Surfaces and Interfaces 32 (2022) 102154

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Surfaces and Interfaces

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Experimental and numerical studies of polyamide 11 and 12 surfaces

modified by atmospheric pressure plasma treatment
M. Bahrami a, *, D. Lavayen-Farfan b, M.A. Martínez a, J. Abenojar a, c
a
Materials Science and Engineering Department, In-service material performance group, Álvaro Alonso Barba Institute of Chemistry and Materials Technology, University
Carlos III of Madrid, Avda. Universidad, 30, 28911 Leganés, Madrid, Spain
b
Department of Mechanical Engineering, University Carlos III of Madrid, Avda. Universidad, 30, 28911 Leganés, Spain
c
Mechanical Engineering Department, Universidad Pontificia Comillas, Alberto Aguilera, 23, 28015 Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Polyamide 11 and 12 (PA11 and PA12) have been applicable in various industries, including automotive, oil and
Polyamide gas, and sporting goods, over the past 70 years. Although they have good dyeability, their adhesion to other
APPT materials is limited due to relatively poor surface properties, which can be promoted by good wettability and
Adhesion strength, CZM, Finite element model
high surface energy. This study aims to improve the surface properties of PA11 and PA12 by employing the
Surface energy
advanced method of Atmospheric Pressure Plasma Torch (APPT) treatment. In this regard, the adhesion strengths
of four commercially available adhesives were evaluated with the pull-off test on PAs plates before and after
APPT treatment. The numerical simulation of this test was carried out in commercial finite element software
using a cohesive zone model (CZM) to predict the fracture of adhesively bonded joints. Moreover, the modified
PAs were analyzed using XPS, DSC, ATR-FTIR, optical profilometer and surface energy measurement. The results
indicated that the surface properties, including wettability, polar surface energy and adhesion bonding,
improved by employing the plasma treatment on PAs surfaces. The numerical simulation outcomes showed that
the pull-off test might be a viable alternative to determine the CZM laws for fracture mode I.

1. Introduction Fig. 1 compares the PA11 and PA12 with polypropylene (PP) and
polyethylene (PE) from a structural point of view. The PP and PE,
After the discovery of polyamides (PAs) by Carothers in 1940 [1], generally polyolefins, which are the most widely used commercial
they have received tremendous interest in various industries such as polymers, are made of nonpolar covalent bonds of C–C and C–H,
automotive, textile, sports, and oil and gas due to their excellent prop­ resulting in poor surface adhesion properties [8,9]. They resist being
erties like mechanical strength, chemical resistance, ease of processing, wetted by adhesives due to the low surface energy. In other words, PP
high melting point and low permeability for oxygen [2,3]. Despite their and PE with a surface energy of 31 mJ/m2 [10] do not make enough
satisfactory bulk properties, PAs surface typically possesses poor surface intimate contact with adhesives, coatings or other more polar polymers
properties, including low surface energy, poor adhesion and insufficient which is necessary for good bonding. On the other side, polyamides are
wettability, leading to processing problems in various applications, made up of amide groups (linkage of amine with carboxylic acid group)
especially when coated, printed or joined with other materials [3,4]. that interact along linear alkane chains [11]. The hydrogen bonding
These shortcomings are mainly caused by low reactivity of the surface, e. between amide groups of neighboring chains plays a major role in the
g., absence or dearth of reactive functional groups on the surface. surface properties of polyamides. Although polyamides like polyolefins
Along with PA6 and PA66, the most applicable polyamides (90% of are categorized as low surface energy (LSE) plastics, their higher re­
the world’s consumption of PAs [5]), PA11 and 12, which are ported surface energy than polyolefins (35–53 mJ/m2 [10,12-14]) is
semi-crystalline polyamides, have attracted increasing interest over the more favorable in terms of surface properties.
past 70 years. PA12 is an oil-based engineering thermoplastic, while the From the adhesion point of view, the adhesion of PAs to more polar
PA11 is a bio-based polyamide synthesized from renewable resources (e. polymers or other substrates is a challenging issue that should be solved
g., castor plants) with a lower carbon footprint [6,7]. before final application. The dominant parameters to promote adhesion

* Corresponding author.
E-mail address: mbahrami@ing.uc3m.es (M. Bahrami).

