a r t i c l e
i n f o
Article history:
Received 1 October 2010
Received in revised form
26 November 2010
Accepted 29 November 2010
Available online 9 December 2010
Keywords:
Aramid ber
Air DBD plasma
Treatment time
Surface characterization
Wetting behavior
a b s t r a c t
Aramid ber samples are treated by air dielectric barrier discharge (DBD) plasma at atmospheric pressure;
the plasma treatment time is investigated as the major parameter. The effects of this treatment on the
ber surface physical and chemical properties are studied by using surface characterization techniques.
Scanning electron microscopy (SEM) is performed to determine the surface morphology changes, X-ray
photoelectron spectroscopy (XPS) is analyzed to reveal the surface chemical composition variations and
dynamic contact angle analysis (DCAA) is used to examine the changes of the ber surface wettability. In
addition, the wetting behavior of a kind of thermoplastic resin, poly(phthalazinone ether sulfone ketone)
(PPESK), on aramid ber surface is also observed by SEM photos. The study shows that there seems to be
an optimum treatment condition for surface modication of aramid ber by the air DBD plasma. In this
paper, after the 12 s, 27.6 W/cm3 plasma treatment the aramid ber surface roughness is signicantly
improved, some new oxygen-containing groups such as CO, C O and O CO are generated on the ber
surface and the ber surface wettability is greatly enhanced, which results in the better wetting behavior
of PPESK resin on the plasma-treated aramid ber.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Aramid ber, combining high specic modulus and strength
with excellent thermal stability and chemical inertness, is one of
the best candidates as reinforcement for high-performance composites. However, the employing aramid ber as reinforcement
has been limited by poor ber/matrix interfacial adhesion, because
of the ber having smooth surface and inert chemical structure,
which prevents interfacial bonding with most of the commercially
available resins used in composites [15]. In order to optimize the
aramid-ber/matrix adhesion, a variety of research efforts have
been directed towards the improvement of ber surface properties by various surface treatment techniques [611]. Traditional
chemical treatments are often accompanied by the use of water
and/or organic solvents, thus pose such problems as the disposal
of drained water and recovery of organic solvents, which are
energy-, time- and cost-intensive and involve pollution of water
resources. Therefore, non-thermal plasma technology, which is ef-
Corresponding author at: Dalian University of Technology, Department of Polymer Material, Zhongshan Road 158-42#, Dalian, Liaoning 116012, China.
Tel.: +86 0411 89393866.
E-mail address: chenping 898@126.com (P. Chen).
0169-4332/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2010.11.190
4166
Description
4.7 cm (steel)
0.3 cm
0.1 cm (quartz)
143.5 W (27.6 W/cm3 )
Air and at atmosphere pressure
0 s (untreated), 6 s, 12 s, 18 s
The surface chemical composition of Twaron ber was analyzed by X-ray photoelectron spectroscopy (XPS; ESCALAB 250,
Thermo), making use of monochromatic Al K (h = 1486.6 eV)
X-ray source (15 kV, 250 W) radiation from a dual AlMg anode.
The measurements were performed at an operating vacuum lower
than 3.0 109 mbar. Spectra were acquired at a take-off angle of
90 relatively to the sample surface. The pass energy and energy
step set for elemental quantication were 100 eV and 1 eV, respectively, and for C1s peak shape identication purpose the pass
energy and energy step were xed at 20 eV and 0.05 eV, respectively. The non-linear least squares tting (NLLSF) program with a
GaussianLorentzian production function was used for curve tting
of C1s spectra.
2.5. DCAA
The surface free energy and contact angles of Twaron ber were
measured through a dynamic contact angle analysis system (DCAA;
DCA-322, Thermo). The ber sample was cut into about 1 cm in
length and xed indirectly to a wire hook suspended from the
microbalance of the system. The ber was immersed into the testing liquid media by raising the elevating stage at a constant speed of
1 mm/min and then the dynamic contact angles () were obtained
schematically by the measurement. There are two equations (Eqs.
