ARTICLE IN PRESS

Journal of Electrostatics 65 (2007) 269–273

www.elsevier.com/locate/elstat

Stability of atmospheric-pressure plasma induced changes on

polycarbonate surfaces$
Rajesh Sharmaa,, Edward Holcomba, Steve Trigwellb, Malay Mazumdera
a
Department of Applied Science, University of Arkansas at Little Rock, 2801 S. University Avenue, Little Rock, AR 72204, USA
b
Electrostatics and Surface Physics Laboratory ASRC Aerospace, ASRC-20, Kennedy Space Center, FL 32899, USA
Received 20 June 2006; accepted 12 October 2006
Available online 9 November 2006

Abstract

Polycarbonate films are subjected to plasma treatment in a number of applications such as improving adhesion between polycarbonate
and silicon alloy in protective and optical coatings. The surfaces that undergo changes in surface properties due to plasma treatment have a
tendency to revert back to their original states. Thus, the stability of the plasma induced changes on polymer surfaces over a desired time
period is an important issue. The objective of this study was to examine the effect of ageing on atmospheric-pressure helium-plasma treated
polycarbonate (PC) sample as a function of treatment time. The ageing effects were studied over a period of 10 days. The samples were
plasma treated for 0.5, 2, 5 and 10 min. Contact angle made by water droplet on polymer surfaces were measured to study surface energy
changes. Modification of surface chemical structure was examined using X-ray photoelectron spectroscopy (XPS). Contact angle decreased
from 931 for untreated samples to 301 for samples treated with plasma for 10 min. After 10 days the contact angle for the 10 min plasma
treated sample increased to 671, but it never reverted back to that of the untreated surface. Similarly, the oxygen-carbon (O:C) ratio
increased from 0.136 for untreated samples to 0.321 for 10 min plasma-treated samples, indicating an increase in surface energy.
r 2006 Elsevier B.V. All rights reserved.

Keywords: Plasma chemistry; Plasma processing; Polymer film; Contact angle; Surface energy

1. Introduction of the substrate bonds break, making the surface more

Plasma treatment is one of the most versatile techniques
in surface modification. It has been widely used to alter the
surface properties of materials in a number of applications
such as improving adhesion of coatings to metals and
polymers [1], increasing wettability and printability of
polymers [2,3], enhancing biocompatibility of implants [4],
and the manufacturing of semiconductor devices [5,6].
Plasma surface modification uses the active species of
plasma such as radicals, ions and electrons to alter the
surface chemistry of polymers. The collision of these
energetic active species with the surface results in the
transfer of their energy to lattice atoms. As a result, some
$
This paper was presented at the June 2006 Joint Conference of the
Electrostatics Society of American, IEEE-Industrial Applications Society,
Institute of Electrostatics Japan, and the Société Francaise d’Electro-
statique, Berkeley, CA, USA.
Corresponding author. Tel.: +1 501 569 8245; fax: +1 501 683 7222.
E-mail address: rxsharma@ualr.edu (R. Sharma).
reactive. Depending upon the type of precursor gas used
to generate the plasma, certain new functional groups
can be grafted onto the surface. Thus, plasma surface
modification can be used to induce a specific surface
chemistry without changing the bulk properties of the
materials. A large number of studies have shown that
plasma treatment of polymers can develop surfaces with
controlled and specific surface chemistry [7,8]. Surface
chemistry can be tailored by varying the different opera-
tional parameters involved in the process. Previously, we
have shown that atmospheric pressure plasma treatment
can be employed to reduce surface charge density caused
by tribocharging and also decrease the surface resistivity of
polymer powders [9–12].
Plasma surface modification of polycarbonate films is
utilized in a number of applications such as enhancing
biocompatibility [13] and improving adhesion between
polycarbonate and silicon alloy in protective and optical
coatings [14]. It has been observed that plasma treated

