used as solvent instead
of acetone. To seek deep insight into the effect of TFEMA
concentration and TFEMA/TMPTA mass ratio on the size
of the PTFEMA/TMPTA-crosslinked nanoparticles, photografting polymerization of TFEMA/TMPTA with different
TFEMA concentrations and TFEMA/TMPTA mass ratios
were conducted.
LDPE Film Grafted with Micro- and Nanoscale
Hierarchical Structure
Micro- and nanoscale hierarchical architectures were fabricated through a two-step photo-grafting process. First, threedimensional (3D) patterned crosslinked PTMPTA cylinders
were obtained with the help of a photomask. The reaction
mixtures were prepared by dissolving TMPTA and BP in acetone. The concentration of TMPTA was 25 wt % and BP was
5 wt % to TMPTA. A micropatterned photomask, circular
hole with diameter about 10 lm, was used instead of the
top quartz plate for the preparation of a micropatterned
polymer surface. The height of micropatterned polymer layer
was controlled by varying UV irradiation time. The micropatterned polymer films were extracted with acetone before the
subsequent photo-grafting of PTFEMA brush and PTFEMA/
TMPTA nanoparticles.

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to be 70 wt %, and TMPTA was 10 wt % to that of TFEMA,

respectively.
Characterization
The grafting efficiency of monomer and thickness of polymer
layer were calculated based on the following equations:
Grafting efficiency of monomer5W2 W1 =W3 3100% (1)
Thickness of polymer layer 5 W2 W1 =q=S

(2)

where, W1 is the weight of the blank film; W2 is the weight

of the film after the grafting polymerization of monomer; W3
is the weight of the monomer coated between the two films;
q is the density of PTFEMA which is 1.45 g cm23;28 and S is
the area of the model substrate.
The chemical composition of the films was characterized by
Fourier transform infrared spectroscopy (FTIR) with a Nicolet Nexus 670 spectrometer (Thermo-Nicolet) with a 4 cm21
resolution. CA measurements were performed on a Contact
Angle System OCA (OCA 20, made in Germany by Dataphysics Instruments). The value was the average of at least 10
readings for each specimen. The surface roughness was studied with an atomic force microscope (AFM) (Digital Instruments, Version 6.12). Surface morphology of the film was
observed by a scanning electron microscope (SEM) (Zeiss
SUPRA 55) with an accelerating voltage of 5.00 kV, combined
with energy dispersive spectroscopy (EDS) for the determination of elemental composition.
RESULTS AND DISCUSSION

FIGURE 2 (a) SEM, AFM, and water contact angle images of

LDPE-g-PTFEMA/TMPTA 3D network. (b) Thickness of PTFEMA/
TMPTA network versus irradiation time. (c) Water contact angle
of the LDPE-g-PTFEMA/TMPTA versus PTFEMA/TMPTA network thickness.

For the photo-grafting of PTFEMA brush, certain amount of

reaction solution (60 lL) composed of TFEMA and acetone
was transferred onto the micropatterned film by a microsyringe. The TFEMA concentration was set to be 70 wt % and
BP was 5 wt % to that of TFEMA (light intensity 6000 lW
cm22 at k 5 254 nm) for a certain time at room temperature.
For the photo-grafting of PTFEMA nanoparticles, the fabrication procedure was similar to that of PTFEMA/TMPTA nanoparticles described above. The TFEMA concentration was set

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LDPE Film Grafted with PTFEMA Brushes

In order to obtain PTFEMA brushes, acetone was used as
reaction medium due to its good solubility for both TFEMA
and PTFEMA. The FTIR spectra of the blank LDPE film and
the LDPE film grafted with PTFEMA (LDPE-g-PTFEMA) are
presented in Figure 1(a). The strong absorbance at 1170
cm21 was attributed to the fluorinated carbonate groups
(CF3). Another characteristic peak appears at 1745 cm21
was corresponding to stretching vibration of the ester carbonyl (C@O). In addition, there were no any visible peaks at
16801640 cm21, which was characteristic absorption band
for the C@C stretching vibration, indicating that there was
no residual TFEMA.
With a TFEMA concentration of 50 wt % and a BP concentration of 5 wt % to that of TFEMA, the grafting process of
TFEMA was investigated in detail, and the results are presented in Figure 1(b). The result demonstrated that the
thickness of the PTFEMA grafted layer increased almost linearly from 9 nm to about 68 nm with increasing irradiation
time from 30 to 180 s, indicating living characteristic of
the surface photo-grafting polymerization process. Low grafting efficiency was a defect of the photo-grafting system, and
the grafting efficiency was only 6.2% with 180-s irradiation
time although the grafting efficiency increased gradually.
There were two possible reasons for this low grafting efficiency. On one hand, the affinity between TFEMA monomer

