Coatings 09 00145 PDF

coatings
Article
Modification of Polyethylene by RF Plasma in
Different/Mixture Gases
Aya E. Abusrafa 1 , Salma Habib 1 , Igor Krupa 1 , Mabrouk Ouederni 2 and Anton Popelka 1, *
1 Center for Advanced Materials, Qatar University, P.O. Box 2713 Doha, Qatar;
aya_abusrafa94@yahoo.com (A.E.A.); salma.m.habib@hotmail.com (S.H.); igor.krupa@qu.edu.qa (I.K.)
2 QAPCO R&D–Qatar Petrochemical Company, P.O. Box 756 Doha, Qatar; m.ouederni@qapco.com.qa
* Correspondence: anton.popelka@qu.edu.qa; Tel.: +974-4403-5676

Received: 21 January 2019; Accepted: 11 February 2019; Published: 22 February 2019
Abstract: Herein, low-density polyethylene (LDPE) films were treated using radio-frequency plasma
discharge in the presence of air, nitrogen, oxygen, argon, and their mixtures to introduce new
chemical functionalities. The surface properties of treated LDPE were qualitatively and quantitatively
characterized using various analytical and microscopic techniques. It was found that the optimum
plasma treatment for LDPE occurs in the presence of air plasma at an exposure time of 120 s and
80 W of nominal power. The plasma formed layer had tendency to increasing thickness with
increasing treatment time up to 60 s using air and oxygen and even more with inert gases. An aging
study of plasma-treated LDPE samples stored in ambient air or water medium revealed the partial
hydrophobic recovery.
Keywords: RF plasma; polyethylene; surface modification
1. Introduction
Low-density polyethylene (LDPE) has become one of the most extensively used commodity
polymers in various technological applications, such as adhesives, microelectronics, coatings, thin-films,
catheters, medical implants, and orthopedic devices [1–7]. Its versatility is mainly attributed to its
outstanding material properties, including low density, ease of finishing, durability, flexibility, and
chemical resistance, as well as its current commercial availability. Although the bulk properties
of LDPE comply with various mechanical and thermal requirements, its surface properties are
undesirable. The LDPE surface is characterized by a low surface free energy that results in poor
wettability, adhesion and biocompatibility, making it unsuitable for several applications [4,7–10].
Surface free energy (wettability) of LDPE achieves values about 30 mJ/m2 . However, for applications
such as printing or lamination processes, surface free energy is required to be greater than 37 or
42 mJ/m2 , respectively [11]. Moreover, untreated LDPE has a predisposition to a biofouling effect.
When pristine LDPE is implanted in a biological environment, biofouling is most likely to occur as
a result of poor biocompatibility [12]. To overcome similar issues, there has been a longstanding
interest to chemically or physically modify and control the surface properties of polymeric materials by
incorporating polar groups onto the surface to enhance hydrophilicity, adhesion, and biocompatibility
characteristics [2,13,14]. The incorporation of new polar functionalities onto the polymer surface can be
performed using wet chemical methods by acid etching or chemical oxidation. Nevertheless, practical
use of those methods is complex and environmentally unfriendly as it requires handling and disposal of
harmful chemicals. Therefore, for ecological requirements, different technologies have been developed
to replace wet finishing processes in several domains to modify the surface properties of polymeric
films without generating harmful wastes [15]. Low pressure reactive gas glow discharge, known as cold
plasma, technology, is prevalently utilized to enhance the surface properties of polymers by changing
Coatings 2019, 9, 145; doi:10.3390/coatings9020145 www.mdpi.com/journal/coatings

Coatings 2019, 9, 145 2 of 24
the chemical composition and morphology [16]. Its usage has become one of the most versatile and
effective means for surface modification applied throughout the food industry, physics, chemistry,
material science, and medicine [17]. Several other surface modification strategies include flame, UV,
and direct fluorination [18–23]. However, plasma technology has gained more preference over other
techniques because it represents an alternative effective, clean, dry, economical, and environmentally
friendly method. Another distinctive attribute of this technique is easy and fast processing, as the
surface treatment is achieved in a single step without requiring further surface treatments. Apart from
surface modification, plasma is enormously employed for cleaning, decontamination and sterilization
applications [16].
Different treatment methods, as well as working gases and plasma sources, are used for
surface modification. Gaseous corona discharge, radio-frequency (RF) discharge, dielectric barrier
discharge, microwave discharge, direct current, and laser-based sources are the most common plasma
sources available today [4,24]. RF plasma systems provide homogenous surface treatments that
can be employed for three-dimensional and complex objects and are hence not confined to treating
only flat thin 2D surfaces [25]. Plasma treatment leads to a formation of a new layer of treated
materials with different properties compared to the bulk. During plasma treatment, an ionized gas
is formed, consisting of different active species including electrons, positive and negative ions, free
radicals, photons and neutral species with high energy [26–28]. The bombardment of the polymer
surface by these highly energetic species initiates reactions that ultimately modify the chemical and
physical properties of the surface. Several surface processes, such as etching, ablation, cross-scission,
cross-linking, and degradation result in the formation of a new layer [29–35]. Effects could be either
individual or combined based on the applied plasma conditions. In a typical modification process,
the initial step involves breaking the existing chemical bonds and forming new ones, resulting
in new groups at the surface, which then undergo further oxidation as the surface is exposed to
air [24]. Monomers also undergo plasma polymerization because the treated surface is rich in
radicals. Furthermore, plasma treatment is known to immensely enhance surface properties, while its
penetration depth is limited to only a few nanometers [36–40]. In fact, the thinness/surface-specificity
of the newly formed layer at the polymer interface is often regarded as an advantage of plasma
treatment as the propitious bulk properties are preserved.
In this work, we report a thorough study of the surface properties of low density polyethylene
(LDPE) films modified by low-temperature RF plasma using pure gases and their mixtures, namely,
air, argon, oxygen, and nitrogen. An improvement of LDPE hydrophilicity with maximum efficiency
using this technology was examined and can be applicable in printing, laminating, or antibiofouling
applications. This improvement implied the determination of optimum processing conditions by
changing the nominal power, exposure time, and gas type/mixtures. A comparison was done between
the different gases in terms of surface wettability and aging behavior over time. Different inert
(nitrogen, argon) and reactive gases (oxygen, air) were selected to analyze their effect on the resulted
wettability of the LDPE surface. Generally, reactive gases are more susceptible to functionalization
reactions, while inert gases predominantly lead to the crosslinking structures by recombination
reactions of radicals or creation of alkenes (disproportionation reactions of radicals). However, after
plasma treatment of LDPE using inert gases, functionalization reactions occurred between plasma
generated radicals and oxygen from ambient air. Particular attention was given to find the extent to
which wettability is affected by the chemistry and morphology on the surface area.
2. Materials and Methods

Commercial grade low-density polyethylene (LDPE) FE8000 was supplied in pellet form by Qatar
petrochemical company (QAPCO, Doha, Qatar). Thin homogenous films approximately 0.41 mm thick
were prepared by compression molding using an industrial mounting press machine (Carver, Wabash,
IN, USA). The pellets were melted at 160 ◦ C and compressed for 2 min using 0.2 MPa of pressure
while maintaining the set temperature to obtain a film with a desired smooth surface. Samples were
Coatings 2019, 9, 145 3 of 24
Coatings 2019, 9 FOR PEER REVIEW 3

cooled down to RT using water before being peeled of the plates. The LDPE films were cleaned with
acetone to remove any additives, residuals or other possible contaminants from the molding process
Small strips (5 cm × 1 cm) were cut out and directly used for surface treatment and subsequent
that might affect the surface properties and were then dried in air for 20 min at RT. Small strips (5 cm
analyses.
× 1 cm) were cut out and directly used for surface treatment and subsequent analyses.
Ethylene glycol (>98% FLUKA, Morris Plains, NJ, USA), formamide (>98% FLUKA), ultra-pure
Ethylene glycol (>98% FLUKA, Morris Plains, NJ, USA), formamide (>98% FLUKA), ultra-pure
water (prepared by Purification System Direct Q3, Millipore Corporation, Molsheim, France), and
water (prepared by Purification System Direct Q3, Millipore Corporation, Molsheim, France), and
acetone (99.9% Scharlau, Barcelona, Spain) were used as testing liquids for wettability analyses.
acetone (99.9% Scharlau, Barcelona, Spain) were used as testing liquids for wettability analyses.
2.1. Plasma Treatment
2.1. Plasma Treatment
Plasma treatment of LDPE films was performed using an enclosed low-temperature plasma
Plasma treatment of LDPE films was performed using an enclosed low-temperature plasma
generating system, Venus75-HF (Plasma Etch Inc, Carson, CA, USA). The plasma excited species
generating system, Venus75-HF (Plasma Etch Inc, Carson, CA, USA). The plasma excited species
were generated using an RF generator operating at a frequency of 13.56 MHz. The chamber of the
were generated using an RF generator operating at a frequency of 13.56 MHz. The chamber of the
plasma system was evacuated to a pressure of approximately 0.2 Torr using a rotary vacuum pump
plasma system was evacuated to a pressure of approximately 0.2 Torr using a rotary vacuum pump
before plasma ignition. Optimization of the treatment process was carried out by varying the nominal
before plasma ignition. Optimization of the treatment process was carried out by varying the nominal
power, treatment time and working gas to obtain the maximum level of hydrophilicity in the LDPE
power, treatment time and working gas to obtain the maximum level of hydrophilicity in the LDPE
surface. The applied nominal power varied from 50 to 120 W, and the range of treatment time was
surface. The applied nominal power varied from 50 to 120 W, and the range of treatment time was
from 10 to 180 s at a constant optimal nominal power of 80 W. The gas flow rate was 10 cm 3·min−1.
from 10 to 180 s at a constant optimal nominal power of 80 W. The gas flow rate was 10 cm ·min−1 .
3
The film surfaces were treated from both sides using four different gases, namely, air, oxygen, argon,
The film surfaces were treated from both sides using four different gases, namely, air, oxygen, argon,
and nitrogen, and their mixtures with different ratios. Repeatability of the plasma treatment process
and nitrogen, and their mixtures with different ratios. Repeatability of the plasma treatment process of
of the LDPE surface was proven by contact angle measurements of three different LDPE samples
the LDPE surface was proven by contact angle measurements of three different LDPE samples treated
treated at 80 W for 120 s, which were carefully controlled by PC software Plasma Etch v1.3.0. The
at 80 W for 120 s, which were carefully controlled by PC software Plasma Etch v1.3.0. The standard
standard deviation of surface free energy obtained from three independent measurements was less
deviation of surface free energy obtained from three independent measurements was less than 3% of
than 3% of the mean indicating high reproducibility of the obtained results. The single step
the mean indicating high reproducibility of the obtained results. The single step modification process
modification process using RF plasma is shown in Figure 1.
using RF plasma is shown in Figure 1.
Figure
Figure 1. Schematic
1. Schematic diagram
diagram of the modification
of the surface surface modification process
process using using radio-frequency
radio-frequency (RF) plasma(RF)
setup.
plasma setup.
2.2. Surface Wettability Measurements
2.2. Surface Wettability Measurements
The changes in hydrophilicity induced after plasma treatment of LDPE films were evaluated by
The changes in hydrophilicity induced after plasma treatment of LDPE films were evaluated by
static contact angle measurements using the sessile drop method. Surface energy analysis system
static contact angle measurements using the sessile drop method. Surface energy analysis system
OCA35 (DataPhysics, Filderstadt, Germany) equipped with CCD camera was employed for this
OCA35 (DataPhysics, Filderstadt, Germany) equipped with CCD camera was employed for this
purpose. Water, formamide and ethylene glycol were used as testing liquids to evaluate the total
purpose. Water, formamide and ethylene glycol were used as testing liquids to evaluate the total surface
surface free energy, polar and dispersive components using the conventional Owens-Wendt-Rabel-
free energy, polar and dispersive components using the conventional Owens-Wendt-Rabel-Kaelble
Kaelble method by considering a geometric mean of the polar (γsp) and dispersive (γsd) components
method by considering a geometric mean of the polar (γs p ) and dispersive (γs d ) components of the
of the surface free energy of solid γs = γsp + γsd and surface tension components of liquid (polar-γ lp
surface free energy of solid γs = γs p + γs d and surface tension r components of liquid (polar-γl p and
γγdγγd − 2− 2γ γ γ p. γBy
q
and dispersive-γ ld) of liquid γsl = γs + γl − 2 p the subsequent substitution in the

d
dispersive-γ l ) of liquid γsl = γs + γl − 2 s l s l . By the subsequent substitution
Young
in equation
the Young γs = γγsls += γ
equation γlcosθ, a linear
+ γ cosθ, equation
a linear of the
equation of type y = ymx
the type + c+isc is
= mx obtained (γ(γ
obtained l(1 +
(1
sl l l
cosθ))/(2 γ )= γ γ / γ + γ . A droplet of approximately 3 µL from each testing
liquid was placed on air-facing samples. The contact angle was calculated approximately after 3 s to
allow thermodynamic equilibrium between the liquid and the sample interface to be reached. The
Coatings 2019, 9, 145 4 of 24
q r r q
p p
γld ) = γl )/(γld

