Applied Surface Science 258 (2012) 1016810174

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Applied Surface Science

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

Surface treatment of para-aramid ber by argon dielectric barrier discharge

plasma at atmospheric pressure
Ruxi Gu a , Junrong Yu a, , Chengcheng Hu a , Lei Chen a , Jing Zhu a , Zuming Hu b
a
b

State Key Laboratory for Modication of Chemical Fibers and Polymer Materials, Shanghai 201620, PR China
Key Laboratory of High-performance Fibers & Products, Ministry of Education, Donghua University, Shanghai 201620, PR China

a r t i c l e

i n f o

Article history:
Received 27 April 2012
Received in revised form 26 June 2012
Accepted 27 June 2012
Available online 11 July 2012
Keywords:
Para-aramid ber
Dielectric barrier discharge
Argon plasma
Adhesive performance
Wettability

a b s t r a c t
This paper is focused on inuence of argon dielectric barrier discharge (DBD) plasma on the adhesive performance and wettability of para-aramid bers and three parameters including treated power, exposure
time and argon ux were detected. The interfacial shear strength (IFSS) was greatly increased by 28% with
300 W, 60 s, 2 L min1 argon ux plasma treatment. The content of oxygen atom and oxygen-containing
polar functional groups were enhanced after the argon plasma treated, so as the surface roughness, which
contributed to the improvement of surface wettability and the decrease of contact angle with water. However, long-time exposure, exorbitant power or overlarge argon ux could partly destroy the prior effects
of the treatment and damage the mechanical properties of bers to some degree.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Para-aramid ber is a compound linear chain macromolecule
material which has high crystallization and high orientation [1].
As it has the properties of low density, high strength, good toughness, excellent thermal-resistance, chemical corrosion-resistance
and good impact resistance, para-aramid ber has been widely used
as an reinforce composite material in the elds of aviation, automobile, shipbuilding [2,3]. However, owing to the smooth surface
and chemical inertness, the bers interfacial adhesive performance
with the resin is limited and the wettability properties of the ber
are low, which are to disadvantage of its applying to the composite materials. So the surface modication of the para-aramid ber
becomes a must [4].
The common methods of surface modication on the paraaramid ber are chemical and physical methods [57]. Chemical
methods include chemical etching, chemical surface grafting and
polymerization modication, which could efciently enhance the
interfacial adhesive performance of the ber and the effects are
highly durable. In spite of these merits, chemical treatments may
destroy the mechanical properties and produce large amount of
waste water and organic solvents, which leads the production process environmentally unfriendly. In contrast, physical treatment

Corresponding author. Tel.: +86 21 6779 2945.

E-mail address: yjr@dhu.edu.cn (J. Yu).
0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2012.06.100

would be more advocated. Low-temperature plasma modication

technique is one of the most important physical methods [8,9].
Low-temperature plasma technique has lots of discharge methods, such as, direct current glow discharges [10], corona discharges
[1113], and radiofrequency glow discharges [1416]. In recent
years, dielectric barrier discharges (DBD) was more and more
favored with the advantages of high efciency, exible and environmentally friendly. In contrast to other discharge methods, the
DBD technique could be used under atmosphere pressure without
the vacuum device, and maintain the possible of the large-scale
industrialization [17,18].
DBD treatment is the interaction of the oxidation and etching
effects. On the one hand, the bombardment of the atom, electron, UV radiation onto the ber surface induces some new polar
functional groups; on the other hand, the plasmas are etching the
surface of ber, making the surface more rough to enhance the contact area of the ber with resin. With the effects of oxidation and
etching, the wettability and adhesive properties have been greatly
improved [19,20].
Despite of the fact that DBD surface modication technique has
been regarded as the most potential method to the para-aramid
ber, the related reports are relatively rare recently. Jia et al. [21,22]
had employed an air DBD plasma at atmospheric pressure for
Twaron and Armos bers, the results revealed that the content of
polar functional groups such as C O,C O,O C O was obviously
increased. According to the previous articles, the DBD plasma modication were all under the air atmosphere, the effects with the
argon atmosphere had not been reported. However, Liu et al. [23]

R. Gu et al. / Applied Surface Science 258 (2012) 1016810174

10169

Fig. 1. Schematic of the argon DBD plasma apparatus.

