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Research Article

Received: 14 August 2007

Revised: 25 September 2007

Accepted: 25 September 2007

Published online in Wiley Interscience: 26 November 2007

(www.interscience.com) DOI 10.1002/sia.2611

Surface characterization of plasma-modified


polyethylene by contact angle experiments
and ATR-FTIR spectroscopy
N. De Geyter, R. Morent and C. Leys
Polymers such as polyethylene (PE) have a low surface free energy and therefore often require a modification of their surface
properties before any use. Nonthermal plasma treatment is a convenient and environmentally friendly way to obtain these
modifications by introducing new chemical groups at the surface without affecting the bulk properties. Therefore, in this article,
a PE film is treated with a dielectric barrier discharge (DBD) operating in air at medium pressure (5.0 kPa). The surface properties
of the plasma-treated PE films are characterized using contact angle measurements, surface free energy calculations and
ATR-FTIR spectroscopy. The polymer films show a remarkable increase in surface free energy after plasma treatment. ATR-FTIR
spectroscopy of the plasma-treated PE films reveals that plasma treatment introduces oxygen-containing functionalities, such
as ketones, aldehydes, alcohols and carboxylic acids on the PE surface leading to the increased surface free energy. Copyright
c 2007 John Wiley & Sons, Ltd.

Keywords: dielectric barrier discharge; polyethylene; surface free energy and ATR-FTIR spectroscopy

Introduction

608

Polyethylene (PE) is one of the most widespread polymers


used for industrial and medical applications due to its excellent
material properties (low density, high flexibility and high chemical
resistance).[1] However, despite these excellent characteristics, PE
is often unsuitable for use due to its low surface free energy,
leading to poor wettability and poor adhesion.[2] For optimum
adhesion, the surface free energy of the polymer should be larger
than that of the material to be bonded with. Similarly, for effective
wetting by a liquid, the surface free energy should exceed the
surface tension of the liquid. The surface free energy of PE is
approximately 32 mJ/m2 whereas the surface tensions of typical
water-based adhesives are 4450 mJ/m2 and those of water-based
inks are 5456 mJ/m2 . As a result, PE surface modification is usually
required to increase the overall surface free energy above that of
these classes of adhesives and inks, thereby enabling bonding and
printing.[3]
An increase in surface free energy can be obtained using
wet chemical processes; however, ecological requirements force
the industry to search for alternative environmentally friendly
methods.[4] Recently, plasma treatment of polymers has been
gaining popularity as a surface modification technique since it
does not require the use of water and chemicals. Therefore, it
can be considered as an environmentally benign technology.[5]
Moreover, it is a versatile technique: a large variety of specific
functional groups can be attached to the polymer surface
depending on the type of gas or precursor used during plasma
treatment.[6]
Many surface treatment techniques, such as plasma treatment,
limit the thickness of the transformed layer to approximately
10 nm or less.[7,8] In most practical cases, the treated surface
layer is located on top of the bulk material, the amount of
which is usually several orders of magnitude larger. In this
situation, most of the classical tools for chemical structural

Surf. Interface Anal. 2008; 40: 608611

analysis [such as nuclear magnetic resonance (NMR) and attenuated total reflectance Fourier transform infrared (ATR-FTIR)
spectroscopy] are not able to detect structural changes after plasma surface treatments. The amount of material which
has to be analyzed is just too small for NMR spectroscopy
and the sampling depth of ATR-FTIR techniques is usually
too large to detect structural alteration upon plasma surface treatment.[8] Only in some experiments with ultrathin
polymer layers, IR spectroscopy has been used successfully
to obtain structural information of plasma-treated polymer
surfaces.[9,10]
However, in this article, it will be shown that by choosing
the appropriate ATR accessory, ATR-FTIR spectroscopy is able
to detect structural alteration upon plasma surface treatment.
This work focuses on ATR-FTIR analysis of plasma-modified PE
films. The plasma treatment is performed using a dielectric barrier
discharge (DBD) operating in air at medium pressure (5.0 kPa).
Generally, a DBD is generated by covering at least one of the metal
electrodes in a parallel-plate assembly with a dielectric material
and by applying a sufficiently large alternating voltage to the
electrodes.[11] This results in a temporally and spatially nonuniform
discharge in the gap between the electrodes, consisting of a
series of filamentary discharges.[11] The surface properties of the
plasma-treated PE films are characterized using contact angle
measurements, surface free energy calculations and ATR-FTIR
spectroscopy.

Correspondence to: N. De Geyter, Department of Applied Physics, Research Unit


Plasma Technology (RUPT), Faculty of Engineering, Ghent University, Jozef
Plateaustraat 22, B-9000 Ghent, Belgium. E-mail: nathalie.degeyter@ugent.be
Department of Applied Physics, Research Unit Plasma Technology (RUPT),
Faculty of Engineering, Ghent University, Jozef Plateaustraat 22, B-9000 Ghent,
Belgium

c 2007 John Wiley & Sons, Ltd.