+ cosθ))/(2 γs + γsd . A droplet of approximately 3 µL from each
testing liquid was placed on air-facing samples. The contact angle was calculated approximately after
3 s to allow thermodynamic equilibrium between the liquid and the sample interface to be reached.
The reported value for each testing liquid corresponds to the mean of at least five measurements taken
on different parts of the substrate surface.
2.3. Peel Test Analysis

A 90◦ peel test was performed to measure the adhesion characteristics of LDPE samples in terms
of the peel resistance using a standard Lloyd 1K Lf plus-UTM testing machine (Lloyd Instruments,
West Sussex, UK). Samples of 19 mm width and 6 cm length were attached to a polypropylene tape
containing poly(2-ethylhexyl acrylate) adhesive (Scotch tape). The test was conducted with Scotch
tape pressed on to the top of the treated LDPE surface. The unboned end of the testing tape was peeled
off at 90◦ at a crosshead speed of 10 mm·min−1 . The test was stopped after 6 min when the tape was
completely detached from the LDPE surface, and six separate readings were carried out to obtain
average values of peeling force.
2.4. Surface Chemistry Characterization

Fourier transform infrared spectroscopy with attenuated total reflectance mode (FTIR-ATR) was
used to qualitatively investigate chemical composition changes of plasma treated LDPE surfaces. FTIR
Spectrometer Frontier (PerkinElmer, Waltham, MA, USA) equipped with a ZnSe crystal was used for
these analyses, capturing data from 1.66 µm penetration depth. The spectra in the 4000–550 cm−1
range were obtained using an average of 8 scans with a resolution of 4 cm−1 .
Chemical composition changes caused by corona treatment of the LDPE surface were quantified
by X-ray photoelectron spectroscopy (XPS). The XPS system AXIS (Kratos Analytical, Manchester, UK)
was used for this study. The XPS system contains a spherical mirror analyzer and a delay-line detector
for fast chemical composition screening, ensuring high spectral resolution and sensitivity. This system
allows for analyzing data from 1–10 nm of sampling depth.
2.5. Surface Morphology Analysis

The surface morphology of LDPE films before and after plasma treatment was assessed by
performing profilometry analysis using an optical surface metrology confocal system (profilometer),
Leica DCM8 (Leica Microsystems, Wieselaar, Germany). This optical system was used for high accuracy
surface profiling and to investigate morphological changes induced by plasma treatment on the film
surfaces. Images of size 29.22 µm × 21.99 µm were scanned using 100× magnification objective and
6× zooming. Surface roughness was quantitatively characterized in terms of arithmetic mean height
(Sa ), which was calculated over the entire measured array.
Detailed information about three-dimensional changes in the surface topography of LDPE surface
after plasma treatment was obtained using atomic force microscopy (AFM). The AFM device MFP-3D
(Asylum Research, Abingdon, Oxford, UK) was used in these experiments. Scanning was carried out
under ambient conditions using a silicon probe (Al reflex coated Veeco model–OLTESPA, Olympus,
Tokyo, Japan) in the tapping mode in air (AC mode), allowing for obtaining images from 10 × 10 µm2
surface area. Moreover, the roughness parameter value (Ra ) was calculated from the AFM images
using the Z-Sensor.
Scanning electron microscopy (SEM) was used to obtain 2D images of the plasma modified
surfaces. For this purpose, a Nova NanoSEM 450 microscope (FEI, Hillsboro, OR, USA) was used.
A thin Au layer a few nanometers thick was sputter-coated onto LDPE samples to obtain high resolution
images and to avoid the accumulation of electrons on the measured layer.
Coatings 2019, 9, 145 5 of 24
2.6. Plasma Film Thickness Measurement

Thickness measurements were performed using an F20 film thickness analyzer (Filmetrics,
San Diego, CA, USA) to evaluate the increase in the plasma formed layer thickness. As a reference
sample, 4.5 mm thick LDPE substrate (refractive index 1.5) was placed on a sample stage with an
Coatings 2019,lens
adjustable 9 FOR PEER under
height REVIEWa UV light source. Measurements of plasma treated LDPE were carried out5
in air by including a refractive index of 1.4, which generally decreases with RF plasma treatment [41] as
probably the result of an incorporation of oxygen functional groups, or the presence of low-molecular
probably the result of an incorporation of oxygen functional groups, or the presence of low-molecular
weight oxidative products. The data were collected from the near-UV and visible light regions
weight oxidative products. The data were collected from the near-UV and visible light regions
(wavelength range of 380–1050 nm). The spectrum was analyzed by varying the measured
(wavelength range of 380–1050 nm). The spectrum was analyzed by varying the measured parameters
parameters to obtain the best fit between the theoretical and measured data using FILMeasure
to obtain the best fit between the theoretical and measured data using FILMeasure software v7.19.0.
software v7.19.0. At least five measurements from different areas were taken for each sample, and an
At least five measurements from different areas were taken for each sample, and an average value
average value was reported.
was reported.
3.
3. Results
Results and
and Discussion
Discussion
3.1. Surface Wettability Analysis

The wetting behavior changes
changes of LDPE surfaces exposed to plasma treatment using different
gases and their mixtures were examined using contact angle measurements. Several Several key
key parameters,
parameters,
which are crucial in the plasma
plasma treatment
treatment process,
process, including
including nominal
nominal power,
power, gas
gastype/mixture,
type/mixture, and
exposure time, have been varied to analyze the optimum treatment process. An initial optimization
of the plasma treatment was achieved by analyzing the influence of the nominal power on changes
in surface
surface wettability.
wettability. Series
Seriesof oftreatments
treatmentshave
havebeen
beencarried
carriedout
outininthe
thepresence
presenceofofairairplasma
plasma forfor
a
fixed
a fixedtreatment
treatmenttimetimeofof6060s sunder
undervarious
variousinput
inputpowers
powersstarting
startingfrom
from50 50up
uptoto 120
120 W.W. Figure
Figure 2
presents the
the contact
contactangle
angleand
andsurface
surfacefree
free energy
energy with
with respect
respect to the
to the nominal
nominal power.
power. It was
It was foundfound
that
that the optimum
the optimum plasma
plasma effect,
effect, under under which
which the treated
the treated filmfilm exhibited
exhibited the lowest
the lowest contact
contact angleangle
andand
the
the highest
highest surface
surface free free energy,
energy, was achieved
was achieved at 80
at 80 W. W. Therefore,
Therefore, furtherfurther
plasmaplasma treatments
treatments were
were carried
carried
out at aout at nominal
fixed a fixed nominal
power of power
80 Wofto80avoid
W toalso
avoid
anyalso any possible
possible degradation
degradation processes processes
at higherat
higher
nominal nominal
powers.powers.
60 60
Surface free energy (mJ m )
50 50
-2
SFE
Contact angle (°)
40 Water 40 Dispersive
Formamide Polar
Ethylene glycol
30 30
20 20
10 10
40 50 60 70 80 90 100 110 120 130 50 60 70 80 90 100 110 120 130

Nominal power (W) Nominal power (W)
(a) (b)
Figure 2. Surface wettability of low-density polyethylene

polyethylene (LDPE)
(LDPE) asas a function of nominal power for
LDPE modified using air plasma for 60 s: (a) contact angle; (b) surface free energy (SFE).
The impact
The impact of of plasma
plasma treatment
treatment using
using air,
air, argon,
argon, oxygen,
oxygen, andand nitrogen
nitrogen onon the
the surface
surface
hydrophilicity of LDPE in terms of the water contact angle and surface free energy
hydrophilicity of LDPE in terms of the water contact angle and surface free energy as a function of as a function
of treatment
treatment timetime is presented
is presented in Figure
in Figure 3. As 3. Asthe
seen, seen,
waterthecontact
water angle
contactforangle forLDPE
pristine pristine LDPE
substrate
substrate was initially ◦ ◦
was initially 95.7°. Any 95.7 . Any
material material
with contactwith contact
angle greaterangle
than greater than 90 istoconsidered
90° is considered to be
be hydrophobic
hydrophobic [42]. It is therefore evident that untreated LDPE corresponds to a hydrophobic
[42]. It is therefore evident that untreated LDPE corresponds to a hydrophobic surface. In fact, this surface.
In fact,
poor this poor
surface surface wettability
wettability behavior was behavior
expectedwasbecause
expected because
LDPE LDPE
surface surface is chemically
is chemically inert
inert and lacks
and lacks
polar activepolar active
species. species.
This outcome Thisconfirms
outcomethatconfirms that LDPE
LDPE shows a lowshows a low
affinity affinity
to water andtoother
waterpolar
and
liquids in general. Nevertheless, immediately after 10 s of plasma treatment, the LDPE surface
exhibited a highly hydrophilic behavior, where the water contact angle is sharply reduced along with
treatment time to 48°–61°, depending on the working gas. On the other hand, the total surface free
energy has markedly improved in a time dependent manner. This improvement mainly occurs due
to the increase in the value of the polar component of the total surface free energy, which validates
Coatings 2019, 9, 145 6 of 24
other polar liquids in general. Nevertheless, immediately after 10 s of plasma treatment, the LDPE
surface exhibited a highly hydrophilic behavior, where the water contact angle is sharply reduced
along with treatment time to 48◦ –61◦ , depending on the working gas. On the other hand, the total
surface free energy has markedly improved in a time dependent manner. This improvement mainly
occurs due to the increase in the value of the polar component of the total surface free energy, which
validates the functionalization of LDPE surfaces. For a plasma treatment time of 60 s, the surface
hydrophilicity improves
Coatings 2019, 9 FOR further. However, as treatment time was prolonged up to 120 s, the contact6
PEER REVIEW
angle of water levels off, where LDPE is not susceptible to any further reduction in the contact angle
of water.
shows thatThis showssaturation
a plasma that a plasma
state saturation
on the filmstate on the
surfaces wasfilm surfaces
reached. Thiswas reached.
finding This
mainly finding
addresses
mainly addresses the extent to which LDPE substrates could be modified using plasma
the extent to which LDPE substrates could be modified using plasma discharge. Plasma treatment of discharge.
Plasma treatment
LDPE surface of LDPE
under surface
air has under
resulted air has resulted
in maximum in maximum
hydrophilicity, hydrophilicity,
considering considering
the effects the
of surface
effects of surface functionalization
functionalization and roughness on and roughnessAs
wettability. on seen
wettability. As seenmorphological
later, surface later, surface morphological
changes were
changes were indeed
indeed observed observed
for plasma for plasma
treated LDPE treated
films. LDPE films.
100 Air 55
Argon
90 Nitrogen
50
Surface free energy (mJ m )
Oxygen -2
Contact angle of water (°)
80
45
70
40
60
35
50 Air
Argon
40 30 Nitrogen
Oxygen
30 25
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Treatment time (s) Treatment time (s)
(a) (b)
Figure 3. Surface wettability of LDPE as a function of plasma treatment time for LDPE treated using
different gases: (a) contact angle of water; (b) surface free energy
energy (SFE).
(SFE).
The hydrophilicity using