used the argon DBD plasma to treat on the PBO ber, which acquired
a more obviously effect in comparison to air, with a 40% improvement of the interlinear shear strength (ILSS). In this article, the
argon DBD plasma technique was used to modify Kevlar ber and
the optimum treated parameters were obtained.
In addition, this article elaborately studied the effects of several
parameters, including treatment time, power and argon ux, and
used the interfacial shear strength (IFSS) to characterize the interfacial adhesive performance. The surface chemical composition was
examined by X-ray photoelectron spectroscopy (XPS). The surface
morphology and roughness were analyzed by scanning electron
microscopy (SEM) and atomic force microscopy (AFM); the wettability of the ber surface was inspected by the contact angle
measurements in this paper.
2. Experimental
2.1. Materials
Kevlar29 aramid bers were supplied by DuPont Company with
the 1.5 cN dtex1 of average single lament. The samples were
cleaned in hot water bath at 100 C for 2 h and ultrasound device
for 1 h then dried in the room temperature for 3 days. The matrix
used in this paper was epoxy resin prepared with E-51 (A type of
epoxy), epoxy curing agent (No. 593) and acetone at the ratio of
10:3:2, all provided by Shanghai resin Co. Ltd., China.
2.2. Argon DBD plasma treatment
The DBD plasma device was a patent invited by Donghua University. The schematic diagram of the DBD apparatus is displayed

in Fig. 1. Kevlar29 ber samples were treated by going through the

argon DBD plasma part under atmospheric pressure with different
experimental conditions. The treated powers of the DBD plasma
were 100400 W and the treated time was at an interval of 30 s
from 30 s to 120 s. The ux of argon was changed from 1 L min1 to
4 L min1 .
2.3. Interfacial shear strength
The interfacial shear strength (IFSS) was measured by microbond test: the epoxy resin beads were rst treated on the single
lament, then the samples were dried for over 36 h at 40 C.
The diameters of the bers (D) and the embedded lengths (L)
were metered by the Olympus CH-2 microscope equipped with a
Panasonic WV-GP410/A digital photomicrography system. And the
interfacial shear peak load (F) was measured by XQ-1 ber tensile
testing machine (Shanghai Lipu Research Institute, China).
The IFSS (the schematic diagram was shown in Fig. 2) was calculated by the following equation. In this paper, every samples had
been acquired the average value through over 20 times tests.
IFSS =

F
DL

2.4. Contact angle measurements

The wettability of aramid ber was measured by the water contact angle (using the sessile drop method). The test was performed
by the OCA40 Contact Angle system (Data physics Instrument produced by Filderstadt, Germany). A small droplet of distilled water
(about 50 L) was dropped onto the ber with a matched syringe.

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R. Gu et al. / Applied Surface Science 258 (2012) 1016810174

Fig. 2. The schematic diagram of microdebonding test.

A Nikon video camera was used to play the photograph of the process and then the immediately contact angle was calculated with
SAC 20 software.
2.5. XPS analysis
The X-ray photoelectron spectroscope (XPS) was detected using
PHI 5000 Versaprobe (ULVAC-PHI, Japan) equipped with an Al K
X-ray source. The base pressure in the chamber was about 2e8 Pa
and the energy of X-ray source was 40 W at 15 kV. Spectra were
acquired at a take-off angle of 90 and the non-linear least squares
tting program was used for curving tting of C1s spectra.
2.6. Surface morphology
Scanning electron microscope (SEM, JSW-5600LV, JEOL, Japan)
was selected to observe the surface morphologies of the Kevlar
ber. The samples were jetted with gold onto the surface and the
magnication was set at 5000. Atomic force microscopy (AFM,
NanoScope IV, Veeco, U.S.A.) was used to analyze the surface roughness and morphology of Kevlar bers quantitatively. The images
with a 4 m 4 m scan area were obtained under the tapping
mode. The roughness of ber surface was characterized by mean
square roughness (Rq ) and arithmetic mean roughness (Ra ) calculated automatically from Eqs. (1) and (2) by the software.



N
N 
1
Rq = 
(Zij Zav )2
N2

1 
|Zij Zcp |
N
N

Ra =

(1)

i=1 j=1
N

(2)

i=1 j=1

where N is the number of data points in the image, i and j are the
pixel locations on the AFM image, Zij is the height value at i and j
locations, Zav is the average height value within the given area and
Zcp is the height value from the center plane [24].
3. Results and discussion

Fig. 3. IFSS for untreated and treated Kevlar29 bers at different treatment power,
time and argon ux.

3.1. Inuence of argon plasma treatment on the IFSS

The treated power, exposure time and argon ux were
three important parameters that affected the adhesive properties
between bers and resin. Under the most suitable treatment power,
argon ux and exposure time, the IFSS between the bermatrix
system could be signicantly improved by producing the polar
functional groups and increasing roughness of the bers.
Fig. 3 shows the values of IFSS for treated samples with changing treated power, time and argon ux. It can be observed that

the adhesion between aramid ber and epoxy resin was obviously
improved after the plasma treatment. From Fig. 3a, the samples
were treated for 60 at 2 L min1 argon ux and when the power
was 300 W, the best IFSS was acquired with a 28% improvement.
Under the most suitable treated power of 300 W and xed the exposure time at 60 s, the IFSS changing with argon ux was shown in
Fig. 3b, the result showed that the optimum ux was 2 L min1 . In
Fig. 3c, the treated power and argon ux were selected as 300 W