https://doi.org/10.1016/j.surfin.2022.102154
Received 9 March 2022; Received in revised form 6 June 2022; Accepted 25 June 2022
Available online 1 July 2022
2468-0230/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

properties are high surface energy, a large contact surface area, and electrodes. This process has been widely used in adhesives, coatings and
good wettability [15,16]. Consequently, several attempts have been sealants fields because it usually forms hydroxyl and amine functional
made to improve the surface properties of PAs. Among the numerous groups or polar oxygen-containing groups (–COOH, –OH), thus pro­
techniques, plasma treatments have become progressively popular. To moting the surface energy and wettability and enhancing the interaction
cite some examples of research on this matter, Mandolfino et al. [17] with the adhesive [26–28].
treated PA6 and PA6.6 surfaces with a low-pressure plasma to increase The adhesion bonding strength of treated surfaces can be evaluated
wettability properties and shear strength of the bonded joints with PAs. experimentally through different methods such as the pull-off test.
The plasma treatment increased the oxygen-containing polar groups on Nowadays, numerical simulations are considered trending tools to pre­
both polyamides, led to wettability and hydrophilicity improvement of dict or facilitate experimental studies. In the present study, to apply the
the surface. A low concentration of active species, which results in results of the pull-off test to further engineering problems and applica­
longer exposure times, is one of the disadvantages of the low-pressure tions, a numerical model of the test was developed. The numerical
plasma technique, limiting its use commercially and industrially [3]. model aimed to use these results as the cohesive zone laws for finite
Hnilica et al. [18] achieved a significant increase in wettability of PA12 element simulations. The cohesive zone model (CZM), first proposed by
films by microwave plasma jet, which caused chemical and morpho­ Dugdale [29] and Barenblatt [30], is a damage model used in fracture
logical changes on the surface. In another study, Károly et al. [4] mechanics that captures the overall behavior of the crack interface and
modified the surface of PA6 with cold plasma treatment. Due to the incorporates it into a finite element model (FEM) with the crack path
formation of oxygen-containing functionalities on the surface, the sur­ and geometry previously defined. This model has also been used for
face energy, wettability, and adhesion shear strength of PA6 improved. fracture prediction of adhesively bonded polymeric joints [31–34]. The
Vlasta et al. [3] could decrease the water contact angle of the PA6 foils to CZM requires the definition of the traction separation law (T-s law) or
less than half of the initial value by employing plasma treatment with CZM law of the crack (Fig. 2), where the stress in the crack interface and
two different discharge sources. Furthermore, the peel resistance crack separation are related. In general, a CZM law consists of two parts:
improved 19% after 2 s diffuse coplanar surface barrier discharge
(DCSBD) plasma treatment. In various papers [19–21], Geo and his team 1) Hardening: A linear relationship between the stress and separation
investigated the effect of atmospheric pressure plasma jet treatment on until a maximum stress level is obtained. The adhesive and substrates
the PA6 films. In this regard, the plasma-treated samples had higher suffer no damage or plastic deformations during this stage.
roughness, hydrophilic surface groups and higher T-peel strength. Also, 2) Softening: An increase in damage and decrease in stiffness as damage
adding a small amount of O2 to the CF4 and He as plasma gasses grows. Once the maximum stress is reached, damage begins. As it
improved surface properties as well. Moreover, the presence of moisture grows, stiffness is lowered. Unloading and reloading occur along a
and environmental humidity facilitated the effectiveness of plasma curve with lower stiffness, as seen in Fig. 2. The softening portion is
treatment [22]. not necessarily linear and is highly dependent on the adhesives,
The plasma treatment techniques that polymer is exposed to reactive substrates, surface treatment, etc. The softening portion ends when
gaseous particles and radiation from gaseous plasma present noteworthy damage reaches 1 (100%), which marks the total separation of the
advantages in the modification of polymeric surfaces (1) treatment substrates.
confined to a region only several molecular layers deep without
affecting the bulk properties, (2) nontoxic, dry, and environmentally The advantage of using a CZM is that it consists of a constitutive
friendly, (3) applicable for a wide range of materials, (4) easy and fast relation of the fracture that lumps all effects into one single non-linear
process with controllable parameters, (5) capable of surface morphology relationship. However, this means that the CZM law must be obtained
and roughness modification by etching effect, to name but a few by experiments for a specific application. Preparing test specimens for
[23–25]. these cases may not always be feasible since the test specimens may be
In this study, the Atmospheric Pressure Plasma Torch (APPT) treat­ large, and many may be required for repeatability and to define the test
ment was applied on the surface of polyamide 11 and 12 in order to parameters and the shape of the CZM law. For fracture mode I param­
modify the surface properties and improve their adhesion properties. In eters, a standardized test already exists (double cantilever beam test)
the APPT treatment, which is a cold plasma technique, a compressed air [35] and is widely used [36–38]; however, there are still several pro­
flux is expelled through a nozzle after ionization by the action of two posals for improving the data processing, especially for reducing the

Fig. 1. Chemical structure of PA11, PA12, PP and PE (N: number of methylene groups between amide groups).