The hydrophilicity using gas gasmixtures,
mixtures,namely,
namely,argon/oxygen
argon/oxygenand and nitrogen/oxygen
nitrogen/oxygen plasma,
plasma, as
as shown in Figures 4 and 5 has slightly increased from those treated with
shown in Figures 4 and 5 has slightly increased from those treated with pure oxygen upon increasing pure oxygen upon increasing
either argon and
either argon andnitrogen
nitrogenconcentrations.
concentrations.However,
However, thethe effect
effect is smaller
is smaller compared
compared to pure
to pure argon argon
and
and nitrogen.
nitrogen. The useTheofusethe of the nitrogen/argon
nitrogen/argon mixturemixture
presented presented
in Figure in 6Figure
caused6 only
caused only increase
a slight a slight
increase in hydrophilicity
in hydrophilicity of suchLDPE,
of such treated treatedwith
LDPE, with a maximum
a maximum achievedachieved
in the case in the caseuse
of the of of
thepure
use
of pureThe
argon. argon. Theshow
results resultsthatshow that airhas
air plasma plasma has demonstrated
demonstrated the most significant
the most significant effects on
effects on increasing
increasing the wettability of the LDPE surface compared to other gases.
the wettability of the LDPE surface compared to other gases. Plasma treatment time of 120 s at Plasma treatment time of
80 W
120 s at 80 W of nominal power under air provided a minimum contact angle of 43.2 ◦ and maximum
of nominal power under air provided a minimum contact angle of 43.2° and maximum surface free
surface
energy offree energy
54.9 mJ·mof −2, 54.9 mJ·m−2 , optimal
representing representing optimal
conditions forconditions for plasma
plasma treatment treatment
of LDPE of LDPE
surfaces. The
surfaces. The decrease in contact angle and increase in surface free
decrease in contact angle and increase in surface free energy, particularly the polar component, energy, particularly the polar
component,
confirm thatconfirm
RF plasmathat RF plasma generates
generates hydrophilic hydrophilic surface properties
surface properties on LDPE onwithin
LDPE within relatively
relatively short
short exposure
exposure times, times,
which whichcan becan be attributed
attributed to severalto several
factors.factors.
Mainly, Mainly, the formation
the formation of new
of new reactive
reactive
oxygen- oxygen- and nitrogen-containing
and nitrogen-containing functional
functional groups incorporated
groups incorporated onto theonto the surface
surface is promotedis promoted
during
during the treatment
the plasma plasma treatment process. Additionally,
process. Additionally, the LDPE
the LDPE surface surface in
is enriched is free
enriched
radicalsin immediately
free radicals
immediately
after removal after
fromremoval
the plasma from the plasma
reactor, which reactor,
are highly which are highly
susceptible susceptible oxidation
to atmospheric to atmosphericupon
oxidation upon exposure to air. The other factor affecting hydrophilicity
exposure to air. The other factor affecting hydrophilicity increase is the surface roughness, increase is the surface
caused
roughness,
mainly by causedetchingmainly by etching
reactions. reactions.
Moreover, plasmaMoreover,
treatmentplasma cantreatment
possibly can possibly inaugurate
inaugurate superficial
superficial reorientation of the polymer micro-domains, in which the
reorientation of the polymer micro-domains, in which the hydrophilic regions are redirected hydrophilic regions are redirected
to the
to the surface
surface of the substrate
of the substrate [43]. The[43]. effectThe effect
of the latteroffactors
the latter factors wettability
on surface on surface can wettability
be explainedcan be
in
explained
terms of the in terms of the
polarity of polarity of the More
the interface. interface.
polarMore polarresult
groups groups inresult in increased
increased molecular molecular
forces,
forces, consequently
consequently enhancingenhancing the interactions
the interactions between between
surfacessurfaces
that arethatinare in contact,
contact, hence hence increasing
increasing the
the hydrophilicity
hydrophilicity of the
of the surface.
surface.
Coatings 2019, 9,
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9 FOR 7 of 247
Oxygen/Argon Oxygen/Argon
1.00 0.75 Oxygen/Argon
0.50 0.25 0.00 Oxygen/Argon
1.00 0.75 0.50 0.25 0.00
70 1.00 0.75 Oxygen/Argon
0.50 0.25 0.00 Oxygen/Argon
1.00 0.75 0.50 0.25 0.00
70 1.00 0.75 0.50 0.25 0.00 60 1.00 0.75 0.50 0.25 0.00
70
60 60
60 60
) )
-2
60
) -2m
50 50
m(mJ
m
(°) (°) (°) 50 50
-2
(mJ(mJ
50
40 Water 50 SFE
angle
energy
Formamide
Water 40 Dispersive
SFE
40
angle
energy
Ethylene
Formamide
Water glycol 40 Polar
Dispersive
SFE
40
angle
30
energy
Contact
Ethylene glycol
Formamide 40 Polar
Dispersive
free
30
Contact
Ethylene glycol 30 Polar
free
30
Contact
20
Surface
30
free
20
Surface
30
20
Surface
10 20
10 20
10
0 20
0 0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
0 0.00 0.25 0.50
Argon/Oxygen 0.75 1.00 0.00 0.25 0.50
Argon/Oxygen 0.75 1.00
0.00 0.25 0.50
Argon/Oxygen 0.75 1.00 0.00 0.25 0.50
Argon/Oxygen 0.75 1.00
(a) Argon/Oxygen (b) Argon/Oxygen
(a) (b)
(a) (b)
Figure 4. Surface wettability of LDPE treated using argon/oxygen plasma for 120 s as a function of
Figure 4. Surface wettability of LDPE treated using argon/oxygen plasma for 120 s as a function of
gas concentration
Figure 4. Surface ratio: (a) contact
Surface wettability
wettability angle
ofofLDPE
LDPE of water;
treated
treated using (b)
using surface freeplasma
argon/oxygen
argon/oxygen energy
plasma (SFE).
forfor
120120
s ass aasfunction
a function of
of gas
gas concentration ratio: (a) contact angle of water; (b) surface free energy (SFE).
gas concentration
concentration ratio:
ratio: (a) contact
(a) contact angle
angle of water;
of water; (b) surface
(b) surface free free energy
energy (SFE).
(SFE).
Oxygen/Nitrogen Oxygen/Nitrogen
Oxygen/Nitrogen 1.0 0.8 Oxygen/Nitrogen
0.6 0.4 0.2 0.0
1.00 0.75 0.50 0.25 0.00
Oxygen/Nitrogen 1.0 0.8 Oxygen/Nitrogen
0.6 0.4 0.2 0.0
1.00 0.75 0.50 0.25 0.00
60 1.00 0.75 0.50 0.25 0.00 60 1.0 0.8 0.6 0.4 0.2 0.0
60 60
60
50 60
) )
-2
) -2m
50 50
m(mJ
m
50
(°) (°) (°)
50 Water
-2
40
(mJ(mJ
50 SFE
angle
Formamide
Water
energy
40 Dispersive
SFE
Ethylene glycol 40
angle
Formamide
Water
energy
40
30 Polar
Dispersive
SFE
Ethylene glycol 40
angle
Formamide
Contact
energy
30 40 Polar
Dispersive
free
Ethylene glycol
Contact
30 30 Polar
free
20
Contact
Surface
30
free
20
Surface
20 30
10
Surface
20
10 20
10
0 20
0 0.00 0.25 0.50 0.75 1.00 0.0 0.2 0.4 0.6 0.8 1.0
0 0.00 0.25 0.50
Nitrogen/Oxygen 0.75 1.00 0.0 0.2 0.4 0.6
Nitrogen/Oxygen 0.8 1.0
0.00 0.25 0.50
Nitrogen/Oxygen 0.75 1.00 0.0 0.2 0.4 0.6
Nitrogen/Oxygen 0.8 1.0
(a) Nitrogen/Oxygen(b)
Nitrogen/Oxygen
(a) (b)
(a) (b)
Figure 5. Surface wettability of LDPE treated using nitrogen/oxygen plasma for 120 s as a function of
Figure 5. Surface wettability
Figure 5. wettability of
of LDPE
LDPE treated
treated using
using nitrogen/oxygen
nitrogen/oxygen plasma for 120 s as a function of
gas concentration
Figure ratio: (a) contact
5. Surface wettability angle;
of LDPE (b) surface
treated free energy (SFE).
using nitrogen/oxygen plasma for 120 s as a function of
gas concentration
concentration ratio:
ratio: (a) contact angle;
angle; (b)
(b) surface
surface free
free energy
energy (SFE).
(SFE).
gas concentration ratio: (a) contact angle; (b) surface free energy (SFE).
Nitrogen/Argon Nitrogen/Argon
1.00 0.75 Nitrogen/Argon
0.50 0.25 0.00 Nitrogen/Argon
1.00 0.75 0.50 0.25 0.00
1.00 0.75 Nitrogen/Argon
0.50 0.25 0.00 Nitrogen/Argon
1.00 0.75 0.50 0.25 0.00
60 1.00 0.75 0.50 0.25 0.00 60 1.00 0.75 0.50 0.25 0.00
60 60
60
) )
-2
50 60
) -2m
50 50
m(mJ
m
-2
50 50
(°) (°) (°)
(mJ(mJ
40 SFE
energy
50
angle
40 Water Dispersive
SFE
energy
40
angle
40 Formamide
Water Polar
Dispersive
SFE
energy
30 40
angle
Polar
Dispersive
Contact
Ethylene
Formamideglycol
free
30 Water
40 Polar
Contact
Ethylene glycol
Formamide
free
30 30
Surface
20
Contact
Ethylene glycol
free
30
Surface
20
30
Surface
20
10 20
10 20
10
0 20
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
0
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50
Argon/Nitrogen 0.75 1.00
0 Argon/Nitrogen
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50
Argon/Nitrogen 0.75 1.00
Argon/Nitrogen
(a) (b)
Argon/Nitrogen
Argon/Nitrogen
(a) (b)
(a) (b)
using argon/nitrogen
Figure 6. Surface wettability of LDPE treated using argon/nitrogen plasma
plasma for for 120 s as a function of
Figure 6. Surface wettability of LDPE treated using argon/nitrogen plasma for 120 s as a function of
gas concentration:
Figure (a) contactof
6. Surface wettability angle;
LDPE (b)treated
surfaceusing
free energy (SFE). plasma for 120 s as a function of
(SFE).
argon/nitrogen
gas concentration: (a) contact angle; (b) surface free energy (SFE).
gas concentration: (a) contact angle; (b) surface free energy (SFE).
An
An aging
agingstudy
studyhas
hasbeen
beencarried
carriedoutout
forfor
an extensive
an extensive period of time
period after after
of time plasma treatment
plasma to study
treatment to
the An aging
stability of study
the has
polar been formed
groups carried during
out forthe an functionalization
extensive periodprocesses.
of time after
The plasma treatment to
hydrophobic/aging
studyAnthe stability
aging study of
hasthebeenpolar
carriedgroups
out forformed duringperiod
an extensive the functionalization
of time after plasma processes.
treatmentThe to
study the stability
phenomenon of the polar
can be phenomenon
explained groups
in terms formed
of explained
theformed
surfacein during thepost
properties functionalization
plasma treatment. processes.
After The
plasma
hydrophobic/aging
study the stability of the polar can be
groups terms the
during of the surface properties
functionalization post plasma
processes. The
hydrophobic/agingthe
functionalization, phenomenon
surface can be
deviates explained
from itssurfacein termsstate
equilibrium of theduesurface properties post plasma
treatment. After plasma
hydrophobic/aging functionalization,
phenomenon can be the
explained in deviates
terms of from
the itstoequilibrium
surfacean properties
increase in post
statesurface
due tofree
plasma an
treatment.
energy, whichAfter plasma
results in functionalization,
the formation of the
near surface
surface deviates
gradients. from its equilibrium
Therefore, the state
surface due
tends to go
to an
increase in After
treatment. surface free energy,
plasma which results
functionalization, thein the formation
surface deviates of nearitssurface
from gradients.
equilibrium stateTherefore,
due to an
increase
back in
to its surface free energy, which results in the formation of near surface gradients. Therefore,
increase inpre-plasma
the surface surface go stage
tends tofree back byits
to
energy, reconstructing
pre-plasma
which itsthe
results stage
in surface
by to lower
reconstructing
formation theits
of near surface free
surface
surface to energy.
lower the
gradients. The latter
surface
Therefore,
the surface
occurs tends to go back
by reorientation/migration to its pre-plasma
of the polar stage by
groups, reconstructing
which its surface to lower the surface
freesurface
the energy. The latter
tends occurs
to go back to by
its reorientation/migration
pre-plasma stage of theare
by reconstructing redirected
polar itsgroups, back
surface to to
which the
lowerarebulk of the
redirected
the surface
free energy. The latter occurs by reorientation/migration of the polar groups, which are redirected
free energy. The latter occurs by reorientation/migration of the polar groups, which are redirected
Coatings 2019,
Coatings 2019, 99 FOR
2019, 9, FOR PEER REVIEW 8
Coatings 145 PEER REVIEW 8 of 248
back
back to to the
the bulk
bulk of of the
the polymer
polymer [44]. [44]. The
The aging
aging phenomenon
phenomenon mainly mainly depends
depends on on the
the storage
storage
condition,
polymer
condition, material
[44]. properties
The aging
material and
phenomenon
properties treatment type.
mainly type.
and treatment dependsFigures
on the
Figures 7 and
7 and 8
storage show
8 show the
condition, evolution
material
the evolution of the
the water
ofproperties
water
contact
and angle
treatment and
type. surface
Figures free
7 energy
and 8 showwith respect
the to
evolution aging
of the time
water
contact angle and surface free energy with respect to aging time for LDPE treated using different for LDPE
contact treated
angle using
and different
surface free
gases
energy and
gases and with storage conditions
respectconditions
storage to aging time in ambient
for LDPE
in ambient air and water
treated
air and waterusingmedium.
different
medium. As seen,
Asgases
seen, andthe aging effect
storageeffect
the aging (water
conditions
(water
contact
in ambient
contact angle
angle air increase)
and wateroccurs
increase) medium.
occurs predominantly
As seen, theduring
predominantly aging the
during first
effect
the 66 h.
(water
first The
The hydrophobic
h. contact angle increase)
hydrophobic recovery
recoveryoccurs of
of
treated LDPE
predominantly stored
during in air
the occurred
first 6 h. Theat a relatively
hydrophobic faster aging
recovery of rate than
treated
treated LDPE stored in air occurred at a relatively faster aging rate than in the case of LDPE stored in in
LDPE the case
stored of
in LDPE
air stored
occurred in
at
awater
water media.
relatively
media. Interestingly,
faster aging rate than
Interestingly, hydrophobic
in the caserecovery
hydrophobic of LDPEfor
recovery LDPE
stored
for LDPE samples
in water
samples treated
media.
treated with
with air,
air, nitrogen,
Interestingly, hydrophobic
nitrogen, and
and
argon
argon was
recovery wasfor reversed upon
upon immersion
LDPE samples
reversed treated with
immersion in
in water as
as the
the contact
air, nitrogen,
water angle
angle initially
and argon
contact was reversed
initially decreases
decreasesupon after 11 hour
immersion
after hour and in
and
using
water
using asoxygen after
the contact
oxygen 2 h.
after 2angle This
h. This outcome
initially
outcome could
decreases be
could beafterdue to
due1tohourthe polarity
and using
the polarity of water,
of oxygen which
water, which forces
after 2forces
h. This the
the formed
outcome
formed
hydrophilic
could be duegroups
hydrophilic toward
toward the
to the polarity
groups LDPE
of water,
the LDPEwhich surface,
surface, or
or else
forces theadditional
else functional
formed hydrophilic
additional functionalgroupsgroups
groupstowardcould
could be theformed
be LDPE
formed
as
as aa result
surface, or else
result of the
the free
free radicals’
of additional functional
radicals’ interactions
groups could
interactions with
with be water
formed[45].
water as a Increased
[45]. result of theaging
Increased time
time was
free radicals’
aging was probably
interactions
probably
responsible
with water [45].
responsible for
for washing
Increased
washing out of
of these
outaging time
these products, providing
was probably
products, providing them
them with
responsible forsimilar
with washing
similar aging
agingoutbehavior
of these as
behavior treated
products,
as treated
samples
providing stored
samples stored themin in air.
with However,
air.similar
However, agingit was found
behavior
it was foundas that
that this
treated effect was
samples
this effect only
wasstored temporary,
in air. However,
only temporary, because
because the
it was contact
found
the contact
angle
that increases
this effect wasagain
only at prolonged
temporary, aging
because times,
the yet
contact the values
angle still
increases
angle increases again at prolonged aging times, yet the values still fall below the untreated values.fall
againbelow
at the untreated
prolonged aging values.
times,
The
yet
Thethehydrophilicity
values still fall
hydrophilicity of the
ofbelow LDPE
the LDPE surface
the untreated lasted for
values.for
surface lasted Thea longer time
hydrophilicity
a longer for samples
time forofsamples
the LDPE treated
surface
treated in air,
inlasted as
air, asfor the
a
the
contact
longer
contacttimeangle
angle forachieved
samples lower
achieved treatedvalues
lower in air, in
values comparison
as the
in contact angle
comparison to
to other gases
achieved
other used.
gaseslower This
This outcome
used. values in comparison
outcome could
could be to
be
attributed
other gasesto
attributed combination
toused. This outcome
combination effects of
of individual
effectscould be attributed
individual gases
gasestoin air
air plasma
plasma with
combination
in with high
effects oxidation
oxidation energy
of individual
high energyinand
gases air
and
surface
plasma etching
surface with
etching high(roughness changes).
oxidation changes).
(roughness energy and surface etching (roughness changes).
100 Untreated Air

