Thin Solid Films 614 (2016) 25–30

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Thin Solid Films

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

Surface modification of polymethylmethacrylate foils using an

atmospheric pressure plasma jet in presence of water vapors
T. Acsente a, M.D. Ionita a,⁎, M. Teodorescu a, V. Marascu a,b, G. Dinescu a
a
National Institute for Laser, Plasma and Radiation Physics, 409 Atomistilor Street, 077125, Bucharest-Magurele, Romania
b
Faculty of Physics, University of Bucharest, 405 Atomistilor Street, 077125, Bucharest-Magurele, Romania

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

Article history: In this work polymethylmethacrylate foil surfaces are modified using a non-thermal atmospheric pressure
Received 1 September 2015 plasma jet generated by a discharge with bare electrodes. The study focuses on a comparison of the treatments
Received in revised form 16 December 2015 performed using plasma generated in Ar/water vapors mixture (humid plasma) and dry Ar. Injecting small
Accepted 17 December 2015
amounts of water vapors in the discharge, a substantial improvement of the polymeric foils surface wettability
Available online 18 December 2015
was obtained. For a similar improvement of the wettability, the duration of treatment with dry argon plasma
Keywords:
is six times longer. The investigations of the treated surfaces show that the wettability of the polymeric foils is
Plasma jet mainly improved due to the surface roughening during dry plasma treatments, while the chemical changes of
Discharge with bare electrodes the sample surface prevail in the case of humid plasma treatments.
Surface modification © 2015 Elsevier B.V. All rights reserved.
Polymer treatment
Polymethylmethacrylate
Wettability

1. Introduction
Due to its properties, polymethylmethacrylate (PMMA) is the
polymer of choice for many domestic, industrial and even medical
applications. Such as it is, PMMA is transparent, with good resistance
at direct sun exposure and ultraviolet light (UV), exhibits low moisture
and water absorption, presents good mechanical properties (high
mechanical strength, it does not shatter at rupture and it is scratch
resistant) and it has a low cost [1]. Similar to other polymers, the main
drawback of PMMA is its low surface free energy, leading to poor hydro-
philicity and adhesion. These properties can be substantially improved
using different techniques for polymer surface modifications, including
treatments with wet chemicals [2], UV irradiation accompanied by
ozone exposure [3], laser alteration [4] and low temperature plasma at
low [5,6] or atmospheric pressure [7–9]. In particular, the PMMA sur-
faces are dominated by very stable ester methyl groups [10,11], limiting
the efficiency of the standard chemical modification procedures [12];
still, plasma treatments of PMMA are more efficient. A literature inspec-
tion reveals many studies dedicated to PMMA surfaces treatment using
plasma generated in different types of gases: argon, neon, xenon [13,
14], helium [15], oxygen [14,16], nitrogen [17,18], ammonia [19],
carbon dioxide [20], air [18,21] and even water vapors containing
plasma [12,20,22–26]. Only few of these studies (the most recent
ones) are performed at atmospheric pressure [13,15,18,26]. From all
⁎ Corresponding author.
E-mail address: daniela.ionita@infim.ro (M.D. Ionita).
the mentioned feeding gases, water vapor based plasmas are mentioned
in literature to be more advantageous when compared to other types of
plasma due to high chemical reactivity of hydroxyl groups in respect to
ester methyl groups from the PMMA surfaces [12]. In the present paper,
we report our results regarding PMMA foils surface modifications using
an atmospheric pressure plasma jet, operated either with humid or dry
Ar. The treatments were performed for different amounts of humid
argon injected in the discharge and the effects over the discharge char-
acteristics and the material properties of the treated PMMA surfaces
were assessed.
2. Experimental Details
The experimental setup used for the treatment of the polymeric foils
with either dry or humid Ar is presented in Fig. 1. It consists of three
main parts: the atmospheric pressure plasma jet (APPJ) source, the
gas feeding system and the scanning system.
The APPJ is based on a discharge with bare electrodes (DBE); its
operation details were described elsewhere [27]. The plasma source
presents a coaxial design and consists in a central metallic electrode,
surrounded by an internal ceramic insulator and an external grounded
metallic electrode envelope, the last one ending in a conical nozzle.
