Surface & Coatings Technology 204 (2010) 3272–3279

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Plasma modification of polylactic acid in a medium pressure DBD

N. De Geyter a,⁎, R. Morent a, T. Desmet b, M. Trentesaux c, L. Gengembre c, P. Dubruel b, C. Leys a, E. Payen c
a
Research Unit Plasma Technology (RUPT), Department of Applied Physics, Faculty of Engineering, Ghent University, Jozef Plateaustraat 22-9000 Ghent, Belgium
b
Polymer Chemistry and Biomaterials Research Group (PBM), Department of Organic Chemistry, Faculty of Sciences, Ghent University, Krijgslaan 281-9000 Ghent, Belgium
c
Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université des Sciences et Technologies de Lille, Bât. C3, Cité Scientifique, 59655 Villeneuve d'Ascq, France

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, a dielectric barrier discharge (DBD) operating in different atmospheres (air, nitrogen, helium
Received 18 February 2010 and argon) and at medium pressure is employed to modify the surface properties of polylactic acid (PLA).
Accepted in revised form 18 March 2010 Chemical and physical changes on the plasma-treated surfaces are examined using contact angle, X-ray
Available online 25 March 2010
photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements. Results show that the
discharge gas can have a significant influence on the chemical composition of the PLA surfaces: air and argon
Keywords:
PLA
plasmas introduce oxygen-containing groups, while nitrogen discharges add nitrogen groups to the PLA
Dielectric barrier discharge surface. Quite surprisingly, also helium plasmas incorporate a small amount of nitrogen-containing
Contact angle functionalities: this observation can however be explained by the fact that the helium discharge operates in
XPS the glow mode. In the near future, it will be examined whether the performed plasma treatments can
AFM enhance PLA cell attachment and proliferation, which might open the door to many interesting biomedical
applications.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction properties of PLA need to be altered to create additional functional

Non-thermal plasmas are commonly used to modify the surface
properties of polymers [1–3]. Due to excellent properties such as a high
strength to weight ratio, thermal stability, transparency, etc. polymers
are frequently used as structural materials, for packaging and sealing
applications and as protective coatings [4,5]. Despite these excellent
properties, polymers are not employable for many industrial uses due to
their low surface energies and their normally poor chemical reactivity
[4,6,7]. Thus, surface pre-treatment is usually required to achieve
satisfactory surface wetting and adhesion, while retaining the advan-
tageous bulk properties. In the past decades, plasma modification of
polymers has been actively studied, however, this research has mainly
focussed on well-known polymers, such as polypropylene [8–10],
polyethylene [3,11,12], polyethylene terephthalate [5,8,13], polyamide
[14,15], etc. Although plasma treatments have been successfully applied
to these popular polymers, only more recently they have been used to
modify the surface properties of uncommon biodegradable polymers,
such as for example polylactic acid (PLA) [16–25]. PLA is a well-known
biodegradable aliphatic polymer and has been previously used for
several biomedical applications such as bone fixation devices (plates,
pins, screws, etc.) and as tissue engineering scaffolds [16,20]. Although
PLA is known to be biocompatible and widely used in the field of
medicine, its low wettability and surface energy affect cell attachment
and proliferation and remain an important issue [16]. Therefore, surface
⁎ Corresponding author. Tel.: + 32 9 2643837; fax: + 32 9 2644298.
E-mail address: nathalie.degeyter@ugent.be (N. De Geyter).
groups, which can in turn be used to link peptide sequences (for
example the tripeptide sequence arginine–glycine–aspartate) to the
PLA surface [26]. These short peptide sequences are recognized by cell
membrane receptors leading to the promotion of cell attachment and
spreading [26].