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FIGURE 3 SEM, AFM and water contact angle images of the LDPE films grafted with PTFEMA/TMPTA nanoparticles. (a) TMPTA
was 10 wt % to that of TFEMA, and the TFEMA concentrations were: (a1) 30 wt %, (a2) 50 wt %, and (a3) 70 wt %, respectively. (b)
TFEMA was 70 wt % in cyclohexanone, the TMPTA concentrations were (b1) 2 wt %, (b2) 6 wt %, (b3) 10 wt %, (b4) 15 wt %, and
(b5) 20 wt %, respectively. (BP was 5 wt % to that of TFEMA, UV light intensity was 6000 lW/cm2 and irradiation time was 3 min.)

and the LDPE substrate was very poor, which consequently

affects the addition of TFEMA to surface radicals. This is a
general problem for the polymerization and grafting polymerization of fluorine-containing monomers. On the other
hand, relatively low concentration of radicals was formed at
the LDPE surface during UV irradiation. Figure 1(c) shows
that the water CAs of the LDPE film grafted with PTFEMA
brush were in the range of (99 6 2) to (103 6 2) , independent of the polymer brush thickness. This result indicated that the substrates have been completely covered with
PTFEMA brushes when the thickness was 9 nm with a irradiation time was 30 s, and no water CA increase was
observed with increasing polymer brush thickness.
The surface morphologies of the blank film and the PTFEMA
grafted film were observed by SEM and AFM (LDPE-gPTFEMA with 68-nm PTFEMA brush was taken as an example), and the results are shown in Figure 1(d,e). It can be

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seen from Figure 1(d,e) that the grafted PTFEMA layer was
smooth and showed no visible difference from that of the
blank film. The roughness values (Rq) of the blank film and
the PTFEMA grafted film from AFM images are 16.4 and
18.7nm, respectively. The water CA of the LDPE-g-PTFEMA
was (102 6 2) , about 25 higher than that of the blank
LDPE film (only 77 6 1) . The smooth surface and the high
water CA proved that the PTFEMA brushes were formed on
the LDPE substrate and the PTFEMA brushes could dramatically improved the hydrophobicity of the polymer surface.
LDPE Film Grafted with PTFEMA/TMPTA 3D Network
In order to fabricate a surface grafted PTFEMA 3D network,
10 wt % multifunctional monomer TMPTA was added to
the TFEMA/BP/acetone solution. We first observed the surface morphology of the LDPE-g-PTFEMA/TMPTA film with
an irradiation time of 180 s by SEM and AFM. It was found
that the surface of the LDPE-g-PTFEMA/TMPTA film was

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were only 68 and 75 nm, respectively, while the analysis

depth of the EDS measurements can reach micrometer level.
As a result, the C and H in the LDPE substrate were taken
into account, leading to the obvious discrepancy between
the experimental and theoretical values. In spite of this, the
EDS results could determine the difference in F atom percent of the films (at least qualitatively). This demonstrated
that TMPTA can effectively copolymerize with TFEMA,
which could attribute to the high grafting activity of
TMPTA.
LDPE Film Grafted with PTFEMA/TMPTA Nanoparticles
When cyclohexanone was used as grafting medium instead
of acetone, the photo-grafting polymerization of TFEMA/
TMPTA could directly introduce nanoparticles onto the polymer substrate, and the reason for the formation of nanoparticles might be that PTFEMA showed poor solubility in
cyclohexanone. To seek deep insight into this new system,
the photo-grafting polymerization of TFEMA/TMPTA with
different TFEMA concentrations and TFEMA/TMPTA mass
ratios were conducted through a one-step method and the
results are presented in Figure 3.

FIGURE 4 (a) Evolution of the cylinder height versus irradiation

time and (b) water contact angle of the film grafted with patterned cylinders versus the cylinder height. The patterned cylinders were obtained through one-step photo-grafting
polymerization of 25 wt % TMPTA in acetone, with BP as photoinitiator (5 wt % to that of TMPTA).

very smooth [Fig. 2(a)] similar to that of the LDPE-gPTFEMA [Fig. 1(e)], implying the formation of an even
grafted layer of 3D-PTFEMA/TMPTA crosslinking network.
From Figure 2(b) and by comparing with Figure 1(b), we
can see that the grafting polymerization of TFEMA can be
further improved by the addition of TMPTA.2931 The grafting layer thickness could reach up to about 75 nm when
the irradiation time was 180 s, superior to that of the polymer brushes which was about 68 nm. However, the water
CA is in the range of (92 6 2) to (95 6 2) , which was
about 8 lower than that of the PTFEMA brushes. In order
to clear up the reason for the result, we measured EDS of
the grafted layer, and the EDS analysis showed that the
atom percentage of F on the surface of film 1e (PTFEMA
brushes) and 2a (PTFEMA 3D network) were 1.43 and
1.23%, respectively. These results were much lower than
the theoretical values based on the F atom percent in the
pure TFEMA monomer and in the TFEMA-TMPTA mixture
(16.6 and 13.7%). That is because the thicknesses of the
PTFEMA grafted layer and PTFEMA/TMPTA grafted layer