The feeding gas flows along the gap delimited between the central
electrode and the ceramic insulator, and the discharge is generated in
the space between the central electrode and the conical nozzle using a
13.56 MHz radiofrequency (RF) power supply. Due to the gas flow,
the ionized gas expands remotely as a plasma jet with dimensions

http://dx.doi.org/10.1016/j.tsf.2015.12.037
0040-6090/© 2015 Elsevier B.V. All rights reserved.
26 T. Acsente et al. / Thin Solid Films 614 (2016) 25–30
Fig. 1. The schematic diagram of the experimental setup used for treatment of the polymeric surfaces.
depending on the working parameters (for example around 1 mm in
diameter and 5 mm length when operated at 4000 sccm mass flow
rate of Ar and 14 W of RF power). The working gas is Ar (99.9999% pu-
rity) with low content of water as impurity (b 1 ppm); it was considered
as dry Ar in our experiment. Humid Ar was obtained by passing a stream
of dry Ar through a bubbler containing double distilled water. Prior
to injection in the plasma source, the humid and dry Ar streams are
mixed. The Ar mass flow rates are adjusted using two mass flow
controllers (with maximum ranges of 10000 sccm for dry Ar and
500 sccm for humid Ar). The mass flow rate of the feeding gas was
8000 sccm, its water content being varied by adjusting the mass flow
of the bubbled Ar between 0 and 400 sccm with steps of 50 sccm
(corresponding to a content of humid Ar in between 0% and 5%, with
steps of 0.625%).
The treated materials are 500 μm thick PMMA foils commercially
available (Goodfellow Ltd.). The treatment procedure is similar with
that presented by us in previous works [28] and consists in exposure
to the plasma jet of the polymeric foils placed on an x–y translation
stage. All samples were treated over a surface of 35 mm × 35 mm fol-
lowing a parallel lines scanning pattern, the duration of a complete
scan being 10 min. Treatments with humid Ar jet were performed for
the minimum duration (1 scan), while the dry plasma jet treatments
were performed increasing the duration of plasma exposure (i.e. 1, 2,
6 and 10 scans). During all treatments, the distance between the
polymeric foil and the plasma source nozzle was kept at 2 mm, while
the applied RF power was 14 W.
The spectral investigation of the plasma jet was performed using an
optical multichannel analyzer (model HR4000, Ocean Optics) with a
spectral resolution of 0.2 nm. The optical radiation was collected from
the treatment region using a collimating lens.
The sample temperature during treatment was evaluated in advance
as follows. A temperature sensor with thermal characteristics close to
that of the PMMA polymeric sample was placed on the substrate holder.
The sensor consists in two self-adhesive polyimide very thin foils cover-
ing a planar winding of solid platinum wire (actually a Resistance
Temperature Detector — RTD sensor). The dimensions of the sensor
active area are 20 mm × 30 mm × 0.3 mm and its measuring range is
in between −80 and +180°C. For temperature evaluation, the sensor
was scanned with the plasma jet using the same experimental method
used during the PMMA foil treatments. Because PMMA and polyimide
have near similar thermal properties [1], the temperatures measured
by using the planar RTD sensor are close to that reached by the PMMA
foils during their treatment.
The wettability of the PMMA foils was evaluated by static contact
angle (WCA) measurements; these were performed by sessile drop
method using droplets (1 μL volume) of distilled water in room envi-
ronment. The WCA values were measured using a computer con-
trolled CAM 101 (KSV Instrument Ltd.) contact angle meter. Each
WCA value reported in this work represents the average of six simi-
lar measurements.
The topography and the roughness of the PMMA surfaces were
evaluated by atomic force microscopy (AFM) using a Park Systems XE-
100 instrument operated in non-contact mode; the scan size was
5 μm × 5 μm. The surfaces morphology was obtained using an FEI S
Inspect Scanning Electron Microscope (SEM) with an acceleration volt-
age of 5 kV; prior the SEM investigations, the polymeric surfaces were
covered with a 20 nm thin gold layer for avoiding the electrostatic
charging. The chemical composition was studied by ATR-FTIR (Attenu-
ated Total Reflection Fourier Transform Infrared spectroscopy) using a
PIKE Technologies Horizontal ATR ZnSe crystal, mounted on a Jasco
spectrometer model FT/IR 6300. Each spectrum was obtained by
accumulation of 256 scans in the spectral range 600–4000 cm−1 with
a spectral resolution of 4 cm−1.