0304-3886/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.elstat.2006.10.001
 ARTICLE IN PRESS
270 R. Sharma et al. / Journal of Electrostatics 65 (2007) 269–273
polymers try to revert back to their original surface
properties over time. Thus the stability of plasma induced
changes on polymer surfaces over a desired time period is
an important issue. The objective of this study was to
examine the effect of ageing on atmospheric-pressure
helium plasma treated polycarbonate samples as a function
of treatment time. The ageing effects were studied over a
period of 10 days. Samples were plasma treated for 0.5, 2, 5
and 10 min. Contact angle measurements were made to
study surface energy changes. The contact angle is defined
as the angle between the solid surface and the tangent of
the liquid vapor interface of a sessile drop [15]. Modifica-
tion of surface chemical structure was examined using
X-ray photoelectron spectroscopy (XPS).
2. Experimental procedure
2.1. Atmospheric pressure plasma reactor
The atmospheric plasma reactor used in this study (Fig. 1)
was constructed using a cylindrical Pyrex glass tube (30 mm
ID, 90 cm long) with its inlet port connected to a gas
flow rate regulator for introducing helium gas into the
plasma reactor [16]. The outlet of the plasma reactor was
connected to an exhaust vent. A pair of copper electrodes
(7.5 cm  3 cm) was placed across the reactor for coupling
the electrical drive to the plasma reactor. The reactor
operated at 12 kV (peak-to-peak) at a frequency of 700 Hz,
delivering 100 W of power. Polycarbonate samples (100  200 )
were placed inside the reactor for plasma treatment.
Following plasma treatment, the samples were subjected to
contact angle measurement and surface chemistry analysis.
2.2. Surface chemistry analysis
XPS was used to analyze the surface chemistry of the
untreated and plasma-treated polycarbonate surfaces. The
XPS data were obtained using a Kratos Axis ESCA
Spectrometer using a Mg Ka (hn ¼ 1253.6 eV) X-ray
radiation source. The X-ray beam used was 100 W, with
a spot diameter of 100 mm. The experimental data were
referenced to the Au4f peak at 84.070.05 eV and the C1 s
Power Supply
12
Particle Trap
Vent
Sample
Fig. 1. Atmospheric pressure dielectric barrier discharge plasma reactor.
peak to 284.6 eV. The high-resolution scans of the C1 s
peak were acquired at a pass energy of 40 eV, in 0.2 eV
steps with a 300 ms dwell time. In order to determine the
carbon chemistry more accurately, scans were performed
over a narrower region of the C1 s peak with a reduced
electron pass energy. This considerably reduces the count
rate, but significantly improves the peak resolution (i.e.
smaller FWHM). Small peak shifts associated with
chemical bonding can now be deconvoluted using curve-
fitting techniques.
The relative concentrations of the C1 s peak components
were determined by measuring the area under each fitted
peak and normalizing the total to 100% to get relative
percentage concentrations. Detection limits for XPS are
approximately 0.05–1.0 atomic percent depending upon the
sensitivity of the elements.
2.3. Contact angle measurements
Contact angle measurements have been used extensively
to elucidate the specific surface-chemical changes imparted
by an array of surface treatments for polymers, including
plasma treatment. The majority of the applications of
polymers rely on their surface properties such as adhesion
or printability, which, in turn depend upon their surface
chemical properties. Contact angle measurement has been
a good macroscopic indicator of the change in surface
chemistry. It has been utilized extensively in a number of
studies pertaining to surface modification of polymers [17].
Contact angle can also be related to surface energy and the
wettability of a surface. To assess the effect of plasma
treatment, contact angle measurements on untreated
and plasma treated polycarbonate films were made using
de-ionized water. A VCA-optima surface analysis system
(AST Products, Inc., MA) was used to measure contact
angle (Fig. 2). All the experiments were carried out under
ambient conditions (50% RH, 23 1C).
3. Results and discussion
Polycarbonate samples were plasma treated for 30, 120,
300 and 600 s. Five sets of samples were plasma treated for
Signal generator
s
A
Signal Amplifier
Helium
 ARTICLE IN PRESS
R. Sharma et al. / Journal of Electrostatics 65 (2007) 269–273
each treatment time. Contact angle measurements were
made on one set of samples immediately following the
plasma treatment. Measurements were made on the other
four sets of samples after 1, 2, 3 and 10 days of plasma
treatment. Contact angle was also measured for an
untreated sample. The contact angle for an untreated
sample was found to be 931. It decreased to 401 after 30-s
exposure to plasma (Fig. 3). There was no significant
decrease in contact angle with further increase in plasma
treatment time. The contact angle for a 600-s plasma
treated sample was 301.
The contact angle measurements made on the samples 1,
2, 3 and 10 days after the end of treatment showed an
increase for all the samples as compared to that of the
samples analyzed immediately after plasma treatment
(Fig. 4). For a 30-s plasma treated sample, the contact
angle changed from 391 immediately after plasma treat-
ment to 511 one day after plasma treatment. It further
Fig. 2. VCA Optima surface analysis system for measuring contact angle.
100
90
Contact angle (degree)
80
70
60
50
40
30
20
10
0 governed by thermodynamics, diffusion of mobile additives
0 30 120 300
Plasma treatment duration (seconds)
Fig. 3. Effect of plasma treatment duration on wettability of polycarbo-
nate sample. Contact angle represents the wettability of a surface.
271
increased to 791 after 2 days. There was no significant
change in contact angle beyond that. Similarly, for 120-s
and 300-s plasma treated samples, the contact angle
increased from 381 immediately after plasma treatment to
541 and 531, respectively, 1 day after the end of plasma
treatment.
The 600-s plasma treated sample showed a trend similar
to 30-s treated sample, where contact angle increased 1 and
2 days after treatment but there were no significant
subsequent changes.
The XPS analysis showed an increase in O:C ratio with
an increase in plasma treatment time up to 300 s (Fig. 5).
This increase in O:C ratio is indicative of the increase in
oxygen-containing polar functional groups on the surface.
An increase in polar moieties on the surface increases
surface free energy, thereby, making the surface hydro-
philic [3,8]. This explains the decrease in contact angle with
increasing plasma treatment time, as shown in Fig. 3.
Further increases in plasma treatment time caused a
decrease in the O:C ratio. The decrease in values of O:C
for the samples that were plasma treated for 600 s suggests
that the treatment time was past optimum for oxidation.
This decrease in the O:C ratio could be due to the breakup
of oxygen functional groups and increased crosslinking
(formation of covalent bonds between molecular chains of
polymers).
Table 1 summarizes the relative concentrations of the
carbon peak components. Increased oxygen concentration
with plasma treatment-time is evident from the increase in
the C–O functional group. A decrease in the C–C/C–H
ratio with an increase in plasma treatment time suggests an
increase in crosslinking, which occurs when plasma species
(typically inert plasma) interact with a polymer surface to
break C–C or C–H bonds, resulting in recombination,
unsaturation, or branching of polymer chains [12].
It was found, however, that the O:C ratio increased with
time after the end of plasma treatment. This result suggests
a multitude of prolonged post-plasma reactions. Free
radicals formed at or below the surface during plasma
treated have been found to be stable for long time
durations [1].
Thus these radicals have an opportunity to react with
atmospheric oxygen or water vapor. This explains the
increase in O:C up to 72 h after plasma treatment. After
72 h, a decrease in O:C was observed, suggesting a
depletion in free radicals on the surface which in turn
prevented introduction of any more oxygen-containing
functional groups. The decrease in O:C beyond 72 h could
also be due to ageing of the surface. The ageing of plasma-
treated polymer surfaces has been described by Liston et al.
[1] as a combination of processes including reorientation of
polar functional groups from surface to sub-surface as
600
from bulk to surface and reaction of free radicals. This also
explains the decreased wettability or increase in contact
angles on samples 1, 2, 3 and 10 days after plasma
treatment.
 ARTICLE IN PRESS
272 R. Sharma et al. / Journal of Electrostatics 65 (2007) 269–273