(1) and (2)) as follows, from which the surface free energy can be
calculated:
l (1 + cos ) = 2
s l + 2
sd ld
total = s + sd
(1)
(2)
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Fig. 2. SEM photographs of the untreated and air DBD plasma treated ber surface: (a) 0 s (untreated); (b) plasma treated for 6 s; (c) plasma treated for 12 s; (d) plasma
treated for 18 s.
Table 2
XPS surface element analysis of Twaron ber before and after treatment.
Samples
0 s (untreated)
Plasma treated for 6 s
Plasma treated for 12 s
Plasma treated for 18 s
Atomic ratio
O/C
N/C
78.9
79.3
75.5
83.1
14.0
13.5
17.6
12.6
7.1
7.2
6.9
4.3
0.177
0.170
0.233
0.152
0.090
0.091
0.091
0.052
4168
Fig. 3. C1s spectra of the untreated and air DBD plasma treated ber surface: (a) 0 s (untreated); (b) plasma treated for 6 s; (c) plasma treated for 12 s; (d) plasma treated for
18 s.
Table 3
Correlative functional groups of Twaron ber surface.
Samples
0 s (untreated)
Plasma treated for 6 s
Plasma treated for 12 s
Plasma treated for 18 s
CO
C O
O CO
74.1
77.5
68.5
89.3
13.3
9.3
17.8
5.3
6.0
8.5
6.8
3.6
6.6
4.7
6.9
1.8
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Table 4
Advancing contact angles and surface free energy of Twaron ber before and after treatment.
Samples
0 s (untreated)
Plasma treated for 6 s
Plasma treated for 12 s
Plasma treated for 18 s
a
Water
Diiodomethane
p
d
total = p + d
64.3(2.5)
48.6(2.4)
42.3(0.4)
35.9(2.7)
41.0(2.0)
47.4(1.8)
42.7(2.7)
41.1(2.3)
11.5
21.8
24.4
27.5
39.1
35.7
38.2
39.1
50.6
57.5
62.6
66.6
Standard deviation.
tle resin is on the ber surface and some smooth ber surface is
visible. After the ber is treated for 6 s (Fig. 4b), there is a little
more PPESK resin being observed and we can also see some undulations on the sample. When the ber is treated for 12 s (Fig. 4c),
the ber is covered with more resin evenly and it can be found
that the resin is present among the ber laments as well. After
the treatment time lasts for 18 s (Fig. 4d), there is a mass of PPESK
resin on the ber surface, however, the resin has a nonuniform
distribution.
The results indicate that the PPESK resin could show a better wetting behavior on Twaron ber surface when the ber is
treated for 12 s by the air DBD plasma at 27.6 W/cm3 , which agrees
with the results of SEM, XPS and DCAA measurements shown in
above sections, showing that suitable treatment of the plasma can
increase the surface roughness of Twaron ber and improve the
surface chemical inertness, enhancing the ber surface wettability and leading to good interfacial adhesion between the ber and
matrix.
Fig. 4. The wetting behavior of PPESK resin on Twaron ber surface: (a) 0 s (untreated); (b) plasma treated for 6 s; (c) plasma treated for 12 s; (d) plasma treated for 18 s.
4170
4. Conclusions
The experimental results presented in this study show that the
air DBD plasma at atmospheric pressure can effectively modify
Twaron ber surface adhesion properties, the plasma treatment
time has great inuence on ber surface physical features and
chemical compositions and there might be an optimum treatment
condition existing for the ber modication. The results indicate
that after a 12 s, 27.6 W/cm3 plasma treatment, the aramid ber
surface roughness is evidently improved as illustrated by SEM,
the concentrations of oxygen and oxygen-containing functional
groups on the ber surface increase signicantly as determined
with XPS, and the ber surface wettability derived from DCAA is
greatly enhanced. The improvements of the physical and chemical
properties induced by the air DBD plasma could account for the
better wetting behavior of PPESK resin on plasma-treated Twaron
aramid ber.
Acknowledgements
This work was funded by the National Natural Science Foundation of China (No. 50743012), National Defense 11th 5-year
Program Foundational Research Program (No. A3520060215), and
Liaoning Province Innovation Organization (No. LT2010083). In
addition, the authors are indebted to Mr. Xinglin Li for XPS analysis
and Dr. Litao Shi for his skillful experimental assistance.
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