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Effect of corona treatment on adhesion enhancement of LLDPE

Article  in  Surface and Coatings Technology · December 2017

DOI: 10.1016/j.surfcoat.2017.12.018

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Accepted Manuscript

Effect of corona treatment on adhesion enhancement of LLDPE

Anton Popelka, Igor Novák, Mariam Ali S.A. Al-Maadeed,

Mabrouk Ouederni, Igor Krupa

PII: S0257-8972(17)31235-5
DOI: doi:10.1016/j.surfcoat.2017.12.018
Reference: SCT 22936
To appear in: Surface & Coatings Technology
Received date: 1 October 2017
Revised date: 30 November 2017
Accepted date: 8 December 2017

Please cite this article as: Anton Popelka, Igor Novák, Mariam Ali S.A. Al-Maadeed,
Mabrouk Ouederni, Igor Krupa , Effect of corona treatment on adhesion enhancement
of LLDPE. The address for the corresponding author was captured as affiliation for all
authors. Please check if appropriate. Sct(2017), doi:10.1016/j.surfcoat.2017.12.018

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 ACCEPTED MANUSCRIPT

Effect of corona treatment on adhesion enhancement of LLDPE

Anton Popelka1,*, Igor Novák2, Mariam Ali S A Al-Maadeed1,3, Mabrouk Ouederni4, Igor
Krupa5

1
Center for Advanced Materials, Qatar University, P.O. Box 2713, Doha, Qatar
2
Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41 Bratislava 45,
Slovakia
3

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Materials Science and Technology Program, Qatar University, P.O. Box 2713, Doha, Qatar
4
QAPCO R&D – Qatar Petrochemical Company, P.O. Box 756, Doha – State of Qatar
5

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QAPCO Polymer Chair Professor, Center for Advanced Materials, Qatar University, P.O. Box
2713

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Abstract
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Polymers/metal laminates are often used to improve physical and mechanical properties,
especially those required in building applications. A flat aluminum composite panel (ACP)
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consisted mainly of two thin metal sheets usually made of aluminum (Al) and a non-metal core,
such as polyethylene (PE). The lack of adhesion associated with the low wettability of PE is a
serious problem. An eco-friendly, dry, non-destructive corona treatment technique can be
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applied to solve this problem. In this work, the use of a corona treatment to enhance the
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adhesion properties of linear low-density polyethylene (LLDPE) was studied. The changes in
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surface and adhesion properties were thoroughly analyzed using various analytical techniques
and methods to obtain the optimal parameters for corona discharge using contact angle
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measurements, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron

spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy
(AFM). AFM force adhesion measurements were used to analyze the effect of the corona
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treatment on the adhesion enhancement of LLDPE, and the peel tests confirmed a significant
increase in peel resistance in the LLDPE/Al laminate. A synergy effect from using the corona
treatment in combination with an ethylene acrylic acid dispersion primer was observed.

Keywords: Corona Treatment, Wettability, Adhesion, Polyethylene, Laminates

* Corresponding author: A. Popelka, anton.popelka@qu.edu.qa

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Introduction
A combination of polymeric materials with metals are used in many applications because of
their enhanced physical and mechanical properties. Laminates made of polyethylene (PE) and
aluminum (Al) sheets are predominantly used for the manufacturing of aluminum composite
panels (ACPs). ACPs are frequently utilized in building applications for facades or claddings as
decorations and energy-saving materials [1]. Linear low-density polyethylene (LLDPE) is
frequently used for many applications due to its high tensile strength, toughness and superior
impact and puncture resistance [2-6].