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 2. Example of a bilinear CZM law and its stages.

need for crack length measurements [39,40]. Thus, employing a pull-off creates linear chains with hydroxyl and epoxy groups, allowing further
test to obtain the CZM laws for different adhesives with different surface crosslinking through amines compost [42]. Araldite® cures in 10 min
treatments would prove to be a valuable alternative. rapidly, but its maximum strength is achieved after 16 h when the ratio
Although the APPT treatment of polyamides has been investigated of hardener to resin is 1:1. It has a rigid behavior; thus, the adhesive
recently, to the best of the authors’ knowledge, research dedicated to the thickness is 0.1 mm. When used to join polymers, it has a lower strength
modification and comparison of PA11 and PA12 with the APPT tech­ and needs surface treatment, as minimum abrasion and cleaning.
nique besides numerical simulation of it has not been reported Polyurethane Sikaflex®− 252 is a structural adhesive. It cures by
elsewhere. atmospheric humidity, as diisocyanates and polyols compost all poly­
urethanes. Its behavior is elastomeric; thus, the adhesive thickness
2. Material and methods should be around 2 mm. Curing time depends on humidity and adhesive
thickness, but as a minimum, it needs six days [43]. In addition, it joins
2.1. Materials metals and ceramics well, but tests should be done before joining
polymers.
Commercial polyamides (PA11 and PA12) were provided by Arkema Cyanoacrylate is composed of ethyl cyanoacrylate. It is a rigid ad­
(Madrid, Spain). Selected characteristic properties of the PAs are listed hesive. It cures due to the humidity of the substrates in a matter of mi­
in Table 1 [41]. In order to evaluate the adhesion properties of PAs, nutes but reaches maximum resistance after 12 h. Therefore, the
rectangular plate specimens with dimensions of 80 mm × 180 mm × 4 thickness of adhesive between substrates is minimal (around 0.1 mm). It
mm were prepared by a hot plate press machine (Fontune Presses can join metals, ceramics, cardboard, wood and some plastics. However,
TPB374, Barendrecht, Netherlands). PA pellets were placed between the it cannot bond with polyethylene, polypropylene, silicone, PVC, and
hot press plates with a specific program with a maximum temperature glass [44].
and pressure of 200 ◦ C and 45 kN. According to the hot-press cycle,
which is shown in Fig. 3, the gradual pressure steps were applied at 20 2.2. Plasma treatment
and 30 kN to facilitate densification and prevent air trapping. Moreover,
each pressure step was held isothermally for 3 min. The Atmospheric Pressure Plasma Torch (Plasma treat GmbH,
Four commercial adhesives were used to perform the adhesion test: Steinhagen, Germany) was used to modify the polymers’ surfaces
2-component epoxy (Ceys, Araldite® Rapido, Barcelona, Spain), (Fig. 4). The device setup and technical details were explained in the
cyanoacrylate (Loctite®- Super Glue-3Precisión, HENKEL IBÉRICA SA, previous paper [25]. Air flux was fed to the system as a feeding gas.
Barcelona, Spain), polyurethane (Sikaflex®− 252 PU; Sika S.A.U. Three substrate-to-torch distances of 10, 20 and 30 mm were tested
Madrid, Spain), and hybrid polyurethane (Sikaflex® − 552 AT; Silane based on the water contact angle measurement. Also, the platform speed
Terminated PU, Sika S.A.U. Madrid, Spain). Sikaflex®− 252 and Sika­ was set at two different values of 10 and 20 mm/s.
flex® 552AT are conventional single-component and hybrid single-
component PU adhesive, respectively. The hybrid type is constituted
2.3. Polyamides wettability and surface energy
by silane terminated PU, which assists in bonding on surfaces without
primer or more complex surface treatments. The adhesives were applied
In order to evaluate the effect of plasma treatment on the PAs, their
in the laboratory with a controlled temperature of 22 ◦ C and relative
wettability was measured using three liquids with different polarities
humidity between 27 and 30%.
(deionized water, diiodomethane, and glycerol) before and after APPT
Most epoxy resins are derivates from the reaction between A-
treatment. The surface tension parameters of the mentioned liquids were
bisphenol and epichlorohydrin. The addition of these two products
obtained from the literature and are presented in Table 2 [45,46]. The
static contact angle measurement according to the UNE-EN828:2013
Table 1 standard was done with the sessile-drop method. In this regard, four
Characteristic properties of PAs.
drops of each liquid with a volume of 6 μl were deposited onto the
Property PA 11 PA 12 polymer surface. The contact angle was measured after stabilization of
Density (g/cm3) 1.03 1.01 the drop by Dataphysics OCA15 plus goniometer and SCA20 software
Yield stress (MPa) 20 64 (DataPhysics Instruments GmbH, Filderstandt, Germany). Then, the
Elasticity modulus (GPa) 1.7 2.9 surface energy (SE) was calculated using the
Melting temperature ( ◦ C) 188–193 178–179
Owens-Wendt-Rable-Kaelble (OWRK) method [47], which considers

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 3. Temperature and pressure profile during PAs hot-press.