All the samples were investigated using the above mentioned tech-
niques. Still, the obtained results are presented only for the samples
showing the optimal modification of the WCA after plasma treatment,
in comparison with the untreated sample. These samples are denoted
with PMMA-D (treatment in dry Ar plasma), PMMA-H (treatment in
humid Ar plasma) and REF (untreated).
3. Results
3.1. Optical Emission Spectroscopy (OES) Measurements
In Fig. 2a are presented the OES spectra of the atmospheric pressure
plasma jet in the spectral range 200–1000 nm, recorded in the treatment
region (i.e. at 2 mm from the nozzle). In both spectra is identified the
emission of the following species: OH radical bands in the range 280–
309 nm (transition A2Σ+–X2Π), of N2 (C-B) second positive system
(SPS) in the range 300–450 nm and the atomic Ar I (transitions between
the excited levels 1s–2p of atomic Ar) lines in the range 696–1000 nm
and the atomic O I (triplet line transitions 3s–3p) at 777.4 nm.
A significant modification of the optical emission spectra is observed
(see Fig. 2a) when water vapors are introduced in the discharge: an
increase of the OH band intensity, accompanied by the decrease of the
atomic species (Ar I and O I) emission is noted. Dependence of the OH,
 T. Acsente et al. / Thin Solid Films 614 (2016) 25–30
Fig. 2. a) Optical emission spectra recorded in the plasma jet operated with: humid Ar (up)
and dry Ar (down) and b) the dependence of the ArI, OI and OH spectral lines intensity
over the mass flow rate of the bubbled Ar (i.e. the amount of water injected in discharge).
Ar I and O I intensities over the mass flow rate of the humid Ar injected
in the discharge is presented in Fig. 2b. The intensity of the OH emission
has a maximum for a value of around 50 sccm of bubbled Ar while the
optical intensity of the atomic species monotonically decreases when
the water vapors content increases. Similar enhancement of the UV
emission in discharges generated in Ar/H2O mixtures was observed at
low pressures [29] and also at atmospheric pressure [26], being attribut-
ed to the decrease of the electronic temperature at higher water content
in the discharge mixture.
Another effect observed when water vapors are injected in the
discharge is the decrease of the plasma jet length, similar with the
results reported in [30]. This effect is prominent at high flow rates of
the humid argon. The length of the dry Ar plasma jet is around 5 mm
and only a small shortening (around 0.5 mm) is observed when small
amounts of bubbled Ar (50–150 sccm) are injected in the discharge. In
contrast, the plasma jet length decreases to around 2–3 mm for
400 sccm of bubbled Ar, partially explaining the decrease of the plasma
optical emission (see Fig. 2). When the bubbled Ar mass flow rate
exceeds 500 sccm the discharge is sustained only inside the plasma
source discharge gap.
3.2. Temperature of the Substrate During Treatment
During the treatments with the dry Ar plasma jet, the sample surface
temperature was 47°C. This value increases with the amount of water va-
pors injected in the discharge, up to 60°C (for 400 sccm of water bubbled
Ar). These values are below the glass temperature of the PMMA material,
27
ranging from 85°C to 165°C [1]. Thereby, the plasma treatments per-
formed using our experimental setup do not degrade the PMMA foil sur-
face by thermal effects (like transitions to rubbery state).
We mention that our previous works devoted to polymer modifica-
tion [28,31] show that similar temperature values are obtained with the
plasma jet operated in dry Ar at 4500 sccm. However, the injection of
water vapors in the discharge in such conditions led to increase of the
temperature up to 100°C, a value inadequate for treating the PMMA
surfaces. Consequently, in the present experiments we increased the
mass flow rate of the working gas up to 8000 sccm, thus lowering the
treatment temperature.
