Effects of Alignment of Graphene Flakes on Water Permeability of Graphene-epoxy Composite Film

Seong-Yoon Jung and Kyung-Wook Paik

Nano Packaging and Interconnection Lab. (NPIL)
Department of Materials and Science Engineering
Korea Advanced Institute of Science and Technology (KAIST)
291 Daehak-ro, Yuseong-gu, Daejeon, 305-701, Korea
Phone: +82-42-350-3386, Fax: +82-42-350-8124
E-mail : Jung_seungyoon@kaist.ac.kr

assembly and curing processing. On the other hand, B-stage,

Abstract
In this study, the electric field-assisted alignment of
graphene flakes in B-stage graphene-epoxy composite film
was demonstrated. Compared with conventional electric field-
induced alignment method which involves curing liquid phase
polymer matrix, the electric field application on B-stage
composite film with controlled viscosity can achieve graphene
flake alignment without any curing reactions, thereby enabling
further processes such as film application, assembly and
curing.
B-stage graphene-epoxy composite was prepared by
solution-mixing method, and electric field was applied parallel
to the film with various temperature and electric field
strengths. Cross-sectional SEM images revealed that graphene
flakes were horizontally aligned better as film viscosity
decreased and electric field strength increased. However,
curing reaction at high temperature should be considered
because high temperature was needed to achieve low
viscosity. The aligned graphene-epoxy composite film showed
lower water vapor transmission rate (WVTR).
1. Introduction
Graphene, which is a layer of carbon atoms in a hexagonal
lattice, has attracted scientists and engineers due to its
excellent mechanical, electrical, and thermal properties [1-3].
In addition, it was theoretically reported that graphene had
good gas barrier properties due to its electronic structure. [4].
One of the application of graphene is graphene-polymer
composite, where graphene flakes are incorporated to
polymeric matrix. It was reported that small amount of
graphene flakes can significantly improve electrical, thermal,
and gas permeability properties of polymeric materials [5].
Therefore, graphene-polymer composite has potential
applications in electronics such as thermal management,
electrical interconnection, and gas barrier materials for
sealing.
In general, the property of composites can be tailored by
arranging or orienting fillers in the matrix. Thus, there has
been many attempts to fabricate oriented polymer composites,
and one of the ways to orient rod-like or planar fillers is to
apply electric field to polymer composite [6-9]. Several
authors have reported oriented composites including CNT-
and graphene-polymer composite by electric field application,
however in most studies; the polymeric matrices were bulk
liquid phase since low viscosity was desired for better flake
alignment. Moreover, the electric field was applied while the
composite was cured. However, this process can limit further
978-1-4799-2407-3/14/$31.00 ©2014 IEEE
or partially-cured adhesive film has processing advantages
over liquid phase paste, due to its ability to precisely control
residues and its compatibility to different kinds of substrates
such as polymeric film, glass and metals. This B-stage
adhesive film is in solid state at ambient temperature, but the
viscosity can be lowered by applying heat, which graphene
flakes can easily interact with external electric field.
In this study, graphene flakes were incorporated to B-stage
epoxy adhesive film, and aligned structure of graphene flakes
was demonstrated by applying external electric field. The
applied electric field direction was parallel to the film
direction, and flake orientation distribution was observed
depending on the electric field strength, film viscosity. In
order to observe the effects of horizontal alignment on
properties of graphene-epoxy composite film, water vapor
transmission rate (WVTR) was also measured.
2. Experimental
2.1. Preparation of graphene-epoxy composite film
Graphene flakes used in this study were commercially
available exfoliated graphene nanoplatelet. The mean size of
flakes was 5 µm and the thickness was 6-8 nm according to
the manufacturer. Also, commercially available bisphenol-A
epoxy, thermoplastic resin, and a curing agent (dicy;
dicyandiamide) were used as polymer materials. In addition,
methyl-ethyl ketone (MEK) was used as an organic solvent.
Procedure of preparing graphene-epoxy composite film is
schematically illustrated in figure 1. Since as-received
graphene flakes were granular powders, mechanical
exfoliation of powders was necessary. The powder was first
mixed with MEK in a bottle and sonicated for 24 hours in the
sonication bath in order to exfoliate powders into individual
graphene flakes. Epoxy resin and curing agent were then
added to the solution, and mixed by using the ball-milling
technique for 24 hours. After that, the remaining organic
solvent was dried out resulting graphene-epoxy composites.
After the graphene-epoxy composites were prepared, film was
coated on the releasing film using comma-roll film coater (Fig.
2).
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Figure 1 Illustration of fabrication of graphene-epoxy
composite film
Figure 2 Image of graphene-epxy composite film coated on
releasing film (3 wt%, 32 µm)
2.2. Electric field application for graphene flake alignment
Experimental setup for electric field application is shown
in figure 2. Graphene-epoxy composite film with 3 wt%
graphene content was coated on the releasing film by using