Fig. 4. Schematic of the APPT device.

calibrated based on the carbon peak (C–C/C–H, 284.6 eV). The XPS
Table 2
spectra were recorded on a Kratos XSAM 800 spectrometer (Kratos
Polar and dispersive surface tension components of the test liquids at 25 ◦ C for
Analytical Ltd. Designs, Shimadzu Group Company, Manchester, UK),
wettability measurement.
operating in fixed analyzer transmission mode, using Mg Kα (1253.6 eV)
Liquid SE (mJ/m2) Disp (mJ/m2) Polar (mJ/m2) excitation. Survey spectra were recorded in the kinetic energy range of
Deionized water 72.8 21.8 51 0–1300 eV with 0.5 eV steps. Photoelectron lines of the principal con­
Diiodomethane 50.8 50.4 0.4 stituent elements, like the O1s, N1s and C1s, were recorded by 0.1 eV
Glycerol 63.4 34 30
steps.
The FTIR spectra of the PA plates before and after plasma treatment
various force components in the solid-liquid-vapor system formed dur­ were recorded by an infrared spectrometer machine (Bruker Optik
ing the drop deposition on the polymer surface. GmbH, Ettingen, Germany) equipped with an attenuated total reflection
The stability of material surface properties after the treatment is an (ATR) technique to analyze the surface chemical modifications. The
essential parameter in the industry since the semi-product might be kept produced spectra were collected with a Bruker Tensor 27 spectrometer
for a long time between the appropriate manufacturing steps. Thus, the at the resolution of 4 cm− 1, 32 scans and an incident radiation angle of
effect of plasma treatment over time with different platform speeds of 45◦ . Three spectra were captured for each PA to ensure homogenous
APPT device was also evaluated in this study. The contact angle test was results.
done with different velocities (10 and 20 mm/s) after 10 min, 30 min, 11
days and 21 days of plasma treatment.
2.5. Thermal characterization

2.4. Chemical characterization of the surface by XPS and FTIR-ATR Differential scanning calorimetry (DSC) analysis (DSC 822e, Mettler
Toledo GmbH, Greifensee, Switzerland) was used to study the effects of
The surface chemical composition of PA11 and PA12 was analyzed APPT on the thermal properties of PAs surface. The DSC was performed
by X-ray photoelectron spectra (XPS) before and after plasma treatment with a heating rate of 20 ◦ C/min in a temperature range of − 60 ◦ C to 200
by an ellipsoid scan probe with a major diameter of 400 μm which was ◦
C. Moreover, the nitrogen as a purge gas was fed at a 50 ml/min rate.

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

2.6. Adhesion pull-off test consists of an aluminum cylinder, representing the dolly, where a
displacement was applied on the upper face; a polymer cylinder repre­
To study the effect of plasma treatment on the bond strength, the senting the substrate, which was fixed to the ground; and a layer of
pull-off test was carried out based on the ISO 4624:2016 standard contact elements with CZM (cohesive zone modeling) capabilities in
(ASTM Standard D 4541), using a Universal Testing Machine EM1/ between, which were representative of the adhesive and its surface
200FR (Microtest, Madrid, Spain) at a rate of 0.5 mm/min at room treatment altogether. These contact elements have zero thickness. The
temperature with a load cell of 1 kN, using aluminum dollies of 20 mm dolly and the substrate were modeled as linear elastic materials, while
diameter (Fig. 5a). The test determines the highest perpendicular force the adhesive was considered as bilinear CZM contact elements. The
(in tension) that a polymer can bear as a substrate before an adhesive model is depicted in Fig. 7. The parameters for the CZM properties are
plug is detached. After the adhesion tests, the mechanism of the adhe­ based on the experimental pull-out test results as follows:
sives’ detachment was also evaluated.
The polymer surfaces for adhesion tests were first polished with • The initial linear portion of the force-displacement curve is taken as
silicon carbide abrasive paper (grit number P1200 and 2000) and then the contact stiffness of the CZM elements.
cleaned with acetone. Then the APPT was employed on half of the • The maximum force is used to determine the maximum stress in the
samples’ surfaces (Fig. 5b). The adhesives were applied onto the poly­ CZM model.
mer surface with a controlled thickness of 2 mm (for PU and PU-hybrid • The maximum displacement measured during the test is used as the
adhesives) and 0.1 mm (for the epoxy and CA adhesives). The thick­ maximum separation.
nesses for PU and PU-hybrid were controlled by small glass balls with an
appropriate diameter and for epoxy and CA with a weight of dolly These parameters are used for a bilinear CZM law, similar to the one
through the proper support. Six dollies were used for each adhesive to depicted in Fig. 2.
perform the pull-off test. According to the manufacturer’s recommen­
dation, prior to using the PU adhesive, Sika® Primer-210 was applied on 3. Results and discussion
the aluminum dolly surface to react with moisture and form a thin layer,
which links polymer and adhesives. 3.1. Polyamides wettability and surface energy