3.3. Material Investigation
3.3.1. Contact Angle Measurements and Ageing Effects
The results of the water contact angle measurements for PMMA
samples treated in dry Ar and humid Ar, compared with that of the un-
treated reference sample are presented in Fig. 3. In the case of samples
treated in dry Ar plasma, the WCA decreases when the duration of
PPMA foils treatment (i.e. the number of scans) increases. The lowest
value of the WCA is 20° and it was obtained after 10 scans (correspond-
ing to 100 min of treatment). This result is in agreement with that
obtained previously by us and other authors for different polymeric
foil types (polyethylene, polyethylene terephthalate, polyvinyl chloride,
polytetrafluoroethylene [31,32] and PMMA [15,21]).
Concerning the samples treated in humid Ar, Fig. 3 shows that the
WCA presents a minimum of 35° at an optimum value of 100 sccm;
further increase of the water content in the discharge leads to increase
of the WCA up to 80°, corresponding to the untreated sample. This evo-
lution of the WCA with the water vapors content, which is similar to
that of the OH radical intensity (Fig. 2b), suggests that OH radicals
present in the plasma jet may play an important role in the increase of
the wettability.
The results presented in Fig. 3 show that the optimized (i.e. using
about 100 sccm of bubbled Ar) humid plasma treatments are more effi-
cient when compared to the dry Ar ones. Indeed, a WCA of 35° obtained
with one scan in humid Ar is obtained only after 6 scans performed with
dry Ar; this result is remarkable and we will focus on explaining it.
The persistence of wettability modifications of PMMA surfaces was
investigated by measuring the variation of the contact angle for
2 months, and the results are presented in Fig. 4. It is observed that
for all treated samples the WCA increases in time to higher values.
This degradation of the wettability is known as the ageing effect and it
was observed in many other works [18,33,34] devoted to plasma
Fig. 3. Comparison of water contact angle after treatments with humid argon (one scan,
variable humid argon flow rate in the upper axis) and with dry argon (variable number
of scans in the bottom axis).
28 T. Acsente et al. / Thin Solid Films 614 (2016) 25–30
Fig. 4. Ageing behavior of the PMMA surfaces treated with: a) dry Ar plasma and b) humid
Ar plasma.
treatment of the polymeric surfaces. As observed in Fig. 4, the wettabil-
ity degradation has the same trend for all PMMA samples treated in dry
plasma (Fig. 4a) and some of the samples treated in humid plasma
(Fig. 4b, limited to 150 sccm of bubbled Ar). For these samples the
WCA increases after 20 days to near the same value (around 70°), still
lower in respect with the untreated PMMA sample. Fig. 4b reveals also
that for amounts of bubbled Ar exceeding 200 sccm the treatments
are not efficient.
Fig. 5. AFM images and the RMS roughness values of the: a) REF, b) PMMA-H and c) PMMA-D samples.
3.3.2. AFM and SEM Investigations
The AFM images of the untreated (REF) and plasma treated (PMMA-
D and PMMA-H) samples are shown in Fig. 5. The untreated REF sample
presents a smooth surface, with a root mean square (RMS) roughness of
24.7 nm. The optimal treatment with humid plasma leads to a negligible
roughening of the treated surface (RMS = 27.1 nm, Fig. 5b) when
compared with that performed in dry Ar plasma (RMS = 32.5 nm,
Fig. 5c). Fig. 6 presents the SEM images of the same PMMA samples,
supporting the AFM results. The roughening of the PMMA foils is the
result of the etching induced by the plasma species and it is partially
responsible for the hydrophilization [35]. It can be concluded that the
treatments with optimal humid Ar plasma lead to hydrophilicity
increase with only a slight alteration of surface topography.
3.3.3. ATR-FTIR Investigations
PMMA, with the chemical formula –[–CH2–C(CH3)(COOCH3)–]n– is
composed of C–C, C–H groups of the backbone chain, C–C, C= O, C–O
of the ester group and C–H units of the methyl substituent [36]. Fig. 7
presents the ATR-FTIR normalized spectra of the untreated (REF) and
plasma treated PMMA samples (PMMA-D and PMMA-H). The spectrum
of the untreated sample is in good agreement with the data presented in
other works [37–39]. For example, the C–C skeletal bands appear at
750 cm−1 and 1063 cm−1. The rocking vibrations of CH2 occur at
840 cm−1 while that of CH3 in the spectral interval is 910–988 cm−1.