R. Gu et al. / Applied Surface Science 258 (2012) 1016810174

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Table 1
Surface elements of aramid bers.
Fiber sample

(a) Untreated
(b) Treated for 30 s
(c) Treated for 60 s
(d) Treated for 90 s

Chemical composition (at.%)

Atomic ratio (%)

O/C

N/C

82.66
77.12
70.37
72.94

13.63
17.67
21.55
19.15

3.71
5.21
8.08
7.91

16.49
22.91
30.62
26.25

4.49
6.76
11.48
10.84

and 2 L min1 , and when the exposure time was 60 s, the best IFSS
value was acquired.
From Fig. 3, it can be concluded that all the three plasma parameters, including the treated power, time and argon ux, have a
parabola tendency in term of the inuence on IFSS after argon
plasma modication, that is, the rst increasing of treated power,
time and argon ux can do great improvement of the adhesive
performance of the bermatrix composite system, however, the
continued increased power, time and argon ux would result in the
rapid decrease in the interfacial adhesion. That may be contributed
to the excessive changes on the ber surface by the long-time exposure, exorbitant power or overlarge argon ux.
In comparison with the three graphs, it was apparent that the
optimum processing condition was existed with 300 W, 60 s and
2 L min1 argon plasma treatment.
3.2. Inuence of argon plasma treatment on surface wettability
The contact angle measurements can reect the surface wettability of the aramid bers to some degree. The inuence of argon
plasma treatment in term of the changing of treated power, exposure time and argon ux was shown in Fig. 4.
The contact angle of original aramid ber is 64.8 which reveals
a poor wettability. After argon plasma treatment on whatever conditions, the contact angles would be decreased rapidly. That was
contributed to the increasing of surface roughness through the
plasma treatment. The argon plasma etched the ber surface to produce more grooves onto the ber, which could store more water on
the ber surface, leading the improvement of the wettability. However, it can be seem from Fig. 4 that the contact angle has a best
value according to the plasma treatment condition. To be specic,
when the treated power was above 300 W, the exposure time was
beyond 60 s, or the ux of argon was over 2 L min1 , the contact
angle was increased which could proved that the ber was excessive treated. The over-treatment of the ber under argon plasma
might ruin the prior produced polar functional groups or roughness of surface; what is more, it could also damage the excellent
mechanical properties of the aramid bers. It can be detected from
Fig. 4 that the minimum contact angle of 48.5 was produced on the
treatment condition with 200 W, 60 s, 2 L min1 argon plasma and
48.6 on the 300 W, 60 s, 2 L min1 , which was roughly agreement
with the results by the IFSS.
3.3. Surface chemical composition
The changes of chemical composition and chemical bonds can
dramatically affects the wettability and adhesive performance of
the bers. XPS technique was used to analyze the concentration of
the elements both original and plasma treated Kevlar bers quantitatively. Tables 1 and 2 list the surface elements of the original
and different time plasma-treated bers.
The exposure time was used as the only changed parameter
to detect the inuence of surface element concentrations by XPS.
The optimum condition of micro-bond test treated power (300 W)
and argon ux (2 L/min) were selected as the xed parameters.
As shown in Table 1, the untreated ber had a relatively high

Fig. 4. Contact angle measurement for untreated and treated Kevlar29 bers at
different treatment power, time and argon ux.
Table 2
Results of deconvolution analysis of C1s peaks.
Fiber sample

Concentrations of different chemical bonds (%)

(a) Untreated
(b) Treated for 30 s
(c) Treated for 60 s
(d) Treated for 90 s

86.60
84.60
61.79
70.37

C C

C N / C O
10.72
9.87
26.88
16.98

CONH
1.35
3.14
5.08
7.95

COO
1.34
2.39
6.24
4.69

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R. Gu et al. / Applied Surface Science 258 (2012) 1016810174

Fig. 5. C1s spectra of Kevlar bers: (a) untreated bers, (b) treated for 30 s, (c) treated for 60 s, (d) treated for 90 s.