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The hydrophobic character of LLDPE is problematic for applications requiring good adhesion
to hydrophilic surfaces. Various methods of surface pretreatment for LLDPE have been

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investigated [7]. Some strong oxidizing agents, i.e., chromic, sulfuric or nitric acid have been

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tested to achieve a stable modified LLDPE surface with higher wettability [8]. The etching
process usually consists of three stages: the first is oxidation and introduction of amorphous
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parts; the second is chain scission and destruction of amorphous parts; the third represents
chain scission and destruction of crystalline parts. However, this pretreatment method is not
widely used because of the very aggressive oxidizing reagents. The increase in etching time
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leads to chain scission and destruction of LLDPE amorphous parts, leading to increases in
surface roughness. Moreover, the degradation of LLDPE caused by this pretreatment resulted
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in a decrease in mechanical properties [8-10]. Mulla et al. [11] chemically modified LLDPE by
chromic acid treatment and then coated the material with clove essential oil to impart
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antimicrobial properties. The morphology of LLDPE modified by chromic acid exhibited

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pitting and a rough surface. The LLDPE films were also modified using chemical-free UV
irradiation. However, the degradation processes led to very fragile mechanical properties. [12].
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Basheer at el. [13] have tested LLDPE modified by  irradiation. Crosslinking in the LLDPE
was two-fold higher at equal doses compared to LHDPE (linear high-density polyethylene).
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Krivoguz et al. [14] grafted LLDPE using polar trans-ethylene-1,2-dicarboxylic acid during
reactive extrusion leading to a 1.5-fold increase in strength. LLDPE packaging foil was also
modified using a low-temperature barrier or radio-frequency plasma to increase its
hydrophilicity [15].
Modification of the upper layer using a low-temperature plasma generated by corona discharge
is a promising physical method for enhancement of surface and adhesion properties in large-
scale industrial applications [16-19]. Corona treatment has advantages such as effectiveness,
low cost and suitability for production lines [20-25].

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The application of corona discharge is not limited to the treatment of thin polymer films, but
can also be used for the treatment of thicker profiles and 3D objects [26]. The corona system
generates a plasma with a series of micro-discharges (usually 100/cm2, with a diameter of 0.01
- 0.1 µm) that modify the surface uniformly and homogeneously [27]. Corona discharge can
lead to the generation of reactive oxidants, such as ozone, oxygen-free radicals or oxygen
atoms. Interactions with free radicals result from electron bombardment at the surface and are
responsible for the creation of carbonyl, carboxyl, hydroxyl or ester functional groups. This
treatment effectively oxidizes only the thin surface layers, without negatively affecting bulk

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mechanical properties. Moreover, etching and ablation processes are important for increasing
surface roughness [28-32]. These oxidation and surface roughness changes lead to improved

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wettability and adhesion characteristics of the polymer surfaces [33, 34].

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In this work, the focus was to clarify the phenomenon at the surface of the corona-treated
LLDPE surface that leads to enhanced adhesion characteristics. Advanced analysis techniques
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and methods were used to describe the parameters affecting adhesion, such as wettability,
chemical composition, surface roughness or the use of primers. Moreover, the stability of the
corona-treated surface with aging time was carefully investigated.
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Experimental
Materials
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LLDPE sheets (0.3-mm thick) were prepared from LLDPE granulates (Lotrène® Q1018 N,
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QAPCO, Qatar) using a mounting hot press machine AutoFour/3012-NE, H (Carver, USA). Al
foils (0.5-mm thick, IB & M Europe, Slovakia) and ultra-pure water (Purification System
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Direct Q3, France) and ethylene glycol (≥ 98 % (FLUKA, Belgium) were used to investigate
the wettability. Dichloromethane (BDH, England) was used to clean the samples. Water-borne
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emulsions primers, ethylene acrylic acid dispersions Michem® Prime 4983 (MICHELMAN,
USA), Michem® Prime 4990R (MICHELMAN, USA) and chlorinated synthetic primer EPA-
W (ICHEMCO, Italy) were used for the adhesion analyses.