100 Untreated Air
Argon
60 Argon
90 Air 60 Nitrogen
90 Air Nitrogen
Argon Oxygen
))
Oxygen
-2
Argon
water(°)(°)
(mJmm
-2
80 Nitrogen
80 Nitrogen
Oxygen
angleofofwater
energy(mJ
Oxygen 50
70 50
70
freeenergy
Contactangle
60
60
Surfacefree
40
50 40
Contact
50
Surface
40
40
30 Untreated
30 Untreated
30
30
0 1 2 3 4 5 6 100 200 300 400 500 0 1 2 3 4 5 6 100 200 300 400 500
0 1 2 3 4 5 6 100 200 300 400 500 0 1 2 3 4 5 6 100 200 300 400 500
Aging time (h) Aging time (h)
(a)
(a) (b)
(b)
Figure 7.
7. Surface
Figure 7.
Figure Surface wettability
wettability of
of LDPE
LDPE treated
treated for
for 120
120 ss using
using different
different gases
gases and
and stored
stored in
in ambient
ambient air:
air:
(a) contact
(a) contact
(a) angle;
contact angle; (b)
angle; (b) surface
(b) surface free
surface free energy
freeenergy (SFE).
energy(SFE).
(SFE).
100 Untreated Air

100 Untreated Air
Argon
Argon
90 Air Nitrogen
90 Air 60 Nitrogen
Argon 60 Oxygen
))
Argon Oxygen
-2
water(°)(°)
(mJmm
Nitrogen
-2
80 Nitrogen
80 Oxygen
angleofofwater
energy(mJ
Oxygen
70 50
70 50
freeenergy
Contactangle
60
60
Surfacefree
50 40
40
Contact
50
Surface
40
40
30 Untreated
30 Untreated
30
30
0 1 2 3 4 5 6 100 200 300 400 500 0 1 2 3 4 5 6 100 200 300 400 500
0 1 2 3 4 5 6 100 200 300 400 500 0 1 2 3 4 5 6 100 200 300 400 500
(a)
(a) (b)
(b)
Figure 8. Surface
Figure 8. Surfacewettability
Surface wettabilityof
wettability ofofLDPE
LDPEtreated
LDPE treatedfor
treated for120
for 120 ss using
120 using different
s using
different gases
different and
gases
gases and stored
and in
in water:
stored
stored (a)
in water:
water: (a)
contact
(a) angle;
contact (b)
angle; surface
(b) free
surface energy
free (SFE).
energy
contact angle; (b) surface free energy (SFE). (SFE).
Coatings2019,
Coatings 2019,9,9 145
FOR PEER REVIEW 9 of 249
3.2. Adhesion Investigation

3.2. Adhesion Investigation
The plasma treatment of LDPE foils led to the improvement of adhesion properties as well,
which Theare closely
plasma related to
treatment of the
LDPE wettability.
foils led toThethesurface
improvementtreatment varied based
of adhesion on the
properties as reactivity
well, which of
the closely
are gases used,
relatedtheir
to theability to introduce
wettability. new treatment
The surface polar functional groupsonand
varied based the the extentofofthe
reactivity etching.
gases
Apparently,
used, as LDPE
their ability contains only
to introduce non-polar
new polar hydrophobic
functional groups groups,
and the newly
extent formed
of etching.polar functional
Apparently,
groups
as LDPE(oxygen
containsand onlynitrogen
non-polar containing)
hydrophobic together
groups, with etching
newly were
formed responsible
polar functional forgroups
the increase
(oxygen in
wettability
and nitrogen and adhesion together
containing) represented withby the peel
etching wereresistance.
responsibleFigurefor 9therepresents
increase the peel resistance
in wettability and
changes of
adhesion LDPE afterbyplasma
represented the peel treatment
resistance. using different
Figure gases. the
9 represents According to the values
peel resistance changes shown,
of LDPE the
use of
after argontreatment
plasma and nitrogen usingled to thegases.
different highest values oftopeel
According resistance.
the values shown, In contrary,
the use ofthe argonplasma
and
treatmentled
nitrogen of to
LDPE in oxygen
the highest gas was
values responsible
of peel resistance. for In
achieving
contrary,the thelowest
plasma values of peelofresistance,
treatment LDPE in
which isgas
oxygen in awas
good correlationfor
responsible with contact angle
achieving results.
the lowest The aging
values of peeleffect on the plasma
resistance, whichtreated
is in a LDPE
good
samples stored
correlation in air Figure
with contact angle 10 and water
results. medium
The aging effectFigure
on the 11 was studied
plasma treated LDPEas well. A re-arrangement
samples stored in air
of mobile
Figure 10 andpolar species
water or low-molecular
medium Figure 11 was weight
studied oxidative
as well.products formed during
A re-arrangement of mobileandpolar
immediately
species
after
or plasma treatment
low-molecular weightwith subsequent
oxidative products airformed
exposure led and
during to the aging phenomenon.
immediately after plasma These polar
treatment
groups
with were reoriented
subsequent towardled
air exposure thetobackbone
the agingofphenomenon.
the material, which Thesecaused the reduction
polar groups of surface
were reoriented
polaritythe
toward over time, and
backbone of thus, surface wettability
the material, which caused andtheadhesion
reduction decreased
of surfaceas the agingover
polarity process
time, occurs
and
[46]. Aging
thus, surfaceresults varied
wettability andbased on thedecreased
adhesion media in whichas the these
aging samples were kept.
process occurs [46].Plasma treatedvaried
Aging results LDPE
samples
based on stored
the media in airin showed
which these an increasing
samples were trend in peel
kept. Plasmaresistance
treatedduring the first stored
LDPE samples 6 h as in post-
air
oxidation
showed anreactions
increasing occur
trend oninthepeeltreated surface.
resistance Additional
during the firstaging
6 h astime led to the deterioration
post-oxidation reactions occur of
adhesion
on properties
the treated surface. and the decrease
Additional agingin peel
timeresistance. The minor decrease
led to the deterioration of adhesionwas observed
properties after
andthree
the
weeks ofin
decrease aging. Nevertheless,
peel resistance. Thetheminorpeeldecrease
resistance waswas still higher
observed afterfor treated
three weeks LDPE than Nevertheless,
of aging. for untreated
LDPE.
the peelAging of samples
resistance was still in higher
water media did not
for treated LDPEprovide
than thefor same results
untreated as inAging
LDPE. air media, as shown
of samples in
in Figure
water media 11. did
Water notasprovide
a polar the molecule can form
same results as hydrogen
in air media, bondsas with
shown theinformed
Figure polar groups
11. Water as ora
attractmolecule
polar low-molecularcan form oxidative
hydrogen products
bondson withthethetreated
formed LDPE polarsurface.
groupsAn orinitial
attractdecrease of peel
low-molecular
resistanceproducts
oxidative until 4 h on wastheobserved
treated for LDPE LDPE samples
surface. Antreated with argon
initial decrease and nitrogen
of peel resistancestored
until in4 hwater
was
medium with subsequent slightly increasing and decreasing tendencies
observed for LDPE samples treated with argon and nitrogen stored in water medium with subsequent with advanced aging time.
The initial
slightly decreaseand
increasing of peel resistance
decreasing for LDPEwith
tendencies treated by oxygen
advanced aging and air The
time. agedinitial
in water medium
decrease was
of peel
observed during
resistance for LDPE thetreated
first 6by and 24 h, respectively.
oxygen and air aged in This adhesion
water medium decrease was probably
was observed during caused
the firstby 6
diffusion
and of plasma produced
24 h, respectively. This adhesionlow-molecular
decrease was weight oxidative
probably products
caused towards
by diffusion of the LDPE
plasma surface,
produced
forced by the water
low-molecular weight medium.
oxidative products towards the LDPE surface, forced by the water medium.
150
Peel resistance (N m )
-1
100
50
Untreated
0
Air Argon Nitrogen Oxygen
Gas used
Figure 9. Peel resistance

Figure 9. resistance of
of LDPE
LDPE treated
treated for
for 120
120 ss using
using different
differentgases.
gases.
Coatings 2019, 9, 145 10 of 24
240 Air
240
220 Argon
Air
Nitrogen
Argon
220
200 Oxygen
Nitrogen
200
180 Oxygen
(N-1)m )
-1
180
160
(N m
resistance
160
140
resistance
140
120
120
100
Peel
100
80
Peel
80
60
60 Untreated
40
Untreated
40 0 1 2 3 4 5 6 100 200 300 400 500
0 1 2 3 4 5 6 100 time
Aging 200
(h) 300 400 500
Aging time (h)
Figure 10. Peel resistance of LDPE treated for 120 s using different gases and stored in air.
Figure 10.
Figure Peel resistance
10. Peel resistance of
of LDPE
LDPE treated
treated for
for 120
120 ss using
using different
different gases
gases and
and stored
stored in
in air.
air.
180 Air
180 Argon
Air
160 Nitrogen
Argon
Oxygen
Nitrogen
160
140 Oxygen
(N-1)m )
-1
140
(N m
120
resistance
120
resistance
100
100
80
Peel
80
Peel
60
60 Untreated
40
Untreated
40
0 1 2 3 4 5 6 100 200 300 400 500
0 1 2 3 4 5 6 100 time
Aging 200
(h) 300 400 500
Aging time (h)
Figure 11.
Figure Peel resistance
11. Peel resistance of
of LDPE
LDPE treated
treated for
for 120
120 ss using
using different
different gases
gases and
and stored
stored in
in water.
water.
Figure 11. Peel resistance of LDPE treated for 120 s using different gases and stored in water.
3.3. Surface Chemistry Analysis
3.3. Surface Chemistry Analysis
3.3. Surface
FTIR-ATR Chemistry
was usedAnalysis
to analyze chemical composition changes of LDPE after plasma treatment.
FTIR-ATR was used to analyze chemical composition changes of LDPE after plasma treatment.
The IR spectrum
FTIR-ATR of untreated LDPE contains mainly –CH stretching, bending and rocking vibrations
The IR spectrumwas used to analyze
of untreated chemicalmainly
LDPE contains − 1
composition changes of
–CH stretching, LDPE after
bending plasma vibrations
and rocking treatment.
in
ThetheIRregions
spectrum of of
2900–2800,
untreated1500,
LDPE600 cm −1 ,mainly
contains respectively, since LDPE
–CH stretching, contains
bending only
and only
rockinghydrocarbon
vibrations
in the regions of 2900–2800, 1500, 600 cm , respectively, since LDPE contains hydrocarbon
chains.
in the Etching
regions caused
of by
2900–2800,plasma
1500, occurred
600 cm at
−1 , the nano-level,
respectively, and
since thus
LDPE the similarities
contains only between
hydrocarbonthese
chains. Etching caused by plasma occurred at the nano-level, and thus the similarities between these
infrared spectra
chains. Etching radiation could not show the high intensity peaks of the new functional groups, as the
infrared spectra caused
radiationby could
plasmanot occurred
show the at thehighnano-level,
intensity peaksand thus thenew
of the similarities
functional between
groups,these
as
graphs
infrared below
spectrashowed. These nano-level changes were reflected in subsequent newcontact angle and XPS
the graphs belowradiation
showed. could
These not show
nano-level the high
changes intensity peaks
were reflected of
in the
subsequent functional
contact groups,
angle and as
analyses.
the graphs Some
belowoxygen
showed.containing
These groups, forchanges
nano-level example, oxygen
were containing
reflected in productscontact
subsequent at the surface
angle of
and
XPS analyses. Some oxygen containing groups, for example, oxygen containing products at the
the
XPSpolymer
analyses. that appeared
Some oxygen after 24 h of aging,
containing groups, show absorbance bands associated with vibrations of
surface of the polymer that appeared after 24 h offoraging,
example,
− 1 showoxygen
absorbance containing products
bands associated
− 1
atwith
the
C=O
surfaceor C=O
of oftheinpolymer
carboxyl that
group (in region
appeared 1800–1500
after h of cm
24region aging, ) and C–O
show vibration (1200
absorbance bands cm ). Moreover,
associated with
vibrations C=O or C=O in carboxyl group (in 1800–1500 cm −1) and C–O vibration (1200 cm −1).
−1
the absorbance band related to the vibration of –OH (wide absorbance band in the 3000–3500 cm−1
vibrations of C=O or C=O in carboxyl group (in region 1800–1500 cm
Moreover, the absorbance band related to the vibration of –OH (wide absorbance band in the 3000–).
−1) and C–O vibration (1200 cm
region)
Moreover, wastheobserved after plasma
absorbance bandaftertreatment.
related The oxidative
to thetreatment.
vibration reaction
of –OH (wideplasma treated band
absorbance LDPEin films led
the LDPE to
3000–
3500 cm−1 region) was observed plasma The oxidative reaction plasma treated
changes
3500 cm in FTIR-ATR spectra with aging time (Figures 12–19). The increased intensity in absorbance
led toregion) wasin observed
FTIR-ATRafter plasma
withtreatment. The oxidative reaction plasma treated LDPE
−1
films changes spectra aging time (Figures 12–19). The increased intensity in
bands
films centered
led to approximately
changes in FTIR-ATR at 3500 andwith
spectra 3250aging cm−1time
was (Figures
likely caused
12–19). byTheincreased
increasedhydroperoxide
intensity in
absorbance bands centered approximately at 3500 and 3250 cm was likely caused by increased−1
−1 was
decomposition
absorbance bands in LDPE after aging
centered approximately effects. The increase in intensity centered at 1630 cm
in LDPE afterat 3500effects.
and 3250 The cm wasinlikely caused by increased
−1
hydroperoxide decomposition aging increase intensity centered at 1630
associated
hydroperoxide with decomposition
carbonyl species in originating
LDPE after from
aging hydroperoxide
effects. The decomposition
increase in intensity because
centered of radical
at 1630
cm was associated with carbonyl species originating from hydroperoxide decomposition because
−1
reactions
cm −1 was of polyethylene
associated with (PE) with oxygen
carbonyl species [47].
originating from hydroperoxide decomposition because
of radical reactions of polyethylene (PE) with oxygen [47].
of radical reactions of polyethylene (PE) with oxygen [47].
Coatings 2019, 9, 145 11 of 24
LDPE samples were treated in different gases (air, (air, oxygen,