Copyright 

Surface characterization of plasma-modified polyethylene

Experimental Setup
Surface treatment
Plasma treatment of the PE films is carried out using a DBD
reactor shown in Fig. 1. To generate the DBD, a sufficiently high
AC electrical field (frequency = 50 kHz) is applied between two
circular copper electrodes (diameter = 7 cm) placed within a
cylindrical enclosure. Both electrodes are covered with a glass
plate (thickness = 2 mm) and the distance between the two glass
plates is 4 mm. The upper electrode is connected to an AC high
voltage source while the lower electrode is connected to earth
through a resistor R (100 ). The discharge power is measured
using a Lissajous figure[12] and is kept constant at 6 W. Between
the two glass plates, air (Air Liquide-Alphagaz 1) is fed into the
system at a rate of 100 sccm. The gas outlet is connected to
a rotary vane pump, which lowers the pressure in the chamber
to 5.0 kPa (medium pressure). During the experiment, a PE film
(Goodfellow-UK) with a thickness of 100 m is placed on the lower
glass plate and the pressure is maintained at 5.0 kPa by the use of
a valve.

to 7. The FTIR spectra are recorded using a liquid nitrogen-cooled


MCT (Mercury-Cadmium-Telluride) detector with a resolution of
4 cm1 and 128 scans are taken for each measurement.
The depth of penetration dp of the IR beam into the sample is
expressed by the following equation[14] :

dp =
2 (n21

sin
2

(1)

n22 ) 2

where = wavelength of the light, = angle of incidence of


the IR beam = 45 , n1 = refractive index of the crystal = 4.0,
n2 = refractive index of the sample (for PE: n2 = 1.51[15] ). With
the reflection element used in this article, the penetration depth
at 1000 cm1 is approximately 0.66 m according to Eqn (1). The
spectra shown in this article are corrected for the wavelength
dependence of the penetration depth and are the average of ten
measurements.

Results and Discussion

Contact angle measurements and surface free energy


calculations

Contact angle measurements and surface free energy


calculations

Wettability changes of the treated PE surfaces are characterized


by static contact angle measurements using the sessile drop
technique. The measurements are performed at room temperature
on a Kruss
using two
EasyDrop goniometer (Kruss-Germany)

different test liquids: distilled water and diiodomethane. The values


of the contact angles shown in this article are the average of at
least eight measurements. The surface free energy is determined
by the method of OwensWendtRabel and Kaelble. A complete
description of this method can be found in Ref. [13].

Figure 2 shows the evolution of the water and diiodomethane


contact angles on the PE films as a function of plasma treatment
time. As can be seen in Fig. 2, the water contact angle of the
untreated PE surface is 101.7 . This water contact angle can be
reduced to 53.5 after 5 s of plasma treatment. The untreated PE
surface has a diiodomethane contact angle equal to 55.6 and
this angle can be reduced to 38.5 after 5 s of plasma treatment.
Longer exposure times do not cause significant changes in contact
angle values, which means that saturation of plasma effect occurs.
The contact angles are measured over an extended area of the
treated sample and show a dispersion lower than 2.5 , which is
within experimental error. This implies that the surface treatment
is uniform at micron scales, despite the fact that the discharge
consists of a series of microdischarges.
The water and diiodomethane contact angles can be used to
calculate the surface free energy. Figure 3 shows the surface free
energy of the PE film for different plasma treatment times. The
untreated PE film has a surface free energy equal to 31.3 mJ/m2 .
The PE surface free energy increases as a function of plasma
treatment time and the maximum value of the surface free energy

ATR-FTIR analysis
Infrared analysis of the untreated and the plasma-treated PE
films is performed on a Bruker Vertex 70 spectrometer purged
with dry, CO2 free air. The spectrometer is equipped with a
multireflection variable angle horizontal ATR accessory (ATRMax
II Pike Technologies). The internal reflection element is a
germanium (Ge) crystal and the angle of incidence on the crystal is
set to 45 . The number of reflections within the Ge crystal is equal

Surf. Interface Anal. 2008; 40: 608611

Figure 2. Evolution of the water and diiodomethane contact angles on the


PE film as a function of plasma exposure time.

c 2007 John Wiley & Sons, Ltd.


Copyright 

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609

Figure 1. Experimental setup of the DBD (1. gas cylinder, 2. mass-flow


controller, 3. plasma chamber, 4. pressure gauge, 5. needle valve, 6. pump).

N. De Geyter, R. Morent and C. Leys

Figure 3. Surface free energy of the PE film as a function of plasma


treatment time.