A few authors [20–25] have studied the effect of non-thermal
plasmas on PLA samples, however, their studies are mostly limited to
vacuum technologies. Although vacuum treatments afford good control
over gas chemistry and provide the possibility to use high energetic
species (in the range of several eV to hundreds of eV) in surface
modification processes, atmospheric pressure technologies offer attrac-
tive perspectives in today's industrial processes due to the elimination of
expensive vacuum equipment, easier handling of the samples and
scalability for industrial in-line processing [27,28]. Therefore, in recent
years, a lot of effort has been put into the development of non-thermal
plasma reactors working at (or near) atmospheric pressure [28,29]. In
between vacuum and atmospheric pressure plasma technology lays a
wide – almost unexplored – pressure range (so-called medium
pressure) which might combine the advantages of both vacuum and
atmospheric pressure technologies. At medium pressure, a large plasma
volume can be easily obtained, which can result in a higher overall
productivity [10]. Recently, it has been shown that at low energy
densities, plasma treatment at medium pressure is more energy-
efficient than at atmospheric pressure [2]. Furthermore, different (toxic)
chemicals and gases can be used, since medium pressure technology
works in a closed system. In addition, at medium pressure, the pumping
equipment is relatively inexpensive [10]. Recognizing the above, a
medium pressure non-thermal plasma will be employed in this paper to

0257-8972/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2010.03.037
 N. De Geyter et al. / Surface & Coatings Technology 204 (2010) 3272–3279
Fig. 1. Experimental set-up of the DBD (1. gas cylinder, 2. mass-flow controller, 3. plasma
chamber, 4. pressure gauge, 5. needle valve, 6. pump).
Table 1
Experimental parameters for the DBDs sustained in different working gases.
Gas Treatment time Discharge power Energy density
(s) (W) (J/cm2)
Air 0–15 4.54 0–6.00
Nitrogen 0–14 4.84 0–5.97
Argon 0–60 1.12 0–5.93
Helium 0–85 0.82 0–6.15
alter the surface properties of PLA. Among various non-thermal plasmas,
DBDs are very convenient for the activation or modification of polymer
surfaces due to the easy formation of a stable regime and due to their
scalability [27]. DBDs are characterized by the presence of one or more
insulating layers (so-called dielectric barriers) with a discharge gap in
the current path between the metal electrodes. The presence of this
dielectric barrier limits the current flowing through the gas, which
prevents the discharge from developing into an electrical arc [30].
Usually, a DBD operates in the filamentary mode: the breakdown starts
at many points, followed by the development of independent current
filaments, named microdischarges [31–34]. These microdischarges are
of nanosecond duration and are randomly distributed over the dielectric
surface. Due to this lack of uniformity, extensive efforts to homogenize
DBDs have been made and it was found that under special, quite
restrictive conditions homogeneous (or so-called glow) DBDs can be
obtained [35,36]. It is generally believed that in the case of a filamentary
DBD, a large number of spike-like current pulses with nanosecond
duration are appearing during certain sections of every half cycle of the
applied voltage [33,34,37]. In contrast, a glow discharge is characterized
by a single current pulse with durations up to a few µs [38,39]. Besides
these 2 well-known modes, some authors also report on what they call
the “pseudoglow” discharge [40–42]. This regime is characterized by the
presence of successive short current pulses (a few µs) and is also called
the “multi-glow” mode, since the current–voltage characteristic for each
current pulse is similar to the one obtained in the glow mode [42].
The present study investigates the potential of medium pressure
DBDs for surface modification of PLA. After the description of the
experimental set-up, DBD surface treatments in 4 different atmo-
spheres (air, argon, nitrogen and helium) will be explored. The
differences in surface modifications among the four discharges will be
investigated by contact angle measurements, XPS and AFM. Contact
angle measurements will be used to evaluate the wettability of the
untreated and plasma-treated PLA films, while the chemical compo-
sition of the films can be studied using XPS. Finally, AFM will be
employed to visualize and compare the topography of untreated and
plasma-treated PLA surfaces.
3273
2. Experimental procedure
2.1. DBD set-up and characterization
The DBD reactor (schematically presented in Fig. 1) contains two
circular copper electrodes (ϕ = 38 mm) both covered by a ceramic
(Al2O3) plate. The distance between the two ceramic plates is kept
constant during plasma modification at 4 mm. The upper electrode is
connected to a high frequency (50 kHz) AC power source, while the
lower electrode is connected to earth through a resistor R (50 Ω) or a
capacitor C (10 nF). Before starting plasma modification, a PLA film with
a thickness of 50 µm is placed on the lower ceramic plate. These
commercially available PLA foils were purchased from Goodfellow
Cambridge Limited (England) and are not subjected to any pre-
treatment step before plasma modification. After introduction of the
polymer foil into the plasma chamber, the reactor is pumped down
below 0.3 kPa using a rotary vane pump and then filled with the
discharge gas at a rate of 3.0 slm (standard litres per minute). Once
atmospheric pressure (101 kPa) is reached, the gas flow rate is kept
constant at 3.0 slm during 3 min, while the pressure is reduced to
20.0 kPa by the use of a valve placed in front of the rotary vane pump.