Corona Treatment
Corona treatment of the LLDPE samples was performed with a corona lab plasma system
(Softal, Germany) through the application of dynamic conditions (a movement of sample
during treatment) to ensure homogeneous treatment. The treatment process was first optimized
by varying operating parameters such as nominal power (100 - 300 W) and treatment time (1 -

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10 s). A set of powered ceramic electrodes (metal embed in alumina) containing special
ceramic insulator assemblies (for optimal isolation of high voltage) generated a macroscopic
homogeneous plasma discharge. The lab corona system consisted of a sample holder to treat
samples with a maximum dimension of 29x19 cm and was equipped with suction control. The
distance between the electrodes and the sample holder was 1 mm. The apparatus contained a
high-efficiency catalytic ozone exhaust system to ensure a safe working environment.

Wettability Measurement

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The contact angle-measuring optical system OCA35 (Data Physics, Germany) was used to
measure the wettability changes in the LLDPE surface after the corona treatment. Static

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measurements of the sessile drop with 3 µL of each testing liquid were used to avoid

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gravitational effects. Ten individual readings from different areas were used to obtain average
values for the contact angles (the angle between the solid/liquid and liquid/vapor interface).
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The obtained results from the contact angle measurements were used for the subsequent
evaluation of surface free energy (γ) and its components, such as polar (γp) and dispersive (γd)
elements using the Owens-Wendt-Rabel-Kaelble regression model [35].
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Chemical Composition Analyses

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For changes in the chemical composition in corona-treated LLDPE samples, Fourier-

transformed infrared spectroscopy (FTIR) with attenuated total reflectance (ATR) accessory,
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was used. Using a Spectrum 400 (PerkinElmer, USA) spectrometer, qualitative information for
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the absorbance of chemical groups in the middle infrared region (4400-400 cm-1) was obtained.
The wavelength resolution and number of scan was set up to 4 and 8, respectively.
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Qualitative information about the chemical composition changes after corona treatment of
LLDPE samples was obtained using X-ray photoelectron spectroscopy (XPS). XPS equipment
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K-Alpha (Thermo Fischer Scientific, UK) was used for this study. Monochromatic Al Kα1,2
radiation at 1,486.6 eV with a 400-µm spot area was used to irradiate the LLDPE samples at 6
mA x 12 kV. Hemispherical analyzer at 45° angle was utilized to detect photoelectrons. The
constant analyzer energy mode with pass energy of 200 eV and 0.4 eV energy step for the
survey was used for obtaining the XPS spectra. The system flood gun providing low-energy
electrons (~0 eV) and argon ions (20 eV) from a single source were used for a charge
compensation. An automated calibration routine and supplied Au, Ag and Cu internal standards
were used for the calibration of the spectra. The spectra charge shift was subsequently
corrected by adjusting the C1s peak at 285 eV. Digital acquisition and data processing was

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performed using Avantage software allowing obtaining surveys and high resolution C1s
spectra.

Surface Morphology Investigation

The surface morphology after corona treatment of LLDPE samples was studied using scanning
electron microscopy (SEM). SEM microscopy (Nova NanoSEM 450, FEI, USA) was employed
to obtain 2D images of the analyzed surfaces. Before measurement, thin Au layers a few
nanometers thick were sputter-coated onto LLDPE samples by Agar sputter coater (Agar

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Scientific, UK) for 40 s at 10 mA to ensure high-resolution SEM images and avoid the
accumulation of electrons in the measured layer. Multiple areas were carefully analyzed to

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capture the representative images.

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The 3D surface morphology changes of the LLDPE samples after corona treatment in the
10x10 µm2 scan area were detected using atomic force microscopy (AFM). MFP-3D AFM
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equipment (Asylum research, USA) was employed for this purpose. Scanning was carried in
the tapping mode in air (AC mode) using a Silicon probe AC160TS (Al reflex coated Veeco
model – OLTESPA, Olympus) with f = 300 kHz and k = 26 N/m. The AFM images and
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roughness parameter (Ra) were obtained by Igor Pro software.