In the region between 1050 and 1270 cm− 1 four bands of the ester
group are noticed: C–O–C bending (at 1150 cm− 1 and 1190 cm− 1)
and C–C–O antisymmetric or C–O symmetric stretching vibrations (at
1240 and 1270 cm−1). Moreover, important absorption bands are ob-
served due to C–H bending in O–CH3 (at 1438 cm−1 and 1465 cm−1)
and C–H bending in C–CH3 (at 1400 cm−1 and 1452 cm−1). The strong
absorption line at 1730 cm−1 is attributed to carbonyl stretching vibra-
tion ν(C = O). In the spectral region 2840–2950 cm− 1, the C–H
stretching vibrations in CH3 and CH2 are seen. Furthermore, the ν(OH)
band is present around 3200–3600 cm− 1. The effects of the plasma
treatments are directly observed in the ATR-FTIR spectra recorded for
PMMA-H and PMMA-D samples. At first glance these spectra present
near similar features, still some differences are present. Thus, in both
spectra is observed an increase of the hydrocarbons (CH2, CH3) in
respect with C = O bond absorptions, suggesting the polymeric side
chain degradation combined with cross linking effects [25]. Supplemen-
tary, both types of plasma treatments induce the broadening of the
carbonyl absorption ν(C=O) peak; a similar result is also reported in
[39]. Thereby, in the inset presented in Fig. 7 can be easily identified
two supplementary peaks at 1703 cm−1 and 1735 cm−1 (marked
with stars); these can be associated with other oxygen containing
groups (like ketone, carboxyl, aldehyde and lactones). We can observe
that humid Ar plasma is more efficient in inducing the broadening of
the ν(C=O) peak. In addition, when compared to the untreated (REF)
sample, the plasma treated ones present stronger absorption of the
 T. Acsente et al. / Thin Solid Films 614 (2016) 25–30
Fig. 6. SEM images of the: a) REF, b) PMMA-H and c) PMMA-D samples.
Fig 7. ATR-FTIR spectra of the samples treated in dry (PMMA-D) and humid (PMMA-H) Ar
plasma and of the untreated one (REF). The spectra were normalized in respect to C=O
peak intensity.
29
OH band (3100–3500 cm−1), suggesting the addition of the OH func-
tional groups on the sample surface. In the case of humid plasma treat-
ments these OH groups originate from the OH radicals produced inside
the plasma source in the discharge region while for the dry plasma
treatment, these groups originate from the ambient water vapors. The
OH band is slightly enlarged in the case of PMMA-H sample suggesting
that humid plasma treatment is more effective in attaching OH func-
tionalities on the treated PMMA surface. Modifications of the PMMA
absorption bands due to plasma treatments can be observed also in
other spectral regions. Thus, in the range 1100–1200 cm−1, the C–O–C
and C–C–O bonds are most affected by the dry Ar plasma treatment
while humid plasma does not affect them significantly.
4. Discussions
The increase of wettability was observed after sample treatment
either with dry or humid plasma. This effect is due to combined rough-
ening and chemical modification of the surface [35]. However, Fig. 3 re-
veals that after one scan of the polymeric surface, the WCA value is
much smaller for the optimized (i.e. 100 sccm bubbled Ar) humid plas-
ma treatment (WCA = 35°) when compared to the dry plasma one
(WCA = 53°). Only after six scans with dry Ar APPJ, the WCA becomes
comparable with that obtained with humid APPJ at one scan. AFM and
SEM measurements show larger roughening of the sample treated at
six scans in dry plasma (sample PMMA-D, RMS = 32.5 nm, Fig. 5c)
when compared with that treated at 1 scan in humid plasma (sample
PMMA-H, RMS = 27.1 nm, Fig. 5b). In fact, the humid plasma treatment
has a very small roughening effect on the treated surface (the untreated
REF sample has RMS = 24.7 nm, see Fig. 5a). These measurements indi-
cate that chemical changes of the treated surface are responsible for the
more efficient humid plasma treatment. Indeed, the ATR-FTIR results
show that both types of plasma treatments produce the polymeric
side chain degradation combined with cross linking effects, and also at-
tachment of new polar functionalities on the sample surface (oxygen
containing groups derived from C = O ester and OH), promoting the
surface hydrophilicity. The ATR-FTIR spectra of the PMMA-H and
PMMA-D are near similar, suggesting close chemical states of the sam-
ples (the small differences between them were mentioned in
Section 3.2.3). Still, it is important to remind that the PMMA-H sample
was treated for 10 min (one scan) while PMMA-D for 1 h (6 scans).