This purging step is performed to ensure a high gas purity. Subsequently
the plasma chamber is pumped down to 5.0 kPa, while maintaining a
working gas flow of 1.0 slm between the electrodes. In this work, four
different feed gases (Air Liquide—Belgium) are used for the plasma
treatments: dry air, nitrogen, helium and argon.
To determine in which mode the DBD is operating for each discharge
gas, current–voltage waveforms are acquired. A 1000:1 high voltage
probe (Tektronix P6015A) is connected to the upper electrode to
measure the high voltage applied to the reactor (VP), while at the same
time the voltage over the 50 Ω resistor (VR) is obtained using a voltage
probe (Tektronix P2100). VP(t) and VR(t) are then recorded with a
2-channel digital oscilloscope (Tektronix TDS210, 60 MHz) and the
discharge current I(t) can be obtained by dividing VR(t) by R.
To calculate the discharge power of the DBD, the resistor R is replaced
by a capacitor C. The voltage across this capacitor (VC) is measured using
a voltage probe (Tektronix P2100) and displayed on the oscilloscope as a
function of time together with the high voltage VP(t). The charge Q(t)
stored on the electrodes is obtained by multiplying VC(t) with C and Q(t)
is represented as a function of VP(t) for one period in order to obtain a so-
called Lissajous figure. This figure is used to determine the discharge
power, since the electrical energy consumed per voltage cycle is equal to
the area enclosed by the Lissajous figure. The discharge power P is then
calculated by multiplying the electrical energy with the frequency of the
feeding voltage (50 kHz) [34]. Table 1 represents these discharge
powers for the different feeding gases, together with the range of
treatment times used to treat the PLA surfaces. Table 1 shows that the
discharge power is much lower for the argon and helium DBDs, since
electrical breakdown occurs at much lower voltages in these gases.
Higher discharge powers lead to plasma instabilities and will therefore
not be examined in this study. Since the discharge power is not the same
for the different DBDs, the results in this paper will be presented as a
function of energy density instead of treatment time to be able to make
an objective comparison between the various plasma treatments. This
energy density is calculated by multiplying the plasma exposure time
with the plasma power and by dividing this by the area of the plasma
electrodes.
2.2. Surface characterization
2.2.1. Contact angle measurements
The contact angles of the foils are obtained at room temperature
using a commercial Krüss Easy Drop system (Krüss Gmbh, Germany)
within 5 min after plasma treatment. This apparatus comprises a
software operated high-precision liquid dispenser, which precisely
controls the drop size of the liquid placed on the sample surface. The
3274 N. De Geyter et al. / Surface & Coatings Technology 204 (2010) 3272–3279

Fig. 2. Current–voltage waveforms of the DBD sustained in air (a), nitrogen (b), argon (c) and helium (d).
 N. De Geyter et al. / Surface & Coatings Technology 204 (2010) 3272–3279
drop image is then stored via a monochrome interline CCD video
camera, using PC-based acquisition and data processing. Using the
software provided with the instrument, measurements of the static
contact angle values are fully automated. In this paper, distilled water
drops of 2.0 µl are used as test liquid. The contact angle values, shown in
this work, are obtained using Laplace–Young curve fitting and are the
average of 7 values measured over an extended area of the plasma-
treated PLA films.