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Measurement of Adhesion Properties

AFM was also used to analyze the physiochemical and mechanical characteristics of the
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LLDPE surface at the nano-scale using a force volume measurement technique. Adhesion force
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mapping was performed in contact mode to ensure good interactions between the tip
(AC160TS) and the LLDPE surface. Measurement of the corona treatment effect on the
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adhesion characteristics was presented in a histogram obtained from adhesion force maps
recorded within a specific area of 1x1 µm2 with 56x56 contacts between the tip and sample. A
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Gaussian approach was subsequently used to calculate the mean of adhesion forces.
The adhesion characteristics at the macro level were studied using a standard test method
ASTM D6862 designated for the measurement of peel resistance at 90° of peeling between
flexible and rigid materials. For this purpose, LLDPE/Al adhesive joints (90 x 70 mm2) were
prepared using a mounting press machine (110 °C, 2 min pressing with subsequent cooling
RT). Analyses were performed using a Peel Tester LF-Plus (Lloyd Instruments, UK) equipped
with a 1 KN cell. The LLDPE/Al adhesion joints (15 mm in width and 70 mm in length) were
delaminated at 10 mm/min to assure a stable peeling process. Six independent measurements
were performed to obtain average values for peel resistance. Peel tests were used to investigate

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the adhesion of LLDPE/Al using only commonly used primers and their combination with
corona treatment. For this purpose, 1 mL of adhesion primer was deposited on each untreated
and corona-treated LLDPE and Al surface using a Pasteur pipette. The layers were spread
evenly, and samples were inserted into the oven (40 °C, 20 min) to evaporate water from the
dispersions. LLDPE and Al with deposited primers were subsequently bonded together using a
mounting hot press machine (110 °C, 2 min with subsequent cooling RT).

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Results and Discussion
Wettability Analyses

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Wettability was evaluated using contact angle measurements of LLDPE samples, with the

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subsequent calculation of surface free energy. Optimization of corona treatment with respect to
wettability improvement by varying treatment time and nominal power are shown in Fig. 1.
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The trend associated with contact angles and surface-free energy of LLDPE after optimization
of nominal power is shown in Fig. 2 for clarity. The chemically inert (hydrophobic) surface of
untreated LLDPE exhibited low wettability. Therefore, the contact angle of water and ethylene
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glycol was relatively high 103.4° and 75.2°, respectively. Therefore, the surface free energy for
untreated LLDPE was relatively low (25.4 mJ/m2). The corona treatment of LLDPE led to
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chemical and structural changes in surface area through functionalization, ablation and/or
etching mechanisms and therefore wettability significantly increased. Even short treatments
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times, e.g., 1 s (300 W), were responsible for a noticeable increase in wettability, while the
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contact angle of water and ethylene glycol decreased to 59.3° and 30.0°, respectively, and
surface free energy reached 42.7 mJ/m2. The additional increase in corona treatment time was
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responsible for slight decreases in contact angle. The maximum increase in wettability of the
LLDPE surface was observed at 7 s corona treatment time and 300 W nominal power.
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Moreover, the corona discharge at this nominal power achieved maximum homogeneity
compare to other tested levels. Using these parameters, the contact angle of water and ethylene
glycol was 53.2° and 24.3°, respectively, and the value of the surface free energy was 46.5
mJ/m2.

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48
105 100W
150W 45
200W
43

Surface free energy (mJ/m )

250W

2
Contact angle of water (°)

100 300W 40

38

95 35

60
100W
55 26 150W
200W
50 250W
300W
45 25
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
Treatment time (s) Treatment time (s)

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a b
Fig.1. Wettability vs. treatment time of LLDPE with varying nominal power: a - contact angle

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of water and b - surface free energy.

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110
Surface free energy and its components (mJ/m )
50
2
Water
100 Ethylene glycol
90 40
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80
Contact angle (°)

30
70

60
20
50
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40
10
30 Surface free energy
Dispersive component
20 0 Polar component
10
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
Treatment time (s) Treatment time (s)
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a b
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Fig. 2. Wettability of corona-treated LLDPE vs. treatment time: a - contact angle of water and
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ethylene glycol and b - surface free energy and its components.