2.7. Surface morphology Tables 3 and 4 show the surface energies, including both polar and
dispersion components. They are presented for 10 mm/s and 20 mm/s as
In order to evaluate the effect of the APPT treatment on the surface a platform speed for treatment optimization. Based on the reported
morphology, roughness analysis of the treated and untreated specimens values, both velocities led to the similar surface energy after 10 min.
was carried out by Motorized Microscope System (BX61, Olympus However, with the lower velocity of 10 mm/s, the energetic ionized gas
Corporation, Tokyo, Japan), which provides 3D surface images. The of plasma had more time to alter the physicochemical nature of poly­
surfaces were scanned with 280X magnification. Moreover, the mean amides’ surfaces, which resulted in higher durability of plasma on the
areal surface roughness (Sa) was calculated for each polymer according surface over the time. This behavior is more tangible after 30 min of
to Eq. (1) APPT treatment. The surface energy of polyamides significantly
) decreased after 30 min for the higher velocity of 20 mm/s, while 10
1 ∑ mm/s could keep the same range of energy after 30 min. Therefore, the
N ∑ M
Sa = z(xi ; yj (1)
MN j=1 i=1 10 mm/s was used in further comparative experiments. Moreover, the
substrate-to-torch distance was set to 10 mm since it had a lower water
where z is the height of the measured points in the coordinates of x and y contact angle with respect to 20 and 30 mm; in addition, less than 10
[48]. This equation measures surface roughness based on the average mm, plasma degraded the substrate surface.
absolute vertical deviation of all data points. Furthermore, other In Table 5, the contact angle values of water, diiodomethane and
roughness parameters such as Spk, Sk, Svk, SMr1, and SMr2 can be derived glycerol are listed. The surface energy values were calculated, including
from the Abbott-Firestone curve [49], which is presented in Fig. 6 [50]. both the polar and dispersive components for the untreated and plasma-
Spk, the reduced peak height, represents the peak height above the treated samples and shown in Fig. 8. The untreated polymers were found
core roughness. Sk, the core roughness depth, shows the peak-to-valley to be rather hydrophobic, with their high-water contact angle values
(core roughness) distance of the surface with the predominant peaks being 93◦ and 83◦ for PA11 and PA12, respectively. APPT treatment
and valleys. Svk, the reduced valley depth, is the valley depth below the could greatly decrease the contact angles, which sums up to at least a
core roughness. SMr1 and SMr2 indicate the percentage of material that 22% reduction for each reference liquid. The high decrease in the water
comprises the peak and valley structures associated with Spk and Svk, contact angle indicates a high increase in the polarity of the surfaces
respectively. after the treatment because the water molecule is polar. Moreover, the
total surface energy significantly increased, mainly due to the rise of
2.8. Adhesion pull-off test simulations polar components. Compared with untreated PA11 and PA12, there was
an approximate increase of 40% and 85% in surface energy, respec­
The numerical simulations were carried out in ANSYS 2021 as a tively. The polar component also follows the same trend observed with
static analysis due to the low velocity of the tests. The numerical model surface free energy. The reduction of wetting contact angles tightly

Fig. 5. a) Schematic of a pull-off test, b) test configuration for each polymer substrate.

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 6. Abbott-Firestone curve showing the construction of the Sk family parameters.

Fig. 7. a) Scheme of the numerical model, b) mesh used for the simulations.