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It can be seen from Figure 3(a) that the size of the nanoparticles increased with increasing TFEMA concentration. When
the TFEMA concentration was 30 wt %, the size of the nanoparticles was very small and not uniform. The size of the
PTFEMA nanoparticles reached up to about 200 nm as the
TFEMA concentration increased to 70 wt %. The variation of
particles size with increasing TFEMA concentration could be
explained based on the formation process of the crosslinking
particles. Due to the presence of crosslinking agent TMPTA,
the grafting polymerization would result in polymer with
crosslinked structure, which would precipitate from the reaction system and formed polymer nanoparticles on the film
surface. The propagating radicals were confined in the particles, and the growth of the particles would be promoted
with high monomer concentration, as a result, the size of the
polymer particles increased with increasing monomer concentration. The size of the PTFEMA nanoparticles had direct
effect on the surface roughness, which consequently influence the water CA. The roughness values of the films a1, a2,
and a3 were 18.6, 25.3, and 51.7 nm, respectively, from AFM
results, and accordingly the water CAs were (94 6 2) ,
(114 6 2) , and (122 6 2) , respectively. These results indicated that the size of the PTFEMA nanoparticles increased
with increasing TFEMA concentration, and the surface roughness and water CA of the film increased accordingly.
Figure 3(b) shows the variation of the size of nanoparticles
with different TMPTA concentration. It can be seen that the
particle size increased when the TMPTA concentration
increased from 2 to 10 wt %. With further increase in
TMPTA concentration, the size of the crosslinked nanoparticles decreased, and the water CAs decreased accordingly
from (122 6 1) to (110 6 2) . This unusual result was due
to the special polymerization kinetic of multifunctional
monomer TMPTA, which was quite different from that of

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FIGURE 5 Three-dimensional AFM images and EDS results of the micropatterned LDPE films. The inset pictures show magnification surface morphology of the micropattern. (a) LDPE-g-PTMPTA cylinders with water contact angle of (105 6 2) ; (b) LDPE-gPTMPTA cylinders-g-PTFEMA brush with water contact angle of (128 6 2) ; (c) LDPE-g-PTMPTA cylinders-g-PTFEMA/TMPTA nanoparticles with a water contact angle of (140 6 1) .

monofunctional monomers.32,33 The multifunctional monomer can lead to the formation of crosslinking network, which
will highly affect the radical termination process, and reaction
diffusion controlled termination becomes the dominant termination due to the diffusion-limited nature of highly crosslinked systems. According to our previous research, serious
radical trapping occurred when the concentration of multifunctional monomer exceeded certain level, leading to low
grafting conversion. In our present research, the grafting polymerization was promoted with increasing TMPTA concentration when the mass ratio of TMPTA/TFEMA was lower than
15 wt %, while the grafting polymerization was retarded as
the mass ratio of TMPTA/TFEMA exceeded 15 wt %.23
The water CAs were (99 6 2) , (117 6 1) , and (121 6 2)
when the TMPTA concentrations were 2, 6, and 10 wt %,
respectively, indicating that the surface hydrophobicity could
be controlled by surface roughness. For hydrophobicity of
the surface, there are two distinct hypotheses to define the
water CA of the nonideal solid surface. Wenzel model considers that drop spread inside the texture of the solid surface.34
Cassie model insists that drop sits partially on the air. In
return, air can remain trapped below the drops, which also
enhance the hydrophobic behavior.35 It should be noted that
the Wenzel equation applies only to thermodynamic equilibrium state. In many cases, it turns out that drops on materials are observed to be in the Cassie regime.36 In the regime
of Cassie equation, the apparent CA on the roughness surface, h0 , described as: cosh0 5 21 1us (1 1 cosh), where us is
the area fraction of solid in contact with the liquid and h is
the flat intrinsic angle (Young CA). When the flat intrinsic
angle remains unchanged and us will decrease with