comma-roll film coater, and the thickness was fixed to be
32µm. Two needles were connected to the DC power supply,
where the electric field direction was parallel to the film.
Figure 3 Illustration of electric field application setup
After the electric field was applied, the processed film on
releasing film was immersed in liquid nitrogen and cut so that
cross-section would be revealed. Cross-sectional scanning
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electronic microscopy (SEM) images of processed film were
obtained. Graphene flakes seen in the SEM images were
analyzed by measuring the flake orientation using image
processing software. In order to compare the degree of
alignment of graphene flakes, the portion of graphene flakes
tilted less than 15 degrees was compared for each
experimental condition.
There were two main variables in this study; temperature
and electric field strength, which were tabled in table 1. In all
electric field application, the time was fixed to be 60 min.
Electric field strength was controlled by adjusting electrical
voltage, and film viscosity was measured as a function of
temperature. In order to compare the effects of film viscosity,
electric field strength of 30 V/mm was applied to the film at
30, 80, 100 oC. In order to investigate the effects of electric
field strength, 30 and 100 V/mm electric field was applied to
the film at 80 oC
Table 1 Summary of temperature, corresponding viscosity and
electric field strength used in the experiment
Temperature Viscosity Electric field
(℃) (Pa · s) strength (V/mm)
30 90440 30
80 4840 10, 30, 100, 200
100 1294 30
2.3. Effects of graphene flake alignment on properties of
graphene-epoxy composite film
In order to investigate the effect of horizontal alignment on
the water permeation property of graphene-epoxy composite
film, water vapor transmission rate (WVTR) was measured by
the method according to ASTM standard F-1249. Graphene
content was fixed to be 3 wt%. The thickness of composite
film was 20 µm and the area was 50 mm x 50 mm. Graphene-
epoxy composite film was first laminated on polyimide (PI, 30
µm) film and then cured at 120 oC for 40 min (Fig. 3). In order
to prepare the electric field applied sample, electric field was
applied on laminated composite film. The electric field
strength was 100 V/mm and the field application was done at
120 oC for 20 min and the temperature was hold for 20 min for
full cure. For reference, WVTR of epoxy film with no
graphene was measured.
3. Results and Discussion
3.1. Graphene flake alignment by electric field application
Theoretical approach on rotation of ellipsoidal particles by
electric field application has been well studied [9-11].
Especially, rotation behavior of a particle in polymer matrix
under electric field was theoretically interpreted in terms of
electrostatic torque by polarized particle and hydrodynamic
torque by viscous polymer matrix. The response time of the
particle under electric field was proportional to viscosity and
inversely proportional of the square of electric field strength
[11]. In addition, computational calculations on graphene
under electric field have demonstrated that graphene in free
space tend to be aligned to the direction of external electric
field by polarization [12]. Therefore, the response time of
graphene flakes in polymer matrix was a function of electric
field strength and polymer viscosity mentioned above.
Figure 4 shows the cross-sectional SEM images of as-
coated and electric field applied graphene-epoxy composite
film. As shown in the figure, graphene flakes in the composite
film appeared as bright lines. Graphene flakes in as-coated
composite film were in a linear shape, which indicates that the
flakes were somewhat oriented in the three-dimensional space.
This might be explained that the coating process caused flakes
to be oriented toward the coating direction. However, the flake
orientation was quite random for as-coated composite film.
After electric field was applied, more flakes were aligned
toward the electric field direction, which demonstrated that
graphene flakes could be aligned in a solid composite film.
Figure 5 Degree of alignment of 200 graphene flakes with
different electric field strength applied.
However, the effect of temperature was quite different.
Figure 6 and 7 shows the film viscosity versus temperature
and the effect of temperature on degree of graphene flake
alignment respectively. As shown in figure 5, film viscosity
decreased with temperature until the minimum viscosity
around 120 Pa•s at 140 oC, then drastically increased because
of the curing reaction of epoxy film. Comparing film viscosity
and the results of electric field application at 80 oC and 100 oC
in figure 6, the degree of alignment was higher at 80 oC than
100 oC even though the corresponding viscosity was 4 times
lower at 100 oC. This phenomenon could occur at 100 oC
since the temperature was maintained for a long period of time
(electric field application time). In order to examine whether
the film at 100 oC has been cured or not, attenuated
reflectance mode of Fourier transform infrared spectroscopy
(ATR-FTIR) was used to measure the degree of curing (Fig.
8). Comparing the spectra between as-coated film and fully
cured film, the peak of 912 cm-1 in the spectrum decreased,
indicating that degree of curing of epoxy can be measured by
this peak. As seen in figure 8, the composite film has partially
cured by heating at 100 oC for 60 min while at the same time,
the film at 80 oC has not been cured.