Table 3 Table 5
Effect of plasma velocity on the surface energy of PA11 and PA12: 10 mm/s Contact angle values of the treated and untreated PAs.
velocity. Polymer θW (◦ ) θ (◦ ) θGl (◦ )
CH2l2
10 mm/s
PA11 93±2 62±1 97±1
10 min after treatment 30 min after treatment
PA12 83±5 63±1 82±2
SE (mJ/ Disp Polar SE (mJ/ Disp Polar
PA11-APPT 26±3 48±6 41±4
m2) (mJ/m2) (mJ/m2) m2) (mJ/m2) (mJ/m2)
PA12-APPT 22±4 40±6 61±6
PA11 58.37 9.20 49.17 60.18 19.46 40.72
PA12 58.5 9.36 49.14 61.64 22.32 39.32
energy was higher for PA11 than PA12 (42 vs. 32 mJ/m2); however,
untreated PA12 had a higher polar component than PA11 (6 vs. 2 mJ/
m2). Once the surface treatment had been carried out, the surface en­
Table 4
Effect of plasma velocity on the surface energy of PA11 and PA12: 20 mm/s ergies for the two polyamides were equalized to around 58 mJ/m2after
velocity. 10 min. This increment in the total surface energy corresponds funda­
mentally to the polar component increment, while the dispersive
20 mm/s
10 min after treatment 30 min after treatment component decreased when the samples were tested after APPT. Con­
SE (mJ/ Disp Polar SE (mJ/ Disp Polar trary to what was previously reported for other polymers [26] that
m2) (mJ/m2) (mJ/m2) m2) (mJ/m2) (mJ/m2) surface hydrophobicity recovered after approximately 30 min of stor­
PA11 58.31 16.44 41.87 35.84 25.82 10.03 age, the effect of plasma treatment has not vanished even after 11 days
PA12 58.5 9.36 49.14 33.35 20.52 12.84 for PAs. Over time, the total surface energy increased slightly and the
dispersive tended to that of the untreated sample. Thus, on the 11th day,
the total surface energy was 35% and 51% higher than the initial for
corresponds with these surface energy changes. Based on the wetting
PA11 and PA12, respectively. However, the polar component has
theory [51], in order to have a high-performance adhesive bond, the
decreased by 1% for PA11 and 4% for PA12 on the 11th day. The aging
surface energy of adherend should be higher than applied adhesive.
of the treatment continues until 21 days, to which the polar component
Fig. 9 shows the evolution of the treatment over time, where time
has reduced by 10% for PA11 and 34% for PA12, higher than initial
zero corresponds to the untreated sample. Before treatment, the surface
values but not sufficient for good wettability. This reduction in surface

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 8. Comparison of surface energy components before and after APPT treatment of PA11 (blue) and PA12 (green). (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)

3.2. Chemical characterization of the surface

3.2.1. XPS analyses

The elemental compositions (atomic%) of the polyamides surfaces
before and after plasma treatment calculated from the survey spectra are
presented in Table 6. The survey spectrum of hot-pressed PAs in Fig. 10
shows the presence of carbon, oxygen, and nitrogen, as predicted from
the chemical structure (C11H21NO and C12H23NO). Furthermore, the
utilized polyamides include some additives or fillers such as P, Ca and
Na, which are beneficial for optimizing the polymer properties [53,54].
After APPT treatment, the concentration of the individual chemical el­
ements changed. Compared to the untreated polyamides, the amount of
oxygen and nitrogen increases while the amount of carbon decreases.
Moreover, Table 6 illustrates how APPT treatment increases the O/C and
N/C ratios. Furthermore, the energetic ionized gas of the plasma source
has affected some of the PA11′ fillers, which resulted in the formation of
P2O5 (134.08 eV (P2s) and 191.8 eV (P2p)), NaCl (1072 eV), CaCO3 (348
and 351 eV). These polar and ionic groups are able to form strong
chemical/physical interactions with the adhesives and improve adhe­
sion bonding with the absorption mechanism [47]. This change in filler
compounds is more evident in PA11 since using plasma, fillers migrate
from inside the PA11 to the surface, in contrast to PA12, in which fillers
are inside and on the surface before plasma treatment..
The peak fitting routines were done to evaluate the bond structure
changes. Fig. 11 and 12 show the deconvolution results for the C1s, N1s
and O1s XPS spectra of PAs surfaces before and after the plasma. The C1s
spectrum was fitted with four peaks, which are identified as aliphatic
carbon atoms (C–C/C–H, 284.58 eV), carbon atoms bonded to the -NH
groups (C–N, 285.59 eV), single-bonded carbon to oxygen (C–O, 286.57
eV) and carbon atoms of carbonyl groups (C = O, 288.27 eV). The
presence of C–O bond on the untreated surfaces can be assigned to the
contamination of the surfaces or partial atmospheric oxidation of the
Fig. 9. Comparison of surface energies after different times from APPT treat­ main chain of the PAs (during the hot press process). Since the hot press
ment: a) PA11, b) PA12.
chamber was not vacuumed, the high temperature of the process (200