2.2.2. XPS measurements
XPS analyses are performed on a VG Escalab 220 XL system (Thermo
Fisher Scientific, USA) equipped with a non-monochromatic Mg Kα
X-ray source (hν = 1253.6 eV) within 1 h after plasma treatment. The
emission voltage and the current of this source are set to 15 kV and
20 mA respectively. The pressure in the analyzing chamber is
maintained at 10− 7 Pa or lower during analysis and the size of the
analyzed area is 8 mm× 8 mm. Survey (0–1100 eV) and high-resolution
(C1s) spectra are recorded at a pass energy of 100 eV and 40 eV
respectively. XPS analyses are performed with a take-off angle of 90°
relatively to the sample surface. The hydrocarbon component of the C1s
spectrum (285.0 eV) is used as calibration of the energy scale and fitting
of the XPS high-resolution C1s spectra is performed using CasaXPS. The
C1s peaks are deconvoluted using Gaussian–Lorentzian peak shapes and
the full-width at half maximum (FWHM) of each line shape is
maintained below 1.8 eV.
2.2.3. AFM measurements
AFM images are obtained in ambient conditions with a Multimode
scanning probe microscope (Digital Instruments — USA) equipped
with a Nanoscope IIIa controler. 5 µm scans are recorded in tapping
mode with a silicon cantilever (OTESPA, Veeco). WSxM software [43]
is used for surface roughness analysis after the recorded images are
modified with an X and Y Plane Fit Auto procedure.
3. Results
3.1. Electrical characterization of the discharge
Fig. 2 shows the current–voltage waveforms of the discharge
operating in air, nitrogen, argon and helium. For the air DBD, the
discharge current consists of numerous short peaks, which are an
indication of the microdischarge activity. Every peak corresponds
to a series of microdischarges and therefore, one can conclude that
the DBD sustained in air operates in the filamentary mode. In case
of the nitrogen DBD, it is quite difficult to determine the discharge
Fig. 3. Water contact angles as a function of energy density for air, nitrogen, argon and helium plasma-treated PLA samples.
3275
mode based on only the current waveform: it could be possible
that the nitrogen discharge operates in the filamentary or in the
multi-glow regime. For the argon and helium DBDs, the discharge
current shows the presence of only one wide peak at every half
cycle of the voltage. This means that the helium and argon
discharges operate in the glow mode.
3.2. Contact angle measurements
Fig. 3 shows the evolution of the PLA contact angles as a function
of energy density after plasma treatments in air, nitrogen, helium
and argon. As can be observed in Fig. 3, the contact angle of the PLA
film is found to decrease from approximately 75° to the lowest value
59° after air plasma treatment with an energy density of 0.1 J/cm2.
However, when the energy density is increased above 0.1 J/cm2, the
water contact angle does not change anymore, showing that there is
a saturation of the air plasma effect on the PLA film. An argon
plasma treatment leads to similar changes in PLA contact angle
values: the water contact angle also decreases to 60°, however, the
energy density necessary to obtain this lowest value (1.0 J/cm2) is
10 times higher compared to the air plasma. Fig. 3 also shows that
the contact angle decrease is much more pronounced in the case of
nitrogen and helium plasma treatments: a helium plasma treatment
can decrease the PLA contact angle to 36°, while a nitrogen
treatment leads to an even lower contact angle (31°). The energy
densities necessary to obtain these lowest values are equal to 1.3
and 3.3 J/cm2 for the nitrogen and helium plasmas respectively,
which are considerably high values compared to air and argon
treatments. The considerable decrease in PLA contact angles after
plasma treatment demonstrates the strongly increased wettability,
suggesting that the PLA surfaces contain an increased number of
hydrophilic groups after treatment.
3.3. XPS results
Table 2 shows the atomic composition of the PLA films before and
after plasma treatment in air, nitrogen, helium and argon with an energy
density of 4.3 J/cm2, meaning that all these plasma-treated samples are
saturated. After air and argon plasma treatment, the O/C atomic ratio
increases from 0.47 to 0.61 and 0.54 respectively. In contrast, a helium
and nitrogen plasma treatment does not lead to the incorporation of
oxygen since the O/C atomic ratio does not significantly change.
However, these plasma treatments introduce a significant amount of
nitrogen on the PLA surfaces: the N/C atomic ratio of the helium plasma-
treated films is 0.04 while for the nitrogen plasma-treated surfaces the
3276 N. De Geyter et al. / Surface & Coatings Technology 204 (2010) 3272–3279

Table 2 conclude that the oxygen incorporation on the argon plasma-treated

Atomic composition and concentration of the different chemical bonds on untreated PLA samples is much less pronounced than on the air plasma-treated
and plasma-treated PLA films (energy density = 4.3 J/cm2).
samples.