The observed differences between dry/humid Ar plasma treatments
can be interpreted in the frame of the two process mechanisms
proposed in [22] for functionalization of the PMMA surfaces using low
pressure Ar/H2O plasma. According to this mechanism, the first type
of processes is produced by Ar ions and consists in reduction (erosion)
of the PMMA surfaces, accompanied by cross linking and apparition of
intermediate compounds. While our plasma is generated at atmospher-
ic pressure, it is reasonable to consider that not only Ar, but also other
species (like O2, N2) take part to reduction of the polymeric surface.
The second type of processes consists in activation of the reduced
PMMA layer by attachment of oxygen rich functional groups, including
OH radicals, responsible for the increase of the wettability.
In view of this model, both plasma jets (either humid or dry) reduce
the polymeric surface, creating sites for the attachment of OH radicals.
Still, during the first scan, only the humid plasma jet will provide
enough OH radicals directly on the reduced polymer surface, such as
to activate the surface. This supposition is suggested by the values of
the WCA after the first scan (35° for humid Ar plasma and 53° for dry
plasma) and it is supported by the increased emission of the OH radical
recorded in the humid plasma jet for low amounts of water vapors
injected in the discharge (see Fig. 2). Supplementary, the enhanced
UV emission of the humid plasma jet may contribute to the activation
of the surface by creation of additional free radicals [7]. During the dry
Ar plasma treatment the OH radicals originate from the ambient atmo-
sphere their amount being smaller when compared to humid plasma;
this fact is also sustained by OES results (see Fig. 2). For this reason,
30 T. Acsente et al. / Thin Solid Films 614 (2016) 25–30
the number of scans has to be increased for obtaining a comparable
surface activation; nevertheless the roughening of surface is enhanced
in this case.
5. Conclusions
Surface modification of PMMA polymeric foils was performed using
atmospheric pressure plasma jets operated either with dry or humid Ar.
Both treatments enhance the wettability of the polymeric foils. Still,
humid plasma jet treatments (using small amounts of water vapors)
are more efficient. Thus, the decrease of water contact angle from 80°
to 35° after 10 min of treatment with humid Ar plasma is obtained
after 1 h of treatment in dry Ar plasma. The higher efficiency of the
humid plasma is assigned to the higher amount of the OH radicals
reaching the surface, leading to a faster attachment of these radicals to
the active sites produced by plasma. The surface roughening is also ob-
served, however its role appears to be minor, except for long treatments
in dry argon. Atmospheric pressure plasma jet treatments with humid-
ified Ar appear as a promising method for improving the wettability
of the PMMA foils in a short period of time, with minor surface degrada-
tion, in absence of pollutant chemicals.
Acknowledgments
The authors are grateful for the financial support from the Romanian
Ministry of Education and Research under the contracts PN-II-ID-PCE-
2012-4-0629 and PN 09 39 04 02.
References
[1] M. F. Ashby, Materials Selection in Mechanical Design, Third edition, Elsevier, 2005,
ISBN 0-7506-6168-2.
[2] J.Y. Cheng, C.W. Wei, K.H. Hsu, T.H. Young, Direct-write laser micromachining and
universal surface modification of PMMA for device development, Sensors Actuators
B Chem. 99 (2004) 186–196.
[3] A.M. Moyano, J.M. Martín-Martínez, Surface treatment with UV-ozone to improve
adhesion of vulcanized rubber formulated with an excess of processing oil, Int. J.
Adhes. Adhes. 55 (2014) 106–113.
[4] T.M. Johnson, D. Ross, M. Gaitan, L.E. Locascio, Laser modification of preformed
polymer microchannels: application to reduce band broadening around turns sub-
ject to electrokinetic flow, Anal. Chem. 73 (2001) 3656–3661.
[5] N. Inagaki, Plasma Surface Modification and Plasma Polymerization, Technomic
Publishing, Lancaster, PA, 1996.