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The achieved wettability immediately after corona treatment does not represent the final state,
and aging effects can lead to the deterioration of wettability with storage time. Various
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parameters are responsible for the aging effect after plasma treatment, such as crystallinity,
aging medium, temperature and humidity. The reorientation of incorporated polar groups from
the top surface area to the polymer layers underneath was affected by the treatment and the
mobility of small segments of polymer chains were primarily responsible for aging effects [36].
The hydrophilicity of polymers surrounded by a hydrophilic environment (water) is maintained
due to the affinity of polar groups with the aqueous environment. In contrast, polar groups in a
non-polar environment are forced into the bulk of the material and result in a significant loss in
hydrophilicity [37]. On the contrary, hydrophobic recovery is slower in dry air than in humid

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air due to the plasticizing effect of water increasing a mobility of the macromolecular chain
[38].
The fastest changes in contact angles and surface free energy of corona-treated LLDPE samples
were observed during the first 24 hours of aging time (Fig. 3). After 24 hours, the surface free
energy decreased by 10.7 %. With the additional increase in aging time, the decrease in surface
free energy was gradual over 240 hours (decrease 18.3 %). After 240 hours of aging time,
hydrophobic recovery was stabilized and no additional changes in wettability were observed.
Moreover, the curve trends point to only partial hydrophobic recovery with retaining enough

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hydrophilicity of the corona treated LLDPE surface after aging time in compare with its
untreated counterpart. These findings confirmed the steady corona treatment of LLDPE.

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Moreover, the rotational and translational motions are minimized by large crystalline regions,

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in the surface region after the plasma treatment leading to only a partial aging effect [39].
Surface free energy and its components (mJ/m )

110 50
2
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105 Water - untreated LLDPE Surface free energy
100 45
Dispersive component
95 Polar component
40
90
85 35
80 Ethylene glycol - untreated LLDPE
Contact angle (°)

75 30
70 Surface free energy - utreated LLDPE
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65 25
Dispersive - utreated LLDPE
60
55 20
50 15
45
40 10
35 Water
30 Ethyleneglycol 5
25 Polar - utreated LLDPE
0
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20
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
Aging time (h) Aging time (h)
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a b
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Fig. 3. Wettability of corona-treated LLDPE vs. aging time: a - contact angle of water and
ethylene glycol and b - surface free energy.
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Investigation of Chemical Composition

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Changes in chemical composition to the surface area of LLDPE after corona treatment caused
by the incorporation of polar groups were analyzed by FTIR using the ATR accessory. The
spectrum of untreated LLDPE consisted of absorbance bands for non-polar groups (Fig. 4).
These were represented by bending in plane vibrations at 1470 cm‒1 (asymmetric -CH3), 1460
cm-1 (asymmetric C-H) and 1377 cm‒1 (symmetric -CH3). Moreover, the doublet at 731 cm‒1
and 720 cm‒1 belonged to the C-H (-CH2-)n≥6 rocking deformation [40] in the spectrum. The
spectra of the corona-treated LLDPE surface demonstrated remarkable changes. Evidence of
incorporated oxygen-containing functional groups was observed at 3500 cm‒1 (-OH) and 1800
– 1500 cm‒1 (C=O). Moreover, an absorbance band with a maximum at 1730 cm-1 (C=O in

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carboxylic acids) appeared. The intensity of absorbance bands associated with polar functional
groups increased with increasing treatment time. Equal clamp pressure (measured by the
equipment) was applied for each measurement. An FTIR technique was also used for studying
the aging effect. The oxidative reaction of corona-treated LLDPE films led to changes in FTIR
spectra with aging time (Fig. 5). The increased intensity in absorbance bands centered
approximately at 3500 cm-1 and 3250 cm-1 (-OH) was likely caused by hydroperoxides
decomposition in the LLDPE after aging effects. The increase in intensity centered at 1630 cm-
1
was associated with carbonyl species originating from hydroperoxide decomposition as a