a 100 b 100
Contact angle (degree)

Contatc angle (degree)

80 80
60 60
40 40
20 20
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
days days
c 80 d 80
70

Contact angle(degree)
Contact angle (degree)

70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
days days

Fig. 4. Effect of ageing on the wettability of polycarbonate surface plasma treated for (a) 30 s, (b) 120 s, (c) 300 s, and (d) 600 s.

0.5 Table 1
24
48 Surface functional groups concentration (%) on untreated and plasma
0.45
72 treated polycarbonate surfaces as determined by XPS
0.4 96
Sample Treatment time C–C/C–H C–O CQO O–CQO p–p*
0.35
24 h 0 90 7.1 0.7 2.2 0.3
0.3 30 s 82 12 3.8 2.2 —
O:C ratio

120 s 86 12 2.1 0.5 —

0.25
300 s 80 12 3.3 3.0 2.1
0.2 600 s 75 18 2.4 4.1 0.5

0.15 48 h 0 91 6.0 — 1.2 1.7

30 s 76 16 2.0 4.7 1.6
0.1 120 s 77 13 3.4 3.2 3.2
300 s 78 14 2.3 4.3 1.4
0.05
600 s 81 13 0.7 3.2 2.0
0
72 h 0 91 6.0 — 2.0 1.6
0 100 200 300 400 500 600 700
30 s 78 16 2.3 3.4 1.3
Treatment time (seconds)
120 s 76 16 1.1 3.9 3.4
Fig. 5. Effect of plasma treatment time on O:C ratio. 300 s 76 14 2.0 3.7 4.0
600 s 79 14 2.3 4.6 0.8
96 h 0 90 2.7 1.1 0.3 5.9
30 s 80 10 3.6 2.1 4.8
120 s 78 14 2.2 2.4 3.9
4. Conclusion 300 s 71 15 4.2 5.6 4.6
600 s 79 12 1.8 3.3 4.0
Atmospheric-pressure helium plasma was used to modify
a polycarbonate surface. The stability of plasma induced
changes on surface chemistry and wettability was studied.
It was found that plasma treatment increased the wettablity oxygen component on the surface until 72 h hrs after
of the surface as indicated by decreasing contact angle. The plasma treatment.
contact angle decreased from 931 for untreated samples to
301 for 600-s plasma treated samples. The plasma-treated Acknowledgements
surface became less wettable over time due to ageing. The
O:C ratio increased with increasing plasma treatment The authors would like to acknowledge the help of
time. The post-plasma reactions continued to increase the Mr. Dwight Hillis of Graduate Institute of Technology,
 ARTICLE IN PRESS
R. Sharma et al. / Journal of Electrostatics 65 (2007) 269–273
UALR in the construction of the plasma generator. The
authors also acknowledge the help Electrostatics and
Surface Physics Laboratory, NASA for the XPS analysis.
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