Treatment %C %O %N O/C N/C 285.0 eV 286.8 eV 289.1 eV Similar to the spectrum of the untreated PLA film, 3 component peaks
No 68.2 31.8 0 0.47 0 49.6 25.4 25.0 were used to fit the C1s envelopes of helium and nitrogen plasma-treated
Air plasma 62.2 37.8 0 0.61 0 38.1 30.5 31.4 samples: a peak at 285.0 eV due to C–C or C–H bonds, a peak at 286.8 eV
Nitrogen plasma 62.1 31.1 6.8 0.50 0.11 41.8 29.1 30.1 which could be due to C–N, C= N, C–O, C≡N,… bonds and a peak at
Argon plasma 65.1 34.9 0 0.54 0 45.6 28.3 26.1
288.9 eV due to O–C O, N–CO–N, N–C–O, N-C = O,... groups. It should be
Helium plasma 66.9 30.4 2.7 0.45 0.04 47.4 26.5 26.1
noted that the insertion of nitrogen atoms into the PLA polymer structure
will likely lead to a broad spectrum of chemical functionalities and that
the reproduction of the observed C1s envelopes with three component
N/C atomic ratio is 0.11. These results suggest that the air and argon peaks is a deliberate over-simplification [45]. The identification of the
plasmas mainly add oxygen atoms to the PLA surfaces, while the functional carbons based on the binding energies of the peaks is rather
nitrogen and helium plasmas mainly incorporate nitrogen atoms. difficult when both nitrogen and oxygen species are present, since the
To obtain further insight into the chemical bonds present on the energy difference between some nitrogen- and oxygen-related groups is
surface of the plasma-treated PLA films, curve fitting of the high- too small to allow separation by mathematical reconstruction within
resolution C1s peak can be performed. Fig. 4 shows the C1s peaks of the error bars. The C1s binding energy of the different oxygen-containing
PLA films before and after plasma treatment in air, argon, nitrogen and carbon groups are well defined in literature [44], in contrast, for the
helium (energy density= 4.3 J/cm2). The C1s envelopes of the untreat- carbon–nitrogen species, one can observe large discrepancies in binding
ed, air plasma-treated and argon plasma-treated PLA films can be energies. Moreover, also the N1s peak cannot give a decisive answer
decomposed into 3 distinct peaks: a peak at 285.0 ± 0.1 eV correspond- about the nitrogen-containing functionalities on the PLA surface, since
ing to C–C and C–H bonds, a peak at 286.8 ± 0.1 eV due to C–O functional the N1s peak of the samples lies between 397 and 403 eV. In this energy
groups and a peak at 289.1 ± 0.1 eV, which can be attributed to O-C = O range, one can find several carbon–nitrogen species, such as amides,
groups [44]. As shown in Fig. 4, following air plasma treatment, large imides, nitriles, … [44]. However, Fig. 4 clearly shows that after nitrogen
changes in the C1s peak can be seen: the peak at 285.0 eV decreases, plasma treatment, the peaks at 286.8 and 289.1 eV increase. Together
while the peaks at 286.8 and 289.1 eV increase. Fig. 4 also shows that the with the results of the XPS survey scans, one can conclude that a
difference in C1s peak of the untreated and argon plasma-treated PLA significant amount of nitrogen-containing functionalities are incorporated
sample is less pronounced, however, it can be observed that the peaks at on the PLA surfaces after nitrogen plasma treatment. Fig. 4 also shows that
286.8 and 289.1 eV tend to slightly increase after argon plasma the difference in C1s peak of the untreated and helium plasma-treated PLA
treatment. Based on these deconvoluted C1s peaks, the concentrations sample is less pronounced: the peaks at 286.8 and 289.1 eV only slightly
of the different chemical bonds in the PLA films can be obtained. Table 2 increase, suggesting that only a very small amount of nitrogen is
presents the concentration of the chemical groups for samples plasma- incorporated in the helium plasma-treated PLA films, which is consistent
treated with an energy density of 4.3 J/cm2. Table 2 clearly shows that with the atomic concentrations shown in Table 2.