Figure 4 Cross-sectional SEM images of (a) as-coated

composite film and (b) electric-field applied film sample. The
electric field was applied at room temperature.

In order to compare the degree of alignment, the angle

relative to the electric field direction was statistically
analyzed. Figure 5 compares the portion of graphene flakes
under 15 degrees, with different electric field strengths at 80
o
C for 60 min. As indicated in the figure, more graphene Figure 6 Temperature vs. viscosity of 3 wt% graphene-epoxy
flakes were horizontally aligned when applying higher electric composite film.
field strength at same field application time of 60 min. The
portion drastically increased even by weak electric field
strength, and the maximum portion of 84.5 % was obtained by
applying 100 V/mm for 60 min at 80oC.

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 30V/mm, 60min Table 2 WVTR of graphene-epoxy composite film laminated
105
on PI film. Film thickness of polyimide substrate was 30 µm,
90440
100 while the composite film was 20 µm
81.1 Sample WVTR
In detail
under 15 degrees

78.5
80 description (g/m2/day)
% of flakes tilted

75

Viscosity (Pa·s)
104
60 4840 Polyimide (PI) 96.90 Reference

Epoxy No
40 1294 48.26
103 (No graphene) graphene

20 3 wt% graphene 33.25

0 102 3 wt% graphene 100V/mm

30℃ 80℃ 100℃
Temperature
Figure 7 Degree of alignment of graphene flakes after electric
field application with different temperature. The
corresponding viscosity was also indicated.
Figure 8 FTIR spectra of graphene-epoxy composite films
3.3. Effects of graphene flake alignment on water
permeation property of graphene-epoxy composite film
In order to investigate the effects of horizontal alignment
on properties of graphene-epoxy composite film, Water vapor
transmission rate (WVTR) was measured. In preparing the
samples for WVTRs of the films were shown in table 2. As
demonstrated in table 2, the aligned graphene-epoxy
composite film showed the lowest WVTR of 22.85 g/m2/day.
Several authors have reported improved gas barrier property
of graphene-polymer composites [13-14]. Theoretically, the
gas barrier effect maximizes when the flakes were aligned to
the direction perpendicular to gas permeating direction by
diffusion length increase [14]. Therefore, the lower WVTR of
graphene-epoxy composite film was achieved by horizontally
aligning graphene flakes.
22.85
(aligned) 20min
4. Conclusion
In this study, the electric field-assisted alignment of
graphene flakes in B-stage composite film was demonstrated.
This alignment process has advantages over conventional
flake alignment in liquid polymer composite, since further
processing such as assembly and curing can be possible.
Better alignment was achieved by applying high electric field
strength at low viscosity, and the low viscosity was obtained at
high temperature. Also, electric field application at high
temperature for long time caused curing reaction, which in
turn, caused poor alignment by rapid viscosity increase. .
During the curing reaction, viscosity drastically decreases to a
certain degree, in a short time period. By optimizing the
electric field strength and field application time in terms of
curing behavior, B-stage graphene-polymer composite film
with totally aligned graphene flakes can be achieved.
Furthermore, the effect of horizontal alignment on gas
permeation property was investigated. The horizontally
aligned composite film showed lower sheet resistance and
water permeation property. Since graphene has good barrier
properties, aligned structure of graphene flakes could be used
in various applications. Gas barrier membrane, for example, is
one of the possible applications. Graphene has the ability to
prevent gas molecules to be passed through therefore, aligned
graphene-polymer gas barrier membranes could drastically
reduce the gas permeability compared to as-prepared
membranes.
Acknowledgments
This work was financially supported by Graphene
Materials and Components Development Program of
MOTIE/KEIT (10044412, Development of basic and applied
technologies for OLEDs with graphene)
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