energy and wettability after 21 days is due to the surface reactivity and
thermodynamically driven reorientation of polar groups away from the Table 6
surface into the bulk [52]. The Surface composition (atomic%) of the treated and untreated PAs determined
Accordingly, from an application point of view, the achieved results by XPS.
propose that for applying coatings, adhesives or any other functional­ PA12 PA12-APPT PA11 PA11-APPT
izing processes on the plasma-activated polyamides, they can be C% 62.24 42.36 70.16 42.05
expanded in time (around 11 days) after plasma treatment; in this way, O% 24.89 38.9 16.87 42.81
the polar component of the surface energy has a considerably higher N% 12.86 16.56 12.96 13.05
value than untreated surfaces. O/C% 39.99 91.83 24.05 101.81
N/C% 20.66 39.09 18.47 31.03

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Fig. 10. XPS spectra of treated and untreated polyamides; a) PA11, b) PA12.

◦
C) may facilitate the atmospheric oxidation of PA pellets during the 3.2.2. FTIR-ATR analyses
press; polyamides are such types of thermoplastic polymers that can be The FTIR spectra of treated and untreated PAs are illustrated in
readily oxidized when heated above their melting temperature [55]. Fig. 13. Both PA11 and PA12 have very similar peaks. The absorption
After APPT treatment, the intensity area under the peaks corresponding peaks at 1635 cm− 1, 1540 cm− 1 and 1275 cm− 1, which are assigned to
to the C–C/C–H and C–N decreased by 19% and 14% respectively for amide I, amide II and amide III, respectively, are the most typical peaks
PA11 (Fig. 11a) and by 15% and 19% for PA12 (Fig. 12a), whereas the of PA11 and PA12 [56]. The intense bands at 2850.7 cm− 1 and 2918.2
intensity of C–O and C = O peaks respectively increased by 8% and 25% cm− 1 belong to symmetric and antisymmetric stretching vibrations of
for PA11 and by 11% and 22% for the PA12. By classifying the func­ the C–H group, respectively [56]. The complete curve-fitting results for
tional groups into polar and nonpolar, we can quantify the changes in PA11 and PA12 were listed in previous work [41]. After APPT treat­
the surface composition by comparing the polar to nonpolar intensity ment, the peak intensity of amid I and II increased by 19% and 18%
ratio. Peak C–C/C–H is a nonpolar group and the rest are polar. This respectively for PA11 and by 8% and 16% for PA12, meaning the
ratio increased from 0.61 to 1.32 for PA11 and from 0.73 to 1.33 for presence of more functional groups of C = O and NH2, which agrees with
PA12. This is the main reason for increasing the wettability. An increase the XPS results. It is worth mentioning that these increases are lower
in carbon-oxygen bonds concentration would be due to the recombi­ than XPS because the infrared scan depth is more remarkable than XPS.
nation of reactive sites formed on the surface of the polyamides with free
oxygen radicals in the plasma.
These changes are also evident in the deconvolution of O1s spectra 3.3. Thermal characterization
(Fig. 11b and12b). The peaks correspond to the polar groups, including
oxygen bonded with carbon and carbonyl. The intensity of all these Thermal properties including melting temperature (Tm), melting
three peaks increased after the plasma treatment. In addition, the enthalpy (ΔH) and degree of crystallinity (Xc) were measured by DSC for
analysis of the N1s spectrum showed that plasma had excited the anti­ PA11 and PA12 before and after treatment and are summarized in
bonding sigma bonds of orbital 1 s (Fig. 11c and12c). Antibonding sigma Table 7. Moreover, the typical heating thermographs for each PA are
level has more energy than bonding sigma and 1S orbital; thus, plasma compared in Fig. 14. The presented results are consistent with a previous
provided more active sites for reaction with adhesives. paper by the authors [41] and show that the plasma treatment did not
significantly affect the thermal properties of the PAs. This means the

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 11. XPS spectra as a function of binding energies of the untreated (up) and plasma-treated PA11(down): a) C1s, b) O1s, c) N1s.