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increasing degree of roughness, so the Cassie angle will

increase with increasing surface roughness.
LDPE Film Grafted with Hierarchical Structured Layer
To prepare a micro- and nanoscale hierarchical structure
onto the LDPE surface, we devised a two-step photo-grafting
procedure. First, a photo-grafting crosslinking polymerization
of TMPTA was conducted under a photomask with BP as
photoinitiator, to graft 3D patterned PTMPTA-crosslinked cylinders on the LDPE film. Second, photo-grafting polymerization of TFEMA monomers was subsequently initiated by the
dormant group on the PTMPTA cylinders to introduce polymer brushes (TFEMA with acetone as solvent) or nanoparticles (TFEMA/TMPTA with cyclohexanone as solvent) onto
the surface of these cylinders.
In the first-step, a photomask of 10-lm-diameter circular
hole was used, and the height of the patterned cylinders
could be controlled by UV irradiation time. As shown in Figure 4(a), the height of the PTMPTA cylinders gradually
increased and reached about 1015 nm at 180 s. For the
LDPE-g-PTMPTA cylinder patterned film, the water CA was
in the range of (105 6 1) to (108 6 2) , about 30 higher
than that of blank film, additionally, there was no obvious
relationship between water CA and cylinder height. The
film hydrophobicity was dramatically improved although no
fluorine containing monomer was adopted. Intensive investigations have demonstrated that the surface hydrophobicity
can be controlled by both the surface energy and surface
roughness. The enhanced hydrophobicity might be attributed to the increasing surface roughness of the micropatterned film.

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According to a well-known photo-reduction principle, the

surface of these cylinders should possess certain amount of
BPH dormant groups (Scheme 1) which could further initiate the photo-grafting polymerization.37 It should be noted
that there was no dormant group anywhere on the film
except the micro-patterned cylinder area, which was introduced in the first-step photo-grafting polymerization. That is
to say, the re-initiation in the second- step could only occur
on the top and side surface of the cylinders. Taking the topdown vertical UV irradiation into consideration, the photografting polymerization mainly took place on the top surface
of the cylinders. With this re-initiating living polymerization,
we could introduce either PTFEMA brushes or PTFEMA/
TMPTA nanoparticles on top of the PTMPTA cylinders. As
shown in Figure 5(b), when TFEMA was used as the sole
monomer and acetone as solvent, PTFEMA brushes were
formed on the top of PTMPTA cylinders and the water CA
could be about (128 6 2) . When TMPTA was added to the
reaction system as crosslinker and cyclohexanone as solvent
instead of acetone, PTFEMA/TMPTA nanoparticles were
deposited on the top of the PTMPTA cylinders and the water
CA could reach up to (140 6 1) .
For the LDPE-g-PTMPTA cylinder film 5a, the loose structure
and lack of materials with low surface free energy make it
easy for water droplet to penetrate in the grooves that
between the micro patterns. So the water droplets may
replace the trapped air, which will greatly increase the solid
fraction of the films (us) and thus cause a relatively lower
water CA. As a result, the water CAs for the LDPE-g-PTMPTA
cylinder film 5a is only (105 6 2) [as shown in Fig. 5(a)]. In
order to decrease the surface free energy, fluorinated materials were grafted onto the micropatterned film. In return, the
water CA of film 5b and 5c were much higher than that of
film 5a. According to the EDS analysis, the atom percentage
of F on the surface of film 5b and 5c were 2.48 and 1.65%,
respectively. That is to say, the surface free energy of film 5b
was lower than that of film 5c. However, the water CA of
film 5c was about 12 higher than that of film 5b. This further increase of water CAs is mainly due to the higher
degree of surface roughness. It is well known that hydrophobicity of the film is determined by both the surface free
energy and surface roughness. As shown in Figure 5(c), the
AFM results showed that the nanoparticles were introduced
on the top of the PTMPTA cylinder, which dramatically
increased the surface roughness, leading to much higher
hydrophobicity.

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network were (103 6 2) and (95 6 2) , respectively. The

surface roughness could be dramatically improved with the
introduction of PTFEMA/TMPTA nanoparticles and accordingly the water CAs reached (122 6 2) . The micro- and
nanoscale hierarchical structure can further enhanced the
hydrophobicity, and the water CA of LDPE-g-PTMPTA
cylinders-g-PTFEMA/TMPTA nanoparticles was as high as
(140 6 1) , superior to that of LDPE-g-PTMPTA cylinders-gPTFEMA brush (128 6 2) . This technology provides a new
pathway to construct multilevel structured grafted polymer
layers via UV photo-grafting polymerization.
ACKNOWLEDGMENTS

The Major Project (Grant 51033001), the Fund for Creative

Research Groups (Grant 51221002) and the General Program
(Grant 51273012) from the National Natural Science Foundation of China (NSFC) are gratefully acknowledged for financial
support of this work.

REFERENCES AND NOTES

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In conclusion, a facile and rapid in situ UV photo-grafting

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film grafted with PTFEMA brush and PTFEMA/TMPTA

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