oxygen, nitrogen,
nitrogen, and argon) and they were
aged in airairand andwater
watermediamediatoto monitor
monitor chemical
chemical changes
changes in surface
in surface functionalization
functionalization withwithtime.time.
This
functionalization
This functionalization was analyzed
was analyzed usingusing
FTIRFTIRduring four four
during weeks of aging.
weeks WithWith
of aging. time,time,
temperature,
temperature, and
humidity
and humidity factors fixed,
factors the the
fixed, changes
changes werewere observed
observed andandrecorded
recorded(Figures(Figures12–19). 12–19). PE PE has
has clear
characteristicsbecause
characteristics becauseit it consists
consists mainly
mainly of hydrocarbon
of hydrocarbon chainschains and branches,
and branches, and thusand its IR thus its IR
spectrum
spectrumvibrations
showed showed vibrations
in single CH in stretching
single CHand stretching
bendingand bending at1470–1460
at 2980–2900, 2980–2900, − 1
cm1470–1460
asymmetric, cm−1
asymmetric,
and 730 cm and − 1 730 cm
rocking. −1 rocking. Plasma-initiated
Plasma-initiated radicals on theradicals
hydrocarbon on theskeleton
hydrocarbon skeletoncreated
of PE surfaces of PE
surfaces created covalent bonding between the radicals and new
covalent bonding between the radicals and new functional groups on the PE surface. These groupsfunctional groups on the PE surface.
These
are groups
mainly are mainly
oxygen oxygen
containing containing
groups, groups,byevidenced
evidenced the observed by the observedin
vibrations vibrations
differentin different
regions of
regions
the of the(OH,
IR spectra IR spectra
C–O, C=O, (OH,O–O, C–O,COO).
C=O,Different
O–O, COO). plasma Different
gases will plasmaaffectgases will affect the
the concentration of
concentration
the polar groups of the polarto
bonded groups
PE, whichbondedalsotodepends
PE, which onalso
the depends on theAir
radicalization. radicalization.
plasma is a Air plasma
mixture of
is a mixture
oxygen, nitrogen of oxygen,
and argon nitrogen
with otherand argon with other
gases included, sogases
it has included,
a larger effect so iton has a larger
creating effect on
radicals
creating
PE radicals
surfaces. Thaton PE surfaces.
could be evidenced That could
from thebe evidenced
absorbance from the absorbance
intensity increase after intensity
plasma increase
in theafter
OH
plasma
band in the OH
(3500–3300 −
cmband1 (3500–3300
), carbonyl cm C=O
group −1), carbonyl
and O–C=O group(1800–1700
C=O and O–C=O − 1
cm ), and (1800–1700
ether groupscm ),C–O
−1 and
ether groups
(1100–1000 −1 ). In
cmC–O (1100–1000
oxygen plasma, cm−1). the
In oxygen was plasma,
morethe oxygen was
concentrated in more
the plasma concentrated
and that in ledthe
to
plasma and that led to the same or higher peak intensity, as well
the same or higher peak intensity, as well as more defined shapes in the mentioned vibration peaks. as more defined shapes in the
mentioned
For argon and vibration
nitrogen, peaks.
their For
peaks argon
wereand not nitrogen,
clearly in thetheirsamepeaks were notrange
absorbance clearly in the same
as oxygen, and
absorbance
this range as tooxygen,
can be attributed and this
a low oxygen can be attributed
concentration to a low An
during treatment. oxygen agingconcentration
test was done duringin two
treatment.
media An aging
(air and water)test was done
to measure in effect
their two media (air and
on treated water)
samples withto newly
measure their effect
introduced polaron groups.
treated
samples
In with newly
atmospheric normalintroduced
aerationpolar (withgroups. In atmospheric
temperature and humiditynormalfixed),aeration the(with temperature
increase in intensityand
humidity fixed), the increase in intensity occurred within the first
occurred within the first 24 h only (measurements were done for 672 h in total). After 24 h, the 24 h only (measurements were
done forin672
growth h in total).
intensity slowedAfter 24 h,
with the growth
increasing in intensity
time. This outcomeslowed canwith increasingby
be explained time.
the This outcome
reorientation
cannonpolar
of be explained groups, by leading
the reorientation of nonpolar
to more stabilized groups,
forms on the leading
surface. to The
moreabsorbance
stabilized intensity
forms on has the
surface. The absorbance intensity has increased multiple times more
increased multiple times more for water aged samples than for samples in aeration, because water for water aged samples than for
samples
can form in aeration, with
H-bonding because any water
OH and canNH form H-bonding
containing withwhich
groups, any OH can and formNH highercontaining
vibration groups,
peaks
which
in can formtreated
IR. Samples higherwith vibration
oxygen peaks in IR.showed
plasma Samples treateddefined
a clearly with oxygen increase plasma showed intensity
in vibration a clearly
defined
with time,increase
followed in vibration
by samples intensity
treated with
with time,
air and followed
argon, and by samples
nitrogentreated was least with air and argon,
evidenced by its
and nitrogen
relatively lower waspeakleast evidenced
intensities. Thebyvibration
its relatively lowerafter
stabilized peak336 intensities.
h and began Thetovibration
decreasestabilized
after 504
after
h, with336theh and
lowestbegan to decrease
for nitrogen aftersamples
treated 504 h, with the 17
Figure lowest
agedfor in nitrogen
water. This treated samplesto
is attributed Figure
the low 17
aged in water.
molecular weight This is attributed
materials (LMWM) to thebeing
low molecular
dissociated, weight
leadingmaterials (LMWM)
to a decrease being
in the dissociated,
polarity of the
leading to
surfaces a decrease in the polarity of the surfaces [46].
[46].
1 - Untreated
2-0h val. asym.
3 - 24 h -CH2-
4 - 168 h val. sym.
765 4 3 21
5 - 336 h -CH2-
Absorbance (a.u.)
6 - 504 h
7 - 672 h
1800 1600 1400 1200 1000

def. asym.
-CH def.
O-C=O -CH2-
-O-
7
-OH C=O
6
5
4
3
22
1
4000 3500 3000 2500 2000 1500 1000

-1
Wavenumbers (cm )
Figure 12. FTIR spectra of LDPE plasma treated for 120 s using air and stored in
in air.
air.
Coatings 2019,
Coatings 2019, 9,
9 FOR
145 PEER REVIEW 12
12 of 24
1 - Untreated
2 val. asym.
1 -- 0 h
Untreated
3 - 240 hh -CH -
val. 2asym.
12 -- Untreated
4 - 168 h val.
-CH - sym.
765
23 -- 024h h val. asym.
2
5 - 168
336 hh -CH -
(a.u.)
34 -- 24 h -CHval.- 2sym.
74
6 - 504
336 hh
2
63
45 -- 168 h -CHsym.
-
(a.u.)
val.
5
72
7 - 672
504 hh
2
4
56 -- 336 h
61
Absorbance
-CH2-
(a.u.)
3
54
67 -- 504
672 hh
21
Absorbance
3 21
7 - 672 h 1800 1600 1400 1200 1000
Absorbance
def. asym.
1800 1600 1400 1200
def. 1000
-CH
def. asym.
1800 1600 1400 1200
O-C=O -CH 2-
def.1000
-OH -O-
-CHasym.
def.
C=O
7 7 76
-CH2-
def.
6 6
-OH O-C=O -CH -O-
5 5 54
C=O -CH -
4 4
O-C=O -O- 2
3 3 322
-OH
22 22
C=O
1 1 1
4000 3500 3000 2500 2000 1500 1000
4000 3500 3000 2500
Wavenumbers 2000
(cm ) 1500
-1 1000
4000 3500 3000 2500 2000 -1 1500 1000
Wavenumbers (cm )
-1
Figure 13. FTIR spectra of LDPE Wavenumbers
plasma treated (cm
and stored in water. )
for 120 s using air
Figure 13. FTIR spectra of LDPE plasma treated for 120 s using air and stored in water.
1 - Untreated
2
1 -- 0 h
Untreated
val. asym.
13
2 --- Untreated
24
0 hh -CH -
val. 2asym.
24
3 --- 024
168
h hh -CH - val. sym.
7 65
35
4 --- 24
336 h val. asym.
168h h -CH -
(a.u.)
2
val. 2sym.
74
46
5 --- 168
504 h -CH2- val.
336 hh
67
-CHsym.-
(a.u.)
3
52
57
6 --- 336
672
504 hh
2
h
4
61
Absorbance
-CH2-
(a.u.)
5
34
67 -- 504
672 hh
23
Absorbance
121
7 - 672 h 1800 1600 1400 1200 1000

Absorbance
def. asym.
1800 1600 1400 1200 1000
-CH def.
def. 1200
1800 1600 1400 asym.1000
O-C=O -CH
def. 2-
-CHasym.
C=O def. -O-
7
-OH
O-C=O -CH def. -CH2-
6 6 65
5 5
-O-
7 7
-OH C=O
4 4 43
O-C=O -CH2-
3 3
-OH C=O -O-

22 22 221
1 1
4000 3500 3000 2500 2000 1500 1000

3000 2500
Wavenumbers 20004000
(cm ) 1500
-1 3500
1000
3000 2500 4000
2000 -1 1500 10003500
Wavenumbers (cm )
-1
Wavenumbers
Figure 14. FTIR spectra of LDPE plasma (cm 120
treated for ) s using oxygen and stored in air.
Figure 14. FTIR spectra of LDPE plasma treated for 120 s using oxygen and stored in air.
1 - Untreated
2
1 -- 0Untreated
h
val. asym.
13
2 --- 24 hh
0Untreated -
-CH2asym.
7 6
val.
24
3 --- 0168
24h hh
-
-CHasym.
val. sym.
val.
756
5 -
34 -- 24336 h
168h h 2 -CH -
(a.u.)
-CH2- val. 2sym.