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result of radical reactions of LLDPE with oxygen [41]. Moreover, hydroperoxide
decomposition contributes ester formation, as observed in the increased intensity centered at

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approximately 1030 cm-1 [42] accompanied by a slight broadening absorbance band with a

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maximum at 1730 cm-1. The above-described effects increased with increasing aging time until
168 hours. Further aging time did not lead to significant changes in the spectra. The aging
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effect was stabilized, corresponding to results obtained from contact angle measurements.
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val. asym.
-CH2-
val. sym.
-CH2-
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Absorbance (a.u.)

def.
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def. asym. -CH2-

-CH3 def. asym.
-OH 6 O-C=O C=O -CH
5
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4
3
2
1

4000 3500 3000 2500 2000 1500 1000 500

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-1
Wavenumbers (cm )

Fig. 4. FTIR spectra of LLDPE for various treatment times (1-0s, 2-1s, 3-3s, 4-5s, 5-7s, 6-10s).

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val. asym.
-CH2- val. sym.
-CH2-

Absorbance (a.u.)
def.
-CH2-
def. asym.
-CH3
def. asym.
-CH

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-OH C=O C-O
6 O-C=O
5
4
3
2
1

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4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumbers (cm )

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Fig. 5. FTIR spectra of corona-treated LLDPE for various aging times (1-0h, 2-24h, 3-72h, 4-
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168h, 5-336h, 6-432h).

XPS was employed to quantify chemical composition changes to the LLDPE surface after
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corona treatment. The XPS spectra and a detail of the C1s spectra for untreated and corona-
treated samples are shown in Fig. 6. The highest proportion in the spectrum of untreated
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LLDPE was for C-C/C-H bonds (95.2%) with 285 eV binding energy. The presence of O1s
peak at 532 eV binding energy was caused by the processing additive in LLDPE. Moreover,
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negligible traces of Na, Si, S or Ca present in the spectra of LLDPE likely originated from the
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preparation process. The peaks about 1074 eV, 107 eV and 171 eV represent Na1s, Si2p and
S2p, respectively. Moreover, the peak at 500 eV is associated with NaKL1 (auger). Significant
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changes in the XPS spectra of LLDPE were observed after corona treatment, which led to an
increase in intensity for O1s (C-O, O-C=O) as a result of oxidation processes. The atomic
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percentage of O1s increase was 2.2% and 11.3% in the LLDPE spectrum after 1 s and 7 s of the
corona treatment, respectively. Moreover, the small percentage of nitrogen-containing groups
was observed in the XPS spectrum of LLDPE after 7 s of corona treatment.

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C1s O1s N1s C1s C1s

(at.%) C-C (97.3%)
1. 0s 92.8 4.8 - C-O/C-N (1.2%) C-C
2. 1s 92.3 7.0 - O=C-O (1.5%)
3. 7s 82.3 16.1 1.0
Counts / s

Counts / s
O1s

N1s C-O/C-N
3
2 O-C=O
1

1200 1000 800 600 400 200 0 298 296 294 292 290 288 286 284 282 280
Binding energy (eV)
Binding energy (eV)

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a b

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C1s C1s
C-C (94.8%) C-C (83.9%)
C-O/C-N (3.9%) C-C C-O/C-N (9.3%) C-C
O=C-O (1.3%) O=C-O (6.8%)

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Counts / s

Counts / s
s

s
C-O/C-N C-O/C-N
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O-C=O O-C=O

298 296 294 292 290 288 286 284 282 280 298 296 294 292 290 288 286 284 282 280
Binding Energy (eV) Binding Energy (eV)
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c d
Fig. 6. XPS spectra of: a - untreated and corona-treated LLDPE samples; and C1s spectra of
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LLDPE samples: b - untreated, c - 1 s corona-treated, and d - 7 s corona-treated.