the concentration of the C–C and/or C–H bonds decreases after plasma
treatment in air, while the concentration of the oxygen-containing 3.4. AFM results
groups (C–O and O-C= O) increases. As a result, one can conclude that
the air plasma mainly attacks the C–C and C–H bonds in the PLA polymer Fig. 5 shows the AFM image of an untreated PLA film, together with
chains to form C–O and O-C = O bonds. Table 2 also shows that after the AFM images of PLA films plasma-treated in air, nitrogen, argon
argon plasma treatment there is a decrease in C–C and/or C–H and helium (energy density = 4.3 J/cm2). As can be observed in Fig. 5,
concentration combined with a slight increase in C–O bonds and a plasma treatment significantly alters the surface morphology of the
minor increase in O-C= O bonds. Based on these results, one can PLA films: the pristine material has a considerably smooth surface,

Fig. 4. High-resolution C1s peaks of PLA before and after plasma treatment in air, argon, nitrogen and helium (energy density = 4.3 J/cm2).
 N. De Geyter et al. / Surface & Coatings Technology 204 (2010) 3272–3279 3277

Fig. 5. AFM images of (a) untreated PLA, (b) air plasma-treated PLA, (c) nitrogen plasma-treated PLA, (d) argon plasma-treated PLA and (e) helium plasma-treated PLA (energy
density = 4.3 J/cm2).
3278 N. De Geyter et al. / Surface & Coatings Technology 204 (2010) 3272–3279
Table 3
Rrms values (in nm) of various plasma-treated PLA surfaces.
Energy density Air Nitrogen Argon
(J/cm2)
0 11.7 11.7 11.7
1.1 12.9 12.6 18.7
2.1 13.2 12.9 19.1
4.3 16.4 16.0 19.9
while after plasma treatment in air, argon and nitrogen the surfaces
are quite rough. In contrast, the helium plasma-treated PLA surface is
still quite smooth. Changes in morphology of the plasma-treated PLA
samples can be quantified by root-mean-square roughness values
(Rrms) and these values are determined from four different 5 × 5 μm
AFM images. Table 3 presents the Rrms values for various PLA samples
plasma-treated with different energy densities. Table 3 shows that all
plasma treatments lead to small increases in PLA surface roughness,
however, this increase is the most pronounced after argon plasma
treatment and the smallest after helium plasma treatment.
4. Discussion
To understand the above mentioned results, it is necessary to
determine the influence of both the discharge atmosphere and the
discharge regime on the active species interacting with the PLA surface.
It is well known that a non-thermal plasma contains two types of active
species: on the one hand, species which are chemically reactive (for
example O2, O• and N•) and on the other hand, species which will only
break chemical bonds, like photons, electrons, non-reactive ions, non-
reactive excited atoms or molecules [46]. The chemically reactive
species are able to add new atoms to the polymer surfaces, while the
non-reactive species can excite the polymer or break C–C or C–H bonds,
leading to the formation of polymer radicals [46]. Subsequently, these
created radicals can react with radicals in the near polymer chains,
resulting in the formation of a cross-linked network. Moreover, these
radicals can also react with chemically active species present in the
discharge leading to the incorporation of new atoms at the polymer
surface. The chemically reactive species present in the discharge not
only depend on discharge atmosphere but also on discharge regime as
will be explained in the following section.
In the above results, it was shown that an air plasma increases the
hydrophilicity of PLA foils by introducing C–O and O-C = O groups
onto the polymer surface. AFM results have also shown that an air
plasma considerably etches the PLA surfaces. In an oxygen-containing
discharge (like dry air), the main chemically reactive species are
excited molecular oxygen species, atomic oxygen and ozone: these
species induce the formation of oxygen-containing functionalities
onto the PLA surfaces [46]. However, at extended plasma exposure
times, many chain scissions occur, leading to the formation of
oligomers and desorption of volatile products from the PLA surface
(etching). It is well known that polymer degradation is present in all
atmospheres, however, the presence of atomic oxygen enhances this
mechanism, leading to a more pronounced etching effect in oxygen-
containing discharges [47].