4
75
46
5 --- 168
504
336 hh
h -CHsym.
val. -
(a.u.)
36
57
6 --- 336
672
504 hh
2
4
25
h
Absorbance
-CH2-
(a.u.)
1
34
67 -- 504
672 hh
23
Absorbance
121
7 - 672 h 1800 1600 1400 1200 1000

Absorbance
def. asym.
def. 1000
1800 1600 1400 1200
O-C=O -CH def. asym.
-OH 1800 1600 1400 -O--CH
1200 2-
def.1000
C=O def.
O-C=O -CHasym.
7
-CH
def. -
-OH O-C=OC=O -CH-O- 2
6 6 65
7 7
5 5
-OH -O--CH2-
C=O
4 4 43
3 3
2 2 21
1 1
4000 3500 3000 2500 2000 1500 1000

-1
4000 3500 3000 2500
Wavenumbers 2000
(cm ) 1500 1000
4000 3500 3000
Wavenumbers (cm ) 1500
2500 2000-1 1000
Figure 15. FTIR spectra of LDPE plasma treated for(cm
Wavenumbers 120
-1 s using oxygen and stored in water.
Figure 15. FTIR spectra of LDPE plasma treated for 120) s using oxygen and stored in water.
Figure 15. FTIR spectra of LDPE plasma treated for 120 s using oxygen and stored in water.
Figure 15. FTIR spectra of LDPE plasma treated for 120 s using oxygen and stored in water.
Coatings 2019,
Coatings 2019, 9 FOR
145 PEER REVIEW 13
Coatings 2019, 9,
9 FOR PEER REVIEW 13 of 24
13
1 - Untreated
1 - Untreated
2
1 -0h
2 -- Untreated
0h val. asym.
3
2 - 24hh val. asym.
3 -- 0
24 h -CH2asym.
-
4 -- 168 h val.
-CH -
77
3 24 h
4 - 168 h -CH22- val. sym.
val. sym.
67
5
4 - 336 h
5 -- 168
336 h -CH -
(a.u.)
6
54
h val.
-CH2-2sym.
(a.u.)
5
64
6
5 -- 504
336 h
h -CH -
(a.u.)
3
54
6 - 504 h 2
7 - 672 h
323
6
7 -- 504
672 h
Absorbance
h
2
12
Absorbance
7 - 672 h
11
Absorbance
1800 1600 1400 1200 1000
1800 1600 1400 1200 1000
def. asym.
1800 1600 1400 1200 1000
def. asym.
-CH
def. def.
-CH asym.
O-C=O -CH
def.
-CH -
def.
-CH2
O-C=O -O- 2--
77 7
-OH C=O
O-C=O -CH2
-O-
66 6
-OH C=O
55 5
-OH C=O -O-
44 4
33 3
222222
11 1
4000 3500 3000 2500 2000 1500 1000
4000 3500 3000 2500 2000 1500 1000
4000 3500 3000 2500 2000-1 1500 1000
Wavenumbers (cm-1)
Wavenumbers (cm-1)
Wavenumbers (cm )
Figure 16. FTIR spectra of LDPE plasma treated for 120 s using nitrogen and stored in air.
FTIR spectra
air.
1 - Untreated
1 - Untreated
2
1 -0h
2 -- Untreated
0h val. asym.
val. asym.
3
2 -- 24 h
3-0 24hh -CH -
val. asym.
776
4
3 -- 168
24 h h -CH22- val. sym.
4 - 168 h -CH2- val. sym.
7
5 - 336 h -CH -
6
54
4
5 -- 168
336 h
(a.u.)
h val.
-CH2sym.
-
564
(a.u.)
6
5 - 504 h
6 -- 336
504 h -CH22-
3
54
(a.u.)
h
3
23
7
6 - 672 h
7 -- 504
672 h
Absorbance
2
12
h
Absorbance
11
7 - 672 h
Absorbance
1800 1600 1400 1200 1000

1800 1600 1400 1200 1000
def. asym.
1800 1600 1400 1200 1000
def. asym.
-CH def.
def. asym.
def.
O-C=O -CH -CHdef. -
-OH O-C=O -CH2
C=O -CH -O- 2--
77 7
-OH O-C=O
C=O -O-
-CH 2
66 6
-OH C=O -O-

55 5
44 4
33 3
222222
11 1
4000 3500 3000 2500 2000 1500 1000

4000 3500 3000 2500 2000 1500 1000
4000 3500 3000 2500 2000-1 1500 1000
Wavenumbers (cm-1)
Wavenumbers (cm-1)
Wavenumbers (cm )
Figure 17. FTIR spectra of LDPE plasma treated for 120 s using nitrogen and stored in water.
FTIR spectra of LDPE plasma treated for 120 s using nitrogen and stored in water.
Figure 17. FTIR water.
Figure 17. FTIR spectra of LDPE plasma treated for 120 s using nitrogen and stored in water.
1 - Untreated
1 - Untreated
2
1 -0h
2 - Untreated
0h val. asym.
3
2 - 24hh val. asym.
3-0 24 h -CH2asym.
-
4
3 - 168
24 hh val.
-CH -
77
4 - 168 h -CH22- val. sym.

val. sym.
67
5
4 - 336 h
5 - 168 -CH -
(a.u.)
val.
-CH2sym.
6
56
336 h 2 -
(a.u.)
6 - 504 h
4
54
5 336 -CH -
(a.u.)
6 - 504 h
5
34
2
7
6 - 672
504 h
321
Absorbance
7 - 672 h
3
21
Absorbance
7 - 672 h
21
Absorbance
1800 1600 1400 1200 1000

1800 1600 1400 1200 1000
def. asym.
1800 1600 1400 1200 1000
def. asym.
def.
-CH
def.
-CH asym.
O-C=O -CH
def.
-CH
def. 2-
O-C=O -CH2-
777
-OH C=O -O-

O-C=O -CH2
-O- -
666
-OH C=O
555
-OH C=O -O-

444
333
222222
111
4000 3500 3000 2500 2000 1500 1000

4000 3500 3000 2500 2000 1500 1000
4000 3500 3000 2500 2000-1 1500 1000
Wavenumbers (cm-1)
Wavenumbers (cm-1)
Wavenumbers (cm )
FTIR spectra
Figure 18. FTIR spectra of
of LDPE
LDPE plasma treated for 120 s using argon and stored in air.
air.
Figure 18. FTIR spectra of LDPE plasma treated for 120 s using argon and stored in air.
Figure 18. FTIR spectra of LDPE plasma treated for 120 s using argon and stored in air.
Coatings 2019, 9, 145 14 of 24
1 - Untreated
2-0h
val. asym.
3 - 24 h
-CH2-
7 6 54 32 1
4 - 168 h val. sym.
5 - 336 h -CH2-
Absorbance (a.u.)
6 - 504 h
7 - 672 h
1800 1600 1400 1200 1000

def. asym.
O-C=O -CH def.
-OH C=O -O--CH2-
7
6
5
4
3
2
1
4000 3500 3000 2500 2000 1500 1000
-1
Wavenumbers (cm )
Figure 19. FTIR

FTIR spectra of LDPE plasma treated for 120 s using argon and stored in water.
water.
Changes
Changes inina asurface surface chemical
chemical composition
composition of theofLDPE surfacesurface
the LDPE before and afterand
before plasma
aftertreatment
plasma
were evaluated
treatment were using
evaluatedXPS. using
The chemical
XPS. The composition of elements of
chemical composition existing
elementson the treated
existing onsurface
the treatedwas
obtained from the C1s, O1s, and N1s peaks, as shown in Table
surface was obtained from the C1s, O1s, and N1s peaks, as shown in Table 1. The quantification 1. The quantification report of the
spectra
report offor the untreated
spectra for LDPE revealed
untreated LDPEhighrevealed
carbon and highlow oxygen
carbon and atomic
low oxygenconcentrations (at.%) equal
atomic concentrations
to 97.41equal
(at.%) at.% to and 2.59at.%
97.41 at.%,and respectively.
2.59 at.%, Although
respectively. the Although
LDPE structurethe LDPE doesstructure
not contain doesanynot
oxygen
contain in
its
anynature,
oxygen this
in may be attributed
its nature, this may to be
theattributed
processingtoadditives or residual
the processing air inside
additives the analysis
or residual chamber.
air inside the
Plasma
analysistreatment
chamber. of LDPEtreatment
Plasma using air, of nitrogen,
LDPE usingoxygen air,and argon oxygen
nitrogen, was responsible
and argon forwas
theresponsible
increase in
the oxygen
for the and nitrogen
increase in the oxygen content and at nitrogen
the expense of theatcarbon
content content,
the expense of showing
the carbon a significant decreasea
content, showing
of the C1s peak
significant at ~285
decrease eV of
of the C1sbinding
peak at energy
~285 relative to the untreated
eV of binding surface.
energy relative toThis outcome indicates
the untreated surface.
the
Thisformation
outcome of newly oxygen
indicates and nitrogen
the formation of newlycontaining
oxygen functional
and nitrogen groups, and thus
containing results ingroups,
functional higher
hydrophilicity.
and thus results in higher hydrophilicity. Moreover, some peaks with a relatively low intensity,some
Moreover, some peaks with a relatively low intensity, such as Si2p, represent such
impurities probably
as Si2p, represent someoriginated
impurities from the plasma
probably reactor.from
originated Figure
the 20 shows
plasma the XPS
reactor. spectra
Figure for LDPE,
20 shows the
where the O1s
XPS spectra peak
for LDPE,waswhere
observed the with maxima
O1s peak wasatobserved
~530 eV, and withthe nitrogen
maxima at peak
~530 appears
eV, and at the~400 eV of
nitrogen
the
peak binding
appears energy.
at ~400 The eVatomic
of theconcentration
binding energy. of O1sThefor LDPEconcentration
atomic samples treated in air,for
of O1s oxygen,
LDPE nitrogen
samples
and argon
treated increased
in air, oxygen, tonitrogen
12.75 at.%, and12.51
argon at.%, 11.64 at.%,
increased and at.%,
to 12.75 14.40 12.51
at.%, at.%,
respectively.
11.64 at.%, Interestingly,
and 14.40
surfaces plasma treated
at.%, respectively. using argon
Interestingly, and nitrogen
surfaces exhibited
plasma treated usinghigh incorporation
argon and nitrogen of polar groups
exhibited as
high
well. This result
incorporation of ispolar
likely, because
groups as the
well.incorporation
This result is of likely,
oxygen-containing groups is apparent
because the incorporation when
of oxygen-
samples
containing are groups
treated in is anapparent
inert environment
when samples where are functionalization
treated in an mainly
inertoccurs upon exposure
environment where
to air immediatelymainly
functionalization after plasma
occurs treatment
upon exposure [48]. In to Table 1, the atomic
air immediately concentrations
after plasma treatment of individual
[48]. In
chemical
Table 1, the elements
atomicare summarizedofaccording
concentrations individual to chemical
the used elements
working gas, storing conditions
are summarized and aging
according to the
period. The samples
used working were stored
gas, storing conditionsin two anddifferent humidity
aging period. Therepresenting
samples were media,
stored namely,
in twoair (~50%
different
humidity)
humidity and water (100%
representing media,humidity),
namely, for air
a maximum of 4 weeks.
(~50% humidity) andIntensity
water of O1s and
(100% N1s peaks
humidity), forfora
samples
maximum plasma treatedIntensity
of 4 weeks. using air, ofoxygen,
O1s andand N1snitrogen,
peaks forand storedplasma
samples in air, exhibited
treated using a slight
air, increase
oxygen,
after 24 h of storage
and nitrogen, time, while
and stored in air,the O1s increase
exhibited for samples
a slight increase treated
after 24inhargon occurred
of storage time, after 168 the
while h asO1sthe
result
increaseof post-oxidation
for samples treated reactions and mobile
in argon phase
occurred reorientation.
after 168 h as the Samples
result stored in water medium
of post-oxidation had
reactions
even higher oxygen
and mobile content than samples
phase reorientation. Samplesstored
storedininairwater
medium,mediumwhilehad atomic
evenconcentrations
higher oxygen of content
O1s for
samples
than samplestreated using
stored inair, oxygen, nitrogen,
air medium, while atomicand argon after 672 of
concentrations h ofO1saging time achieved
for samples treated31.02
usingat.%,
air,
23.45
oxygen, at.%, 23.37 at.%,
nitrogen, and 23.92
and argon afterat.%,
672 hrespectively.
of aging timeStorageachieved in31.02
waterat.%,results
23.45in at.%,
an accumulation
23.37 at.%, and of
oxygen-containing
23.92 at.%, respectively. groups on the
Storage insurface of LDPE,
water results in anresulting in higher
accumulation atomic concentration
of oxygen-containing groupsof O1son
with greaterof
the surface loss
LDPE,of elemental
resultingcarbon.
in higher atomic concentration of O1s with greater loss of elemental
carbon.
Coatings 2019, 9, 145 15 of 24

Table 1. Chemical composition of LDPE treated using different gases and aged in air or water.
Atomic Concentration (at.%)