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Surface Morphology Investigation

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Surface roughness is a parameter closely related to wettability. For this reason, analyses of
surface morphology were conducted using SEM. SEM images of untreated and corona-treated
LLDPE surfaces are shown in Fig. 7. An untreated LLDPE sample consisting of crystalline and
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amorphous phases exhibited a characteristic surface texture originating from the production
process. The 1 s corona treatment was responsible for slight changes in surface morphology,
creating larger peak and valley-like areas as a result of etching or ablation mechanisms. The
corona treatment of LLDPE after 7 s led to additional changes in surface morphology
responsible for the rougher surface.
A more detailed study of morphological changes at the LLDPE surface after corona treatment
was also performed using AFM. This technique allowed obtaining 3D images with a high
resolution and was able to quantify surface roughness as a Ra value, which represents the

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arithmetic mean of the absolute height perpendicular to the surface. The representative images
of the LLDPE samples were captured after a careful investigation of different locations. The Ra
values were evaluated by the software from the whole area of the relevant z-sensor images. The
3D height, amplitude and line profile (obtained from Z-sensor) of LLDPE samples are shown
in Fig. 8. The surface of untreated LLDPE exhibited relatively low surface roughness, with an
Ra of 24.8 nm. The 1 s corona treatment of LLDPE only led to a slight increase in Ra value
(approximately 5 %). However, 7 s corona treatment resulted in a remarkable increase in
surface roughness, while the Ra value increased to 46.1 nm. Moreover, in the line profile graph,

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the most indented line was observed for the LLDPE sample treated by the corona discharge at 7
s.

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a b c
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Fig. 7. SEM images of LLDPE: a - untreated, b - 1 s corona-treated, and c - 7 s

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corona-treated.
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a b c
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Fig. 8. AFM images (3D height and 2D z-sensor with line profiles) of LLDPE: a
- untreated (Ra = 24.8 nm), b - 1 s corona-treated (Ra = 26.1 nm), and c - 7 s
corona-treated (Ra = 46.1 nm).

Measurement of Adhesive Properties

Adhesion is a complex phenomenon that includes chemical and physiochemical factors.

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Etching and ablation processes during corona treatment are responsible for roughness changes
to the surface area, leading to adhesion increases (larger contact area). The increase in the

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surface free energy of the polymer surface beyond the surface tension of the adhesive is

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mandatory for sufficient wetting of the polymer by the adhesive. AFM using measurements of
force adhesion between the AFM tip and the sample surface was conducted to obtain
information about the adhesion characteristics of the LLDPE samples at the nano-scale (tip
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radius ~ 7 nm). Histograms and force adhesion distribution images are shown in Fig. 9. The
untreated LLDPE was characterized by relatively poor adhesion characteristics, with a mean
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adhesion force of 297 nN (49 nN peak width) fitted by Gaussian approach. Corona treatment
lead to enhanced adhesion between the AFM tip (AC160TS) and the LLDPE surface, as
confirmed by the increase in the mean adhesion force to 313 nN (37 nN peak width) and 510
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nN (103 nN peak width) for 1 s and 7 s corona treatment times, respectively.

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a b c

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Fig. 9. AFM force adhesion mapping histogram (up) and images of LLDPE
(down): a - untreated (mean adhesion force = 297nN), b - 1 s corona-treated
(mean adhesion force = 313nN), and c - 7 s corona-treated (mean adhesion force
= 510nN).

Adhesion analyses at the nano-scale (by AFM) were extended by macro-scale analyses using

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peel tests at 90 deg. The untreated LLDPE and Al surfaces (cleaned) have poor adhesive
properties associated with the hydrophobic character of LLDPE and Al (e.g., processing

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impurities such as oil from the rolling process), and peel resistance was not measurable, since