In the case of a nitrogen plasma treatment, it was shown that not
oxygen but nitrogen atoms are added to the PLA surfaces. In nitrogen
discharges, the main chemically reactive species are excited molecular
nitrogen species and N•. The N• radical is efficiently created at the PLA
surface due to the interaction of N+ 2 ions with electrons of the PLA
polymer. This latter reaction is exothermic, leading to the release of
energy, which is high enough to break PLA chemical bonds. As a result,
N• can efficiently react with the polymer surface, since radicals are
created at the same time and at the same place in the gas phase and on
the polymer surface [35,46]. As a result, a nitrogen plasma treatment
leads to the formation of nitrogen-containing groups on the PLA
Helium surfaces, as was experimentally observed by XPS measurements. AFM
results have also shown that etching of PLA is somewhat less
11.7 pronounced in a nitrogen discharge compared to an air discharge.
12.3 This is due to the fact that the changes in the PLA polymer chemistry
12.4 induced by nitrogen result in less chain scission and a lower formation
13.2
of volatile products [48].
A pure helium plasma does not contain any chemically reactive
species and normally leads to cross-linking and double bond
formation on polymer surfaces [49]. However, in this work, XPS
results have shown that a small amount of nitrogen atoms are added
to the PLA surfaces after helium plasma treatment. Since nitrogen
cannot be incorporated post treatment, it has to be due to nitrogen
impurities present in the discharge gas. In the used set-up it is very
difficult, if not impossible, to ensure that plasma treatment occurs in
pure helium. As a result, oxygen and nitrogen impurities are always
present in the discharge gas. These atoms can come from the residual
air present in the discharge chamber, the working gas impurities or
from the gaseous products which the plasma desorbs (H2O, O2, N2)
from the reactor walls or etches from the PLA surface. The fact that
nitrogen atoms are added to the PLA surfaces after helium plasma
treatment (and not oxygen atoms) is most likely due to the fact that
the helium discharge operates in the glow mode. Massines et al.
[35,46] have shown that the ratio of helium metastables to electrons is
higher in a glow DBD than in a filamentary DBD. Since these helium
metastables efficiently create N+ 2 ions by Penning ionization, the
density of N+ 2 ions is higher in a glow discharge. Moreover, these N2
+
ions have a higher probability of interaction with the PLA polymer
when the discharge is operated in the glow mode [46]. Both effects
can explain the incorporation of nitrogen on PLA after helium plasma
treatment. AFM images have also shown that the helium plasma does
not lead to a great change in surface topography, which is also most
likely due to the glow discharge regime, which is mild compared to
the filamentary discharges [12].
Similar to the helium discharge, argon plasma treatment is not
carried out in pure argon, since oxygen and nitrogen impurities are also
present in the discharge chamber. However, in contrast to the helium
plasma, it is shown in this work that a small amount of oxygen atoms are
added to the PLA surfaces, which was previously also observed on PP
and PET samples after plasma treatment with a filamentary argon
discharge [8]. These results suggest that the same active species are
created in the gas bulk by both the filamentary and the glow argon DBD.
Both discharges lead to roughly the same level of polymer transforma-
tions, an observation which was also observed for nitrogen glow and
filamentary DBDs [46].
5. Conclusion
This paper describes the effects of different plasma treatments (air,
nitrogen, helium and argon) on PLA films focusing on the chemical and
physical modifications induced on the surface. From contact angle, XPS
and AFM results, it is shown that the discharge atmosphere can have a
significant effect on the PLA surface modifications. Air and argon
plasmas are able to enhance the surface wettability by incorporating
oxygen-containing functionalities. In contrast, nitrogen plasmas add
nitrogen atoms to the PLA films, leading to an even more pronounced
surface wettability compared to the air and argon treatments. Quite
surprisingly, it was also observed in this work that a helium treatment
adds a small amount of nitrogen-containing groups to the polymer: this
could however be explained by the fact that the helium discharge
employed in this work operates in the glow mode. A subsequent study
will examine whether the plasma treatments performed in this work
will be effective in enhancing PLA cell attachment and proliferation,
which could lead to important biomedical applications.
 N. De Geyter et al. / Surface & Coatings Technology 204 (2010) 3272–3279
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