Table 1. Chemical composition of LDPE treated using different gases and aged in air or water.
Aging Time (h)
Element Treated in Atomic Concentration (at.%)
Untreated 24 168 672
Air
Element Air Water Air Time
Aging Water (h) Air Water
Treated in
C1s Untreated
97.41 86.76
Air 87.64 2480.23 83.18 168 81.06 82.08 67267.49
O1s 2.59 12.75 16.11 18.98 16.08 17.76
Air Water Air Water 15.59 31.02
Air Water
N1s
C1s 0.00
97.41 0.29
86.76 0.47
87.64 0.69
80.23 0.58
83.18 0.95
81.06 0.00
82.08 1.41
67.49
O1s 2.59 12.75 16.11 18.98
Aging Time17.76
16.08
(h) 15.59 31.02
N1s 0.00 0.29 in
Treated 0.47 0.69 0.58 0.95 0.00 1.41
Element Untreated 24 168 672
Oxygen Aging Time (h)
Element Untreated
Treated in Air 24Water Air 168 Water Air 672Water
Oxygen
C1s 97.41 86.58 85.82 85.03 85.22 82.61 87.51 72.91
Air Water Air Water Air Water
O1s 2.59 12.51 12.88 14.19 13.68 15.84 12.03 23.45
C1s 97.41 86.58 85.82 85.03 85.22 82.61 87.51 72.91
N1s
O1s 0.00
2.59 0.29
12.51 1.11
12.88 0.65
14.19 0.81
13.68 1.33
15.84 0.31
12.03 3.49
23.45
N1s 0.00 0.29 1.11 0.65 Aging
0.81 Time1.33
(h) 0.31 3.49
Treated in
Element Untreated 24 Aging168
Time (h) 672
Nitrogen
Treated in
Element Untreated Nitrogen Air 24Water Air 168 Water Air 672Water
C1s 97.41 87.84 85.35
Air 73.39
Water 85.90
Air 82.50
Water 86.89
Air 74.90Water
O1s
C1s 2.59
97.41 11.64
87.84 13.53
85.35 26.0873.39 13.16
85.90 15.7582.50 12.40
86.89 23.37
74.90
O1s
N1s 2.59
0.00 11.64
0.52 13.53
0.99 26.08
0.53 13.16
0.81 15.75
1.19 12.40
0.62 23.37
1.51
N1s 0.00 0.52 0.99 0.53 0.81 1.19 0.62 1.51
Aging Time (h)
Treated in Aging Time (h)
Element Untreated Treated in 24 168 672
Element Untreated Argon
Argon
24 168 672
C1s 97.41 84.24 85.06 86.14 84.60 79.31 84.39 72.28
C1s 97.41 84.24 85.06 86.14 84.60 79.31 84.39 72.28
O1s
O1s 2.59
2.59 14.40
14.40 13.72
13.72 13.4713.47 14.55
14.55 19.3919.39 14.81
14.81 23.92
23.92
N1s
N1s 0.00
0.00 1.09
1.09 1.02
1.02 0.40
0.40 0.68
0.68 1.11
1.11 0.48
0.48 3.73
3.73
1 - Untreated C1s
2 - Argon
3 - Nitrogen
4 - Oxygen
5 - Air
Intensity (a.u.)
O1s
N1s
5
4
3
2
1
1200 1000 800 600 400 200 0

Binding Energy(eV)
Figure
Figure 20. XPS
XPS spectra
spectra of
of plasma
plasma treated LDPE using different gases.
3.4. Surface
3.4. Surface Morphology
Morphology Analysis
Analysis
Surface roughness
Surface roughness significantly
significantly affects
affects wettability,
wettability, and
and therefore
therefore an
an investigation of the
investigation of the surface
surface
morphology is
morphology is highly
highly essential.
essential. SEM
SEM and
and surface
surface metrology
metrology systems
systems were
were used
used to
to analyze
analyze surface
surface
morphology changes on the LDPE surface after plasma treatment using various
morphology changes on the LDPE surface after plasma treatment using various gases and gases and their
their
mixtures. Figure
mixtures. Figure 21
21 shows
shows SEM
SEM images
images at
at 20000
20000× × magnification
magnification of
of untreated
untreated and
and plasma
plasma treated
treated
LDPE films at 120 s and 80 W, representing optimal conditions. The surface of untreated
LDPE films at 120 s and 80 W, representing optimal conditions. The surface of untreated LDPE film LDPE film
was characterized by specific nano-sized irregularities in its texture, originating from the
was characterized by specific nano-sized irregularities in its texture, originating from the molding molding
process. It can be observed that LDPE films plasma treated in the presence of air, nitrogen, argon, and
Coatings 2019, 9, 145 16 of 24
process. It can be observed that LDPE films plasma treated in the presence of air, nitrogen, argon,
and oxygen exhibited some textured grooves and cavities. These surface morphology changes are
oxygenattributed
mainly exhibited some
to thetextured grooves
etching action byand cavities.
plasma These
gaseous surface
species morphology
(electrons, ions changes are mainly
or free radicals) on
the LDPE surface, where the polymer surface is modified. This phenomenon is promotedthe
attributed to the etching action by plasma gaseous species (electrons, ions or free radicals) on LDPE
through
surface, where
physical the polymer
bombardment surface
of the is modified.
surface Thisenergetic
with highly phenomenon is promoted
particles generatedthrough
during physical
plasma
bombardment
treatment. of the surface with highly energetic particles generated during plasma treatment.
(a)
(b) (c)
(d) (e)
Figure
Figure 21. SEM images at 20000
20000××magnification
magnificationof ofLDPE
LDPEfilms:
films:(a)
(a)untreated;
untreated;(b)
(b)treated
treated in
in oxygen;
oxygen;
(c) treated in nitrogen; (d) treated in argon; (e) treated in
in air.
air.
The surface
The surface roughness
roughness inin terms of the arithmetic mean height (Saa)) was was obtained
obtained from
measurements
measurements usingusing a surface morphology system. The S parameter for untreated
The Saa parameter for untreated andand plasma
treated LDPE
treated LDPEfilms
filmsusing
usingdifferent
differentgases
gasesand
andtreatment
treatmenttimes
times are
are summarized
summarized in in Table
Table 2. could
2. It It could
be
be expected
expected thatthat roughness
roughness will
will increase
increase alongwith
along withexposure
exposuretime.
time.However,
However,thethe roughness
roughness values
exhibit rather
exhibit rather large
large fluctuations.
fluctuations. The
The precision
precision of
of surface
surface roughness
roughness measurements
measurements depends
depends on on the
Coatings 2019, 9, 145 17 of 24
size of the measured area. Surface topographies with smaller scan areas were obtained using 100×
magnification with 6× zoom, which may offer more accurate observations in terms of micro roughness
parameters. Figure 22 graphically presents surface roughness curves from 29.22 µm × 21.99 µm
scan areas of untreated and plasma treated LDPE films using different gases, with respect to the
treatment time. Initially, from 10–30 s, there were slight variations in roughness in terms of the
treatment time, because the etching processes occurred only at the beginning. However, the trend
stabilizes as etching processes gradually increased with increasing treatment times from 60 up to
120 s. With further increase in exposure time, the surface roughness again increased as possible
degradation processes occurred. This indicates the predominance of the etching process, where the
substrate suffers more material removal, producing a more dissimilar and rougher surface. Surface
roughness increased more significantly for air and oxygen after 120 s because oxidative plasmas are
typically accompanied by a higher etching level at the nano-scale. On the other hand, the use of argon
has relatively presented the least aggressive etching effects over a larger surface area. The effects of
gas mixtures on surface morphology were studied as well (Table 3). The evaluated Sa parameters
with respect to gas mixture ratios are presented in Figure 23. LDPE films treated under pure oxygen
exhibited a roughness value of 23 nm. Samples exposed to different gas mixtures of argon/oxygen,
argon/nitrogen, and nitrogen/oxygen. Increasing argon content in argon/oxygen and argon/nitrogen
mixtures during plasma treatment results in a sequential increasing and decreasing trend in the surface
roughness of the respective LDPE films until argon concentration reached 75%, but with still higher
surface roughness compared to films plasma treated with pure oxygen gas. The surface roughness
of LDPE films treated under nitrogen/oxygen mixture increased to a maximum at 25% nitrogen,
after which the roughness continues to drop. From these observations, it can be concluded that
plasma treatment under gas mixtures results in higher levels of surface roughness compared to their
pure gas counterparts. Given that surface wettability is influenced by surface roughness and the
polarity of the surface, a correlation between contact angle measurements and roughness trends was
observed. This correlation can be explained in terms of the substrate interfacial properties after plasma
treatment. As the roughness of the outer-most molecular layer of the surface increases, the liquid
droplets penetrate more easily into the surface, resulting in better wettability.
Table 2. Surface roughness of plasma treated LDPE.
Surface Roughness Sa (nm)

Treatment Time (s)
Oxygen Nitrogen Argon Air
0 17.4 17.4 17.4 17.4
10 26.2 25.5 28.6 48.9
20 19.7 39.4 26.1 44.6
30 22.9 31.3 21.6 30.9
60 23.0 27.8 24.8 26.1
120 23.1 27.0 21.3 33.1
180 36.2 32.2 30.9 31.5
Table 3. Surface roughness of plasma treated LDPE using different gas mixtures at 120 s.
Surface Roughness Sa (nm)

Gas Concentration Ratio
Argon/Oxygen Nitrogen/Oxygen Argon/Nitrogen
0 23.1 23.1 27.0
0.25 35.2 33.0 37.1
0.5 28.5 30.2 32.5
0.75 31.0 28.7 40.2
1 21.3 27.0 21.3
Coatings 2019, 9, 145 18 of 24
Air
Air
50 Oxygen
50 Oxygen
Nitrogen
Nitrogen
Argon
Argon
(nm)
roughness(nm)
40
40
Surfaceroughness
30
Surface 30
20
20 Untreated
Untreated
0 20 40 60 80 100 120 140 160 180

0 20 40 60 80 100 120 140 160 180
Treatment time (s)
Treatment time (s)
Figure 22. Surface roughness of plasma treated LDPE using air, oxygen, nitrogen, and argon.
Figure 22. Surface
Surface roughness
roughness of plasma treated LDPE using air, oxygen, nitrogen,
nitrogen, and
and argon.
argon.
Argon/Oxygen
Argon/Oxygen
Argon/Nitrogen
40 Argon/Nitrogen
Nitrogen/Oxygen
40 Nitrogen/Oxygen
(nm)
roughness(nm)
Surfaceroughness
30
30
Surface
20
20 Untreated
Untreated
0.00 0.25 0.50 0.75 1.00

0.00 0.25 0.50 0.75 1.00
Gas concentration ratio
Gas concentration ratio
Figure 23. Surface roughness plasma treated LDPE using different
different gas
gas mixtures
mixtures ratio.
ratio.
Figure 23. Surface roughness plasma treated LDPE using different gas mixtures ratio.
Detailed information
Detailed information
information about about the
about the surface
surfacetopography
topographychanges changeson on asmall
smallsurface
surfacearea area(10(10 µm ×
Detailed the surface topography changes on aa small surface area µm
(10 µm ×× 10
10
10 µm)
µm) of of LDPE
of LDPE
LDPE films films
films afterafter plasma
after plasma treatment
plasma treatment
treatment was was obtained
was obtained
obtained usingusing
using AFMAFM measurements.
AFM measurements.
measurements. This This technique
This technique
technique
µm)
was
was also
alsoused
used to quantify
to quantifysurface roughness
surface changes,
roughness represented
changes, by the surface
represented by the roughness
surface parameter
roughness
was also used to quantify surface roughness changes, represented by the surface roughness
(R a ), which (R
parameter characterizes
), which the average the
which characterizes
characterizes height of irregularities
average height of relative to therelative
of irregularities
irregularities sampleto surface in a direction
the sample
sample surface
parameter (Raa), the average height relative to the surface
perpendicular
in aa direction to the
direction perpendicular surface
perpendicular to plane.
to the The
the surface amplitude,
surface plane.
plane. The 3D height
The amplitude,
amplitude, 3D images,
3D height line profiles
height images,
images, line and R a values
line profiles
profiles and
in and
calculated
R from the Z-sensor
a values calculated from theimages
Z-sensor for images
untreated for and plasmaand
untreated treated
plasmaLDPE (120 sLDPE
treated and 80(120W) ssurfaces
and 80
Ra values calculated from the Z-sensor images for untreated and plasma treated LDPE (120 s and 80
are
W) shown
surfacesin Figure
are 24. Untreated
shown in Figure samples
24. had relatively
Untreated smooth
samples had surfaces
relativelywithsmooth
characteristic
surfacestextures
with
W) surfaces are shown in Figure 24. Untreated samples had relatively smooth surfaces with
originating
characteristic from the production
textures originatingprocess.
from the The
the Ra value of
production the untreated
process. The R LDPEof
Raa value
value surface was relatively
the untreated
untreated LDPE
characteristic textures originating from production process. The of the LDPE
low,
surface 15.7was
nm.relatively
Plasma treatmentlow, 15.7ofnm.the samples
Plasma led to noticeable
treatment of the changes
samples in
led surface
to morphology,
noticeable while
changes in
surface was relatively low, 15.7 nm. Plasma treatment of the samples led to noticeable changes in
R increased to
surface morphology,
a 21.3,
morphology, while18.4, 22.9,
while R and 21.6
Raa increasednm
increased to with the
to 21.3, use
21.3, 18.4, of oxygen,
18.4, 22.9,
22.9, and nitrogen,
and 21.6
21.6 nm argon,
nm with and
with the air,
the use respectively.
use ofof oxygen,
oxygen,
surface
The use ofargon,
nitrogen, gas mixtures
and air,ofrespectively.
argon/oxygen The and
use argon/nitrogen
of gas mixtures with
of a ratio of 1:1 led
argon/oxygen and toargon/nitrogen
an increase in
nitrogen, argon, and air, respectively. The use of gas mixtures of argon/oxygen and argon/nitrogen
surface roughness,
with aa ratio
ratio of 1:1 while
1:1 led
led to an
an Ra value
theincrease infor argon/oxygen
surface roughness,and argon/nitrogen
while the RRaa value
value forincreased
for to 18.0 and
argon/oxygen and
with of to increase in surface roughness, while the argon/oxygen and
21.5 nm, respectively
argon/nitrogen increased (Figure
increased to 25).
to 18.0
18.0 andThe R
and 21.5
21.5 value of the LDPE surface treated with
a nm, respectively (Figure 25). The Ra value of the LDPE nitrogen/oxygen
argon/nitrogen nm, respectively (Figure 25). The Ra value of the LDPE
mixture
surface was almost
treated with identical with Ra ofmixture
nitrogen/oxygen untreated wasLDPE, butidentical
almost the surface withmorphology
Raa of showed
of untreated
untreated different
LDPE, but
surface treated with nitrogen/oxygen mixture was almost identical with R LDPE, but
textures.
the surfacePlasma treatment
morphology of LDPE
showed samples
different using Plasma
textures. each gas and theirofmixtures
treatment LDPE led to the
samples regular
using each
the surface morphology showed different textures. Plasma treatment of LDPE samples using each
nano-patterned
gas andand their structures
their mixtures
mixtures ledover the surface
to the
the regular area, with a positive
nano-patterned effect on
structures increase
over in wettability.
the surface
surface area, with
with aa
gas led to regular nano-patterned structures over the area,
positive effect on increase in
positive effect on increase in wettability. wettability.
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2019, 9 FOR PEER REVIEW
9, 145 19 19
of 24
(a)
(a)
(b) (c)
(b) (c)
(d) (e)
(d) (e)
Figure
Figure 24. 24. AFM height images of LDPE: (a) untreated a = 15.7 nm); and plasma treated (120 s) in:
(R15.7
Figure 24. AFM
AFMheightheightimages
imagesof of
LDPE: (a) (a)
LDPE: untreated (Ra =(R
untreated nm); and plasma treated (120 s) in:
a = 15.7 nm); and plasma treated (120 s) in:
(b)(b) oxygen
oxygen (R (R a = 21.3 nm); (c) nitrogen (Ra = 18.4 nm); (d) argon (Ra = 22.9 nm); (e) air (Ra = 21.6 nm).
a = 21.3 nm); (c) nitrogen (Ra = 18.4 nm); (d) argon (Ra = 22.9 nm); (e) air (Ra = 21.6 nm).
(b) oxygen (Ra = 21.3 nm); (c) nitrogen (Ra = 18.4 nm); (d) argon (Ra = 22.9 nm); (e) air (Ra = 21.6 nm).
(a) (a)
Figure 25. Cont.