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films delaminate easily, even during manipulation. Corona treatment of LLDPE and Al led to a
significant improvement in adhesion characteristics (Fig. 10a). The corona treatment of both
surfaces led to a significant enhancement in adhesion. Even 1 s of treatment led to an increase
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in peel resistance from approx. zero to 70±5 N/m. Increasing treatment time led to an
exponential growth tendency in peel resistance up to 7 s, when peel resistance reached 267±11
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N/m. Corona treatments longer than 7 s resulted in only slight changes in peel resistance, to
306±15 N/m at 10 s and the additional treatment time increase did not lead to any significant
changes. The 90 deg peel test technique was also used to analyze the aging effect on the
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adhesion of prepared LLDPE/Al laminates. The changes in peel resistance with aging time are
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shown in Fig. 10b. The post-physical and physiochemical interaction between plasma-treated
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surfaces of LLDPE and Al led to a slight increase in peel resistance of prepared adhesive joints
after 24 hours of their aging time. A subsequent enhancement of adhesion characteristics was
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observed with increasing aging time until 240 hours. The additional increase in aging time did
not lead to significant changes in peel resistance and the aging process was stabilized since post
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physical/physiochemical reactions were completed. Comparison of the corona effect on the

improvement of adhesion characteristics of LLDPE with commonly used adhesion primers in
real applications was also performed using a peel test. Three conventional adhesion primers
were carefully selected (experimental section 2.1 and 2.6) to analyze the adhesion increase in
the LLDPE/Al laminate with and without the corona effect. The results are summarized in Fig.
11. From these findings, it is clear that the adhesion increase using only primers was smaller
than with corona treatment alone. Corona treatment combined with ethylene acrylic acid
dispersion primers (type 2 and 3) led to a significant increase in peel resistance compared to

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primers alone. Moreover, the use of primer 2 and corona treatment had a synergistic effect on
the peel resistance of the LLDPE/Al laminate.

350 500

450
300
400

250 350

Peel resistance (N/m)

Peel resistance (N/m)

300
200
250
150 200

100 150

100
50

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50

0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 0 50 100 150 200 250 300 350 400 450 500
Treatment time (s) Ageing time (h)

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a b
Fig. 10. Peel resistance vs: a - treatment time, b - aging time of LLDPE/Al laminate.

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1000 LLDPE+Primer
LLDPE corona treated+Primer
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800
Peel resistance (N/m)

599.5
600

396.4
400
Corona treated only
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200

17.5 264.2 235.7

0
16.8
1 2 3
Type of primer
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Fig. 11. Peel resistance of LLDPE/Al vs. used primer for untreated and 7-s
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corona-treated samples (1–EPA-W, 2–Michem® Prime 4983R, 3–Michem®

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Prime 4990R); dashed line represents peel resistance of LLDPE/Al-only corona-

treated samples.
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Conclusions
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The effect of the corona treatment on the enhancement of the adhesive properties of LLDPE
was investigated in this paper. The surface treatment resulted in remarkable changes in surface
properties, which led to adhesion enhancement. The wettability of LLDPE significantly
increased even after 1 s of treatment due to the incorporation of polar functional groups, as
confirmed by FTIR and XPS analyses. The maximal wettability increase on the LLDPE surface
was achieved after 7 s of corona treatment, corresponding to a surface free energy increase of
83 %. The surface roughness increase of the corona-treated LLDPE surface also played an
important role in wettability enhancement, as confirmed by SEM and AFM measurements. The

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AFM technique and peel tests showed remarkably enhanced adhesion characteristics, even
compared to some conventional primers. The peel resistance of the LLDPE/Al laminate
increased from near zero to 266.5 N/m after 7 s of the corona treatment. The combination of
corona treatment with ethylene acrylic acid dispersion primers led to an increase in peel
resistance by 68.2 % and 126.9 % for primer types 2 and 3, respectively, compared with
application-only primers.

Acknowledgement

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This publication was made possible by an Award JSREP 07-022-3-010 from the Qatar National
Research Fund (a member of The Qatar Foundation). The statements made herein are solely the

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responsibility of the authors.

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Highlights

 The improvement of surface properties after corona treatment of LLDPE was proven.
 The surface free energy of LLDPE significantly increased after corona treatment.
 The wettability increase was responsible for the significant adhesion improvement.
 The corona treatment with primers had synergistic effect on adhesion improvement.

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