content of carbon atoms and low contents of oxygen and nitrogen

atoms. However, after the argon plasma treated, the concentrations of polar atoms increased. The O and N percentage on the
surface of untreated Kevlar bers were 13.63% and 3.71%, and they
increased obviously after plasma treated. The atomic ratio of O/C
was improved from 16.49% to 39.70% after 60 s argon DBD plasma
treated, then become lower with longer treatment. The same trend
had also shown with the N/C atomic ratio (Fig. 5).
The deconvolution analysis of C1s peaks was performed in
Table 2 and Fig. 5 to measure the change of functional groups quantitatively. There are four kinds of carbon states: C C at 284.8 eV,
C N/C O at 286.3 eV, CONH at 287.7 eV and COOH at
289.0 eV. As shown in Table 3, the C C concentration decreased
sharply from 86.60% to 61.79% after 60 s argon DBD plasma treatment, while the percentages of the polar functional groups such
as C N/C O , CONH , COO had a dramatic increase from
10.72%, 1.35%, 1.34% to 26.88%, 5.08% and 6.24%, respectively.
Besides, it can be found that the C O / C N and COO concentration have an obviously drop after 90 s treatment as a result of
the over etching effects, which agrees with the variations of surface
element concentrations.
The results illustrated that the argon plasma process could introduce some new polar functional groups including C O/C N ,
CONH , and COO onto the surface of the bers, which can
enhance the wettability and adhesive performance of aramid bers.
The reason [25] was that the argon plasma composed of lots of
Table 3
Root mean square roughness (Rq ) and arithmetic mean roughness (Ra ) of Kevlar
bers.
Fiber sample

Rq (nm)

Ra (nm)

(a) Untreated
(b) Treated for 300 W, 60 s, 2 L min1

197.56
271.30

171.07
230.14

non-reactive particles comparing with oxygen and nitrogen plasma

and the energies were transferred by those particles to the ber
surface, activating the surface layer by making the bombardment
of ions, electrons and UV radiation. Nevertheless, there existed an
optimum treated time as the longer treatment maybe etch the
formerly generated concave and convex and smooth the surface
roughness, which probably result in the decrease in the polar functional groups. The study of XPS analysis was corresponded to the
results of IFSS and contact angle measurement.

3.4. Inuence of argon plasma treatment on surface roughness

According to the micro-bond test and contact angle measurement, the optimum treatment condition was selected as 300 W,
60 s and 2 L min1 argon ux. In order to detect the inuence of the
argon plasma on the surface roughness, the SEM and AFM test were
applied on the original Kevlar29 ber and the plasma treated ber
at the optimum condition. Figs. 6 and 7 were the contrast of the
two samples of SEM and AFM, respectively.
The surface morphology of Kevlar ber was investigated by SEM.
The comparison of the SEM images of the original and the argon
DBD treated bers at 300 W, 60 s and 2 L min1 argon ux were
shown in Fig. 6. It can be obviously found that the ber becomes
uneven and quite different in terms of the surface morphology
after plasma treatment. In Fig. 6a, the untreated ber was clean
and smooth, but after plasma treated, a lot of apparent bulges and
ruts were introduced onto the ber surface, which can be clearly
observed in Fig. 6b.
The AFM was used to investigate the surface roughness of the
Kevlar29 bers before and after argon plasma treatment. In Fig. 7,
remarkable difference can be observed in the micrographs, which
could prove that the DBD plasma treatment would change the morphology of the surface on a nanometer level.

R. Gu et al. / Applied Surface Science 258 (2012) 1016810174

10173

Fig. 6. Surface morphology of Kevlar29: (a) untreated and (b) plasma treated argon plasma at 300 W, 60 s and 2 L min1 argon ux.

Fig. 7. AFM images of Kevlar bers: (a) untreated; (b) plasma treated for 300 W, 60 s, 2 L min1 argon ux.

The results of roughness were analyzed with the root mean

square roughness (Rq ) and arithmetic mean roughness (Ra ) which
were summarized in Table 3. As shown in Table 3, the original ber had a relative lower Rq and Ra value of 197.56 nm
and 171.07 nm, respectively. After the argon plasma treatment,
the ber roughness had a dramatically enhancement, with
the Rq and Ra value increasing to 273.10 nm and 230.14 nm,
respectively.
As a consequence of the increasing roughness on the surface, the
interfacial area between the ber and matrix would be expanded,
thereby devoted to more mechanical interlocking, which corresponded to the results increase of IFSS.

4. Conclusion
The experimental results presented that the argon DBD plasma
at atmospheric pressure can enhance the surface adhesive performance and wettability of Kevlar ber. In this study, the plasma
treated power, exposure time and argon ux were detected and all
of the three parameters had a huge inuence on modifying the ber
surface properties. With the argon DBD plasma treatment, the IFSS
and wettability of Kevlar ber would be greatly improved, the contents of oxygen and oxygen containing polar functional groups on
the surface of Kevlar bers were increased. Moreover, the surface
of argon plasma treated bers became much rougher.
The results illustrated that plasma treated bers would acquire
optimal interfacial properties when the treated power was 300 W,
the exposure time was 60 s and the argon ux was 2 L min1 .

Acknowledgements
This work was nancially supported by China National 973
Project (No. 2011CB606103), the Fundamental Research Funds for
the Central Universities (No. 11D10625) and Shanghai Leading Academic Discipline Project (No. B603).
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