Coatings 2019, 9, 145 20 of 24
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2019, 9 FOR
9 FOR PEER
PEER REVIEW
REVIEW 20 20
(b) (c)
(b) (c)
Figure
Figure 25.25.AFM
AFM height
height images
images ofofplasma
plasmatreated LDPE
treated LDPE (120 s) in
(120 s) gas mixtures
in gas with with
mixtures 1:1 ratio: (a)
1:1 ratio:
Figure
(a) 25. AFM height
nitrogen/oxygen
nitrogen/oxygen images
(Ra =(R15.8=nm);
15.8of
(b)plasma
nm); treated
argon/oxygen
(b) (RLDPE
= 18.0
argon/oxygen
a
(120
nm);
(R s)(c)in
= gas mixtures
nitrogen/argon
18.0 nm); with
(R
(c) a = 1:1 nm).
21.5 ratio: (a)
nitrogen/argon
a a
nitrogen/oxygen
(R = 21.5 nm). (Ra = 15.8 nm); (b) argon/oxygen (Ra = 18.0 nm); (c) nitrogen/argon (Ra = 21.5 nm).
a
3.5. Plasma Affected Layer Analysis
3.5. Plasma Affected Layer Analysis
Since the native bulk properties of LDPE play an important role in various applications, the
Since the the native
surface-specificity native bulkproperties
ofbulk
plasma properties
treatmentofis ofLDPE
ofLDPE play
play
considerable anan important
important
interest. To role role
ensure in only
in that various
various applications,
applications,
the free surfacethe
theissurface-specificity
surface-specificity
modified without ofcompromising
of plasma plasma treatment
treatment is ofproperties
is ofbulk
the considerable
considerable interest.
duringinterest.
To Totreatment,
ensure
plasma ensure
that only that the
the only
free the free
surface
thickness
is increase
surface ofwithout
is modified
modified the newly
without formed layer the
compromising
compromising was bulk measured
the bulk using during
properties
properties thin filmplasma
during analysis. Figure 26the
plasmatreatment,
treatment, shows
the the
thickness
variation
increase of
thethe
of the newlyplasma
newly formedlayerlayer
formed thickness
layer was increase
was measured
measured related
usingtothin
using the film
thin 10 s analysis.
film treatment
analysis. timeFigure of 26theshows
plasmathe
formedof
variation
variation layer
thefor
ofthe LDPElayer
plasma
plasma samples
layer treated
thickness
thickness with
increase air,related
increase argon, nitrogen
to
related theto10 sand
the 10oxygen.
treatment The measured
time
s treatment oftime of thickness
the plasma the formed
plasma
increase
layer for LDPEof treated
samples LDPE samples
treated with ranges
air, argon,between
nitrogen 8.3%–153.4%,
and oxygen.
formed layer for LDPE samples treated with air, argon, nitrogen and oxygen. The measured thickness depending
The on
measured the treatment
thickness time
increase
of and used
treatedofLDPE
increase gas.
treated Slight
samples variations
LDPE rangessamples in the
between film thickness
ranges 8.3%–153.4%,
between 8.3%–153.4%,increase
depending have been observed
on the treatment
depending after plasma
time and used
on the treatment time
andtreatment,
gas. Slight
used gas. where
variations
Slightthe thickness
invariations increases
the film thickness
in the film during
increase up to 60
have
thickness beens of observed
increase exposure. Measurements
have after
beenplasma
observed after
treatment,
after60 plasma
swhere
for
thesamples
thickness treated with air
increases and oxygen
during up to 60revealed
s during a sudden
of exposure. drop in the thickness
Measurements 60increase percentage.
treatment, where the thickness increases up to 60 s of exposure.after s for samples
Measurements after 60treated
s for
On the other hand, the thickness increase percentage continues to grow with exposure time to argon
with air and
samples oxygen
treated withrevealed
air and aoxygen
suddenrevealeddrop in the thickness
a sudden drop increase
in the percentage.
thickness increaseOn the percentage.
other hand,
and nitrogen. This latter behavior can be explained in terms of the chemical nature of the working
the
On thickness
the other hand,increase thepercentage
thickness increasecontinues to grow with
percentage exposure
continues timewith
to grow to argon
exposureand nitrogen.
time to argon This
gas being used. Surface modification mainly occurs due to plasma deposition and etching, the effects
latter behavior This
and nitrogen. can be explained
latter behavior in terms
can be of explained
the chemical in nature
terms of of the
the working
chemicalgas being
nature ofused. Surface
the working
of which could be either individual or combined. Given that argon and nitrogen are relatively inert,
modification
gas being used. mainly
Surfaceoccurs due to plasma
modification mainly deposition
occurs due andtoetching,
plasma the effects ofand
deposition which couldthe
etching, beeffects
either
deposition after reactions in air with created radicals in LDPE chains is more prominent than etching,
individual
of hence or combined.
which increasing
could be either Given that
individual argon
or and
combined. nitrogen
Given are
that relatively
argon inert,
and
the layer thickness. In contrast, air and oxygen are considered to be oxidative deposition
nitrogen are after
relativelyreactions
inert,
in air with created
deposition
plasmas, after
where radicals
reactions
the etchingininair
LDPE chains
withdominates.
effect created is radicals
more
Thisprominent
in LDPE
causes the than
outeretching,
chains is morehence
surface increasing
prominent
layer of thanthe
the substrate layer
etching,
to
thickness.
hence In
increasingcontrast,
the air
layerand oxygen
thickness. areIn considered
contrast, to
air
be removed, hence decreasing the layer's thickness with increasing treatment time.be
and oxidative
oxygen plasmas,
are where
considered the
to etching
be effect
oxidative
plasmas, where
dominates. This the etching
causes effectsurface
the outer dominates. layerThis of thecauses
substratethe outer
to besurface
removed, layer of the
hence substratethe
decreasing to
be removed,
layer’s thicknesshence withdecreasing
increasing thetreatment
160 layer's
Oxygenthickness
time. with increasing treatment time.
Nitrogen
140 Argon
Plasma affected layer increase (%)
Air
160 Oxygen
120
Nitrogen
140 Argon
Plasma affected layer increase (%)
100
Air
12080
10060
8040
6020
40 0
20 10 20 30 40 50 60 70 80 90 100 110 120

Treatment time (s)
0
Figure 26. The change in % increase of plasma affected layer of LDPE with increasing treatment time.
10 20 30 40 50 60 70 80 90 100 110 120
Treatment time (s)
Figure 26. The

The change
change in % increase of plasma affected layer of LDPE with increasing
increasing treatment
treatment time.
time.
Coatings 2019, 9, 145 21 of 24
4. Conclusions
In summary, a series of plasma treatments were carried out on LDPE films in the presence of
pure oxygen, nitrogen, argon, air, and their mixtures representing reactive and inert gases to provide
a complex overview of the changes in wettability and adhesion properties, required for various
applications, such as printing, laminating, or antibiofouling. The effect of plasma on the LDPE surface
has been thoroughly characterized by various analytical and microscopic techniques. The LDPE films
exhibited a highly hydrophilic character after plasma treatment due to the incorporation of new polar
functional species on its surface. Plasma treatment of LDPE using air was the most effective in terms
of wettability when compared to plasma treatment using other gases and mixtures. Regarding the
surface morphological changes, plasma treatment led to notable textured structures on the outermost
surface layer of LDPE. Changes in the surface roughness indicate etching due to ion bombardment.
Further plasma treatment times were responsible for the degradation of the LDPE surface occurring
as a consequence of the progression of plasma etching. The maximum wettability of plasma treated
LDPE surface was achieved in 120 s of exposure and with 80 W of nominal power, and this treatment
revealed an 87% increase in the total surface free energy relative to an untreated surface. On the other
hand, plasma treatment of the LDPE surface under argon led to the highest adhesion characteristics
under the same conditions. However, over aging time, there was a reduction in hydrophilicity of
the plasma treated samples due to the reorientation and migration of polar species dependent on
the humidity of the medium in which samples were stored. The aging rate of plasma treated LDPE
samples was different based on the gas used. Moreover, wettability increases when treated samples
are stored in water for a short aging time. This was not in compliance with adhesion characteristics.
Peel resistance of plasma treated LDPE samples stored in air increased after short aging times, while
the use of water media led to the opposite effect. This phenomenon can be attributed to the diffusion
of low-molecular weight oxidative products towards the surface area responsible for lack of adhesion
and increase of wettability during short aging time periods.
Author Contributions: Conceptualization, A.P.; Methodology, A.P.; Validation, A.P.; Formal Analysis, A.P.;
Investigation, A.E.A., S.H. and A.P.; Resources, M.O.; Data Curation, A.P.; Writing—Original Draft, A.E.A.;
Writing—Review & Editing, A.P. and I.K.; Visualization, A.P., A.E.A. and S.H.; Supervision, A.P.; Project
Administration, A.P.; Funding Acquisition, A.P.
Funding: This publication was made possible by an Award JSREP07-022-3-010 from the Qatar National Research
Fund (a member of The Qatar Foundation). The statements made herein are solely the responsibility of the authors.
Acknowledgments: The authors gratefully acknowledge Gas Processing Center (GPC), Qatar University,
for carrying out the XPS analysis.
Conflicts of Interest: The authors declare no conflict of interest.
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© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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Keywords: RF plasma; polyethylene; surface modification

Coatings 2019, 9, 145; doi:10.3390/coatings9020145 www.mdpi.com/journal/coatings

2. Materials and Methods

Coatings 2019, 9 FOR PEER REVIEW 3

2.3. Peel Test Analysis

2.4. Surface Chemistry Characterization

2.5. Surface Morphology Analysis

2.6. Plasma Film Thickness Measurement

3.1. Surface Wettability Analysis

40 50 60 70 80 90 100 110 120 130 50 60 70 80 90 100 110 120 130

Figure 2. Surface wettability of low-density polyethylene

The hydrophilicity using

Ethylene glycol 30 Polar

100 Untreated Air

100 Untreated Air

3.2. Adhesion Investigation

Figure 9. Peel resistance

LDPE samples were treated in different gases (air, (air, oxygen,

1800 1600 1400 1200 1000

4000 3500 3000 2500 2000 1500 1000

7 - 672 h 1800 1600 1400 1200 1000

-OH C=O -O-

4000 3500 3000 2500 2000 1500 1000

-CH2- val. 2sym.

7 - 672 h 1800 1600 1400 1200 1000

4000 3500 3000 2500 2000 1500 1000

1800 1600 1400 1200 1000

-OH C=O -O-

4000 3500 3000 2500 2000 1500 1000

4 - 168 h -CH22- val. sym.

1800 1600 1400 1200 1000

-OH C=O -O-

-OH C=O -O-

4000 3500 3000 2500 2000 1500 1000

1800 1600 1400 1200 1000

Figure 19. FTIR

Coatings 2019, 9, 145 15 of 24

Atomic Concentration (at.%)

1200 1000 800 600 400 200 0

Table 2. Surface roughness of plasma treated LDPE.

Surface Roughness Sa (nm)

Surface Roughness Sa (nm)

0 20 40 60 80 100 120 140 160 180

0.00 0.25 0.50 0.75 1.00

Figure 25. Cont.

20 10 20 30 40 50 60 70 80 90 100 110 120

Figure 26. The

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