[6] K.S. Siow, L. Britcher, S. Kumar, H.J. Griesser, Plasma methods for the generation of
chemically reactive surfaces for biomolecule immobilization and cell colonization—a
review, Plasma Process. Polym. 3 (2006) 392–418.
[7] R. Wolf, A.C. Sparavigna, Role of plasma surface treatments on wetting and adhe-
sion, Engineering 2 (2010) 397–402.
[8] M. Šíra, D. Trunec, P. Stahel, V. Buršíková, Z. Navrátil, J. Buršík, Surface modification
of polyethylene and polypropylene in atmospheric pressure glow discharge, J. Phys.
D. Appl. Phys. 38 (2005) 621–627.
[9] C. Sarra-Bournet, S. Turgeon, D. Mantovani, G. Laroche, A study of atmospheric
pressure plasma discharges for surface functionalization of PTFE used in biomedical
applications, J. Phys. D. Appl. Phys. 39 (2006) 3461–3469.
[10] J. Wang, C. Chen, S.M. Buck, Z. Chen, Molecular chemical structure on poly(methyl
methacrylate) (PMMA) surface studied by sum frequency generation (SFG) vibra-
tional spectroscopy, J. Phys. Chem. B 105 (2001) 12118–12125.
[11] D. E. Gregonis, J. D. Andrade, Surface and Interfacial Aspects of Biomedical Polymers,
Surface Chemistry and Physics, Plenum Press, New York, 1985, ISBN 978-1-4684-
8612-4.
[12] T.M. Long, S. Prakash, M.A. Shannon, J.S. Moore, Water-vapor plasma-based surface
activation for trichlorosilane modification of PMMA, Langmuir 22 (2006)
4104–4109.
[13] A.T. Farcasiu, E.C. Stancu, M.D. Ionita, O.C. Andrei, G. Dinescu, Change of acrylic
surfaces umectability by plasma treatment, Ro J Stomatol, LVII2011 262–266.
[14] P. Groning, M. Collaud, G. Dietler, L. Schlapbach, Plasma modification of
polymethylmethacrylate and polythyleneterephthalate surfaces, J. Appl. Phys. 76
(1994) 887–892.
[15] A. Chiper, G. Borcia, M. Dobromir, G. Popa, He and Ar dielectric barrier discharge for
surface modification of polymers, J. Adv. Res. Phys. 2 (2012) 021104.
[16] O. Ozgen, E.A. Aksoy, V. Hasircia, N. Hasircia, Surface characterization and radical
decay studies of oxygen plasma-treated PMMA films, Surf. Interface Anal. 45
(2013) 844–853.
[17] S.H. Mortazavi, M. Ghoranneviss, S. Pilehvar, S. Esmaeili, S. Zargham, S.E. Hashemi,
H. Jodat, Effect of low-pressure nitrogen DC plasma treatment on the surface
properties of biaxially oriented polypropylene, poly (methyl methacrylate) and
polyvinyl chloride films, Plasma Sci. Technol. 15 (2013) 362–367.
[18] T. Homola, J. Matoušek, B. Hergelová, M. Kormunda, L.Y.L. Wu, M. Černák, Activation
of poly(methyl methacrylate) surfaces by atmospheric pressure plasma, Polym.
Degrad. Stab. 97 (2012) 886–892.
[19] K. Schroder, A. Meyer-Plath, D. Keller, W. Besch, G. Babucke, A. Ohl, Plasma-induced
surface functionalization of polymeric biomaterials in ammonia plasma, Contrib.
Plasma Phys. 41 (2001) 562–572.
[20] N. Médard, J.C. Soutif, F. Poncin-Epaillard, CO2, H2O, and CO2/H2O plasma chemistry
for polyethylene surface modification, Langmuir 18 (2002) 2246–2253.
[21] Z. Fang, Y. Liu, K. Liu, T. Shao, C. Zhang, Surface modifications of
polymethylmetacrylate films using atmospheric pressure air dielectric barrier
discharge plasma, Vacuum 86 (2012) 1305–1312.