(56.2 mJ/m2 ) is reached after 5 s of plasma treatment. As shown


in Fig. 3, this maximum value does not change significantly when
the treatment time is further increased.
It is known that air plasma treatment increases the surface free
energy of PE because of strong surface oxidation in the discharge.
Many authors[1,16 18] have performed XPS measurements on
plasma-modified PE films, showing the presence of oxygencontaining functionalities on the PE surfaces after air plasma
treatment. In this article, insights of the final oxide products will
be assessed by ATR-FTIR analyses and will be discussed hereafter.
ATR-FTIR analysis
The PE film is characterized by ATR-FTIR spectroscopy before and
after 10 s of plasma treatment. Figure 4(A) shows the ATR-FTIR
spectrum of the untreated PE. It has two large absorption peaks at
2920 and 2852 cm1 due to CH asymmetric and CH symmetric
stretching vibrations in CH2 respectively. The spectrum also
shows two smaller absorption peaks at 1466 and 723 cm1 .
The peak at 1466 cm1 can be attributed to CH deformation
vibrations in (CH2 )n while the peak at 723 cm1 is due to CC
rocking vibrations in (CH2 )n .[19]
The ATR-FTIR spectrum of the PE film after 10 s of plasma
treatment can be seen in Fig. 4(B). The spectrum is normalized
at 723 cm1 assuming that no chain scission occurs after plasma
treatment. Figure 4 clearly shows that the peaks at 2920 and

610

Figure 4. ATR-FTIR spectrum of the untreated PE film (A) and a 10 s plasmatreated PE film (B) in the region 4000700 cm1 .

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2852 cm1 significantly decrease after plasma treatment. Figure 4


also shows that a broad band appears between 3660 and
3350 cm1 ; this peak can be attributed to OH stretching
vibrations. The most remarkable difference after plasma treatment
can be seen in the region 18301150 cm1 . Figure 5 shows the
detailed ATR-FTIR spectra of the untreated PE film (A) and a 10 s
plasma-treated PE film (B) in the region 2000800 cm1 . As can
be seen in Fig. 5, a large peak at 1737 cm1 arises after treatment
due to C O stretching of ketones, aldehydes and carboxylic acids.
Moreover, a broadening of this large peak occurs at 1640 cm1 ,
which could be attributed to the presence of C C bonds (C C
stretching vibration). Plasma treatment of PE also leads to the
formation of a broad peak at 1357 cm1 . This peak can be due to
CH rocking vibrations of aldehydes, CH bending vibrations of
ketones and OH deformation vibrations. There is also a broad
peak appearing after treatment in the region 12601160 cm1 ,
which can be attributed to CO stretching vibrations in alcohols.
Besides these obvious changes in FTIR spectra before and after
plasma treatment, some minor differences can be seen at 1440
and 907 cm1 . The peak at 1440 cm1 is probably due to CO
stretching of carboxylic acids and OH deformation of carboxylic
acids and alcohols. The peak at 907 cm1 can be attributed to
the out-of-plane deformation of carboxylic acids and the CH
deformation of aldehydes and vinyl groups (CH CH2 ).
Taking into account the above results, one can conclude that
plasma treatment of PE in air leads to the formation of oxygencontaining functionalities, such as alcohols, aldehydes, ketones
and carboxylic acids on the PE surface. These results are in
accordance with the results of Gerenser[18] who studied plasmatreated PE samples by XPS and reported the presence of CO, C O
and OC O groups. Plasma treatment of PE also introduces vinyl
groups on the PE surface, which was also stated by Clouet and
Shi.[20] Oxygen atoms, OH radicals, UV photons and ions present
in the discharge abstract hydrogen atoms from the PE polymer
chains resulting in the formation of radicals. These radicals can then
react with molecular or atomic oxygen leading to the formation
of ketones, aldehydes, alcohols and carboxylic acids. However,
the created radicals can also react with each other leading to the
formation of vinyl groups.[20] The ATR accessory used in this article
can detect the surface oxidation at the top nanometer level despite
its high penetration depth (0.66 m). This is due to the fact that
the use of seven internal reflections enhances the sensitivity of
the ATR accessory toward components in low concentrations.[21]
As shown in this section, ATR-FTIR spectroscopy can provide

Figure 5. ATR-FTIR spectrum of the untreated PE film (A) and a 10 s plasmatreated PE film (B) in the region 2000800 cm1 .

c 2007 John Wiley & Sons, Ltd.


Copyright 

Surf. Interface Anal. 2008; 40: 608611

Surface characterization of plasma-modified polyethylene


qualitative information on plasma-modified PE surfaces. In order
to perform quantitative FTIR measurements, several options (e.g.
chemical derivatization) will be explored in the near future.

Conclusions
In this article, it was found that a DBD treatment in air at medium
pressure is an effective tool to increase the surface free energy
of PE; the surface free energy can be increased from 31.3 to
56.2 mJ/m2 after only 5 s of plasma treatment. This large increase
in surface free energy is due to oxidation of the surface in the
discharge; a wide range of reactive species is generated in the
plasma, which undergo consecutive chemical reactions, creating
oxygen-containing functionalities on the PE surface. As stated in
this article, ATR-FTIR spectroscopy can be used to detect these
oxygen-containing groups.

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c 2007 John Wiley & Sons, Ltd.


Copyright 

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