[22] J.T. Hook, J.A. Gardella, L. Salvati, Multitechnique surface spectroscopic studies of
plasma-modified polymers I: H2O/Ar plasma-modified polymethylmethacrylates,
J. Mater. Res. 2 (1987) 117–131.
[23] C.M. Weikart, H.K. Yasuda, Modification, degradation, and stability of polymeric
surfaces treated with reactive plasmas, J. Polym. Sci. A Polym. Chem. 38 (2000)
3028–3042.
[24] J.H. Lee, J.W. Park, H.B. Lee, Cell adhesion and growth on polymer surfaces with
hydroxyl groups prepared by water vapour plasma treatment, Biomaterials 12
(1991) 443–448.
[25] U. Schulz, P. Munzert, N. Kaiser, Surface modification of PMMA by DC glow dis-
charge and microwave plasma treatment for the improvement of coating adhesion,
Surf. Coat. Technol. 142-144 (2001) 507–511.
[26] A.Y. Nikiforov, A. Sarani, C. Leys, The influence of water vapor content on electrical
and spectral properties of an atmospheric pressure plasma jet, Plasma Sources Sci.
Technol. 20 (2011) 015014.
[27] G. Dinescu, E.R. Ionita, Radiofrequency expanding plasmas at low, intermediate and
atmospheric pressure and their applications, Pure Appl. Chem. 80 (2008)
1919–1930.
[28] E.R. Ionita, M.D. Ionita, C.E. Stancu, M. Teodorescu, G. Dinescu, Small size plasma
tools for material processing at atmospheric pressure, Appl. Surf. Sci. 255 (2009)
5448–5452.
[29] A. Morozov, R. Krücken, T. Ottenthal, A. Ulrich, J. Wieser, Ultraviolet emission from
argon water-vapor mixtures excited with low-energy electron beams, Appl. Phys.
Lett. 86 (2005) 011502.
[30] C. Cheng, S. Jie, X. De-Zhi, X. Hong-Bing, L. Yan, F. Shi-Dong, M. Yue-Dong, C. Paul K,
Atmospheric pressure plasma jet utilizing Ar and Ar/H2O mixtures and its applica-
tions to bacteria inactivation, Chin. Phys. B 23 (2014) 075204.
[31] M.D. Ionita, M. Teodorescu, T. Acsente, M. Bazavan, E.R. Ionita, G. Dinescu, Remote
surface modification of polymeric foils by expanding atmospheric pressure radiofre-
quency discharges, Rom. J. Physiol. 56 (2011) 132–138.
[32] M.D. Ionita, M. Teodorescu, C. Stancu, E.C. Stancu, E.R. Ionita, A. Moldovan, T.
Acsente, M. Bazavan, G. Dinescu, Surface modification at atmospheric pressure in
expanding RF plasmas generated by planar dielectric barrier discharges, J.
Optoelectron. Adv. Mater. 12 (2010) 777–782.
[33] S. Yang, H. Yin, Two atmospheric-pressure plasma sources for polymer surface
modification, Plasma Chem. Plasma Process. 27 (2007) 23–33.
[34] C. Canal, R. Molina, E. Bertra, P. Erra, Wettability, ageing and recovery process of
plasma-treated polyamide 6, J. Adhes. Sci. Technol. 18 (2004) 1077–1089.
[35] M.R. Sanchis, V. Blanes, M. Blanes, D. Garcia, R. Balart, Surface modification of low
density polyethylene (LDPE) film by low pressure O2 plasma treatment, Eur.
Polym. J. 42 (2006) 1558–1568.
[36] B. H. Stuart, Infrared Spectroscopy: Fundamentals and Applications, University of
Technology, Sydney, Australia, John Wiley & Sons Ltd, 2004, ISBN: 978-0-470-
85428-0
[37] H.A. Willis, V.J.I. Zichy, P.J. Hendra, The laser-Raman and infra-red spectra of poly
(methyl methacrylate), Polymer 10 (1969) 737–746.
[38] M.R.H. Mas Haris, S. Kathiresan, S. Mohan, FT-IR and FT-Raman spectra and normal
coordinate analysis of poly methyl methacrylate, Der Pharma Chemica, 22010
316–323.
[39] A. Kondyurin, M. Bilek, Etching and structure changes in PMMA coating under argon
plasma immersion ion implantation, Nucl. Inst. Methods Phys. Res. Sect. B Beam
Interact. Mater. Atoms 269 (2011) 1361–1369.