thermal stability of PAs did not compromise with APPT treatment which results, and they are similar within the confidence limit. The average of
is essential for any surface treatment technique. The minor differences adhesive strengths for each adhesive besides the ANOVA outcomes at
found in Table 7 are within the measurement error. 95% confidence interval (alpha = 0.05) are presented in Table 8. Ac­
cording to this table, the F critical is only lower than the F value for epoxy
3.4. Adhesion pull-off test adhesive, meaning that the APPT treatment had not significantly
affected CA, PU, and PU-hybrid adhesives’ adhesion strength.
Fig. 15 displays the adhesion strength of different adhesives with Regarding the PU-hybrid, although the average value of strength was
PA11 and PA12. Epoxy and PU-hybrid had the highest adhesive strength increased after APPT, this modification is not significant based on
among the other adhesives applied on the PAs. The most considerable ANOVA. This effect is rational since silane added to PU improves the
growth of adhesive strength after APPT treatment was found for the adhesion by chemical anchor between adhesive-substrate. Given the CA,
epoxy. In this case, the adhesive strength increased from 0.86 MPa to the curing mechanism is a moisture-based process that requires hu­
2.2 MPa for PA11 and from 0.67 MPa to 2.6 MPa for PA12, translating to midity on the substrate surface. However, the plasma treatment
approximately 157% and 291% growth, respectively. The positive effect completely dries the surface, which prevents adhesion improvement.
of plasma treatment on epoxy bonding strength can be attributed to the Regarding PU, no improvement in adhesive strength might be due to the
reaction of epoxy groups with functional groups produced after plasma low polar surface tension of PU (5.4 mJ/m2 [57]). The surface tension of
exposure that create covalent linkages between adhesive and polymer adhesives must be lower than the surface energy of solid substrates for
surface. the proper bonding; however, this difference should not be too high. PA
The analysis of variance (ANOVA) was applied to the adhesion has high dispersive surface energy and low polar component. Therefore,
strength values of treated and untreated polymers for each adhesive to they can be joined to dispersive adhesives such as polyurethane but with
evaluate the distribution of results. In ANOVA, there are two main pa­ low strength without treatment since they have similar polar component
rameters of F and F critical. Suppose the calculated value of F critical is energy. However, after APPT, the polar component energy of PA
more than the standard tabulated value of the F for a given confidence increased a lot, resulting in too much energy difference between PA and
interval. In that case, there is no significant difference between the PU.

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 12. XPS spectra as a function of binding energies of the untreated (up) and plasma-treated PA12 (down): a) C1s, b) O1s, c) N1s.

On the other hand, the adhesion strengths of Table 8 give the 3.5. Surface morphology
impression that the APPT treatment did not affect the bonding strength
of the adhesives except epoxy. However, evaluation of the adhesive The 3D images captured by BX61 microscopy from polymers surfaces
failure is an essential part of the adhesion test. Five failure modes are are shown in Fig. 18. The roughness parameters which were calculated
possible depending on the location of the failure interface, Mode A based on the Abbott-Firestone curve and Eq.1, are also presented in
through E, as shown in Fig. 16 [58]. The first mode (A) indicates ad­ Table 9. It is seen that APPT treatment reduced the Sa parameter of
hesive pulled off from the dolly surface. Mode B shows adhesive failed surfaces by 34% and 28% for PA11 and PA12, respectively. The 3D
with partially cohesive-adhesive failure. In mode C, the adhesive de­ images also exhibit the smoother surface of treated surfaces, which
tached from the surface of the substrate. Mode D is similar to mode C, in could be due to the cleaning and ablation effect of plasma which also has
which part of the substrate is also detached. The last mode (E) is a been reported previously [59–62]. Surface ablation is very common in
cohesive failure in the PA substrate. According to Fig. 17, before plasma plasma treatment processes which happens due to the hydrogen removal
treatment, epoxy, CA and PU-hybrid failed with mode C and the that causing weight loss in the treated surface [63,64].
PU-hybrid adhesive failed with mode B. Lower Spk and Svk of APPT treated polyamides imply that plasma has
After APPT treatment, the epoxy adhesive had approximately similar smoothed the peaks and filled the valleys of the surfaces. Lower Sk,
failure modes for both PAs. Although in the case of epoxy/PA11, tiny which is the distance of peak-to-valley or core roughness, is another
parts of the substrate detached by adhesive (mode D), there were also a proof of roughness reduction after APPT. However, higher SMr1 indicates
few cases for epoxy/PA12 with mode D (not the majority). TheCA and that plasma treatment increased the amount of materials with peak
PU-hybrid failure modes changed to B and A, respectively. Both last structures associated with Spk. The reduction of micro-roughness causes
detachments indicate a stronger interface bond between adhesive to the lower mechanical interlocking of a substrate with other substances. In
surface of polyamide substrate compared to untreated samples. In this other words, lower roughness resulted in lower surface area for a
regard, the reported adhesive strengths for PU-hybrid and CA after APPT chemical reaction, which might be another reason for the unchanged
are not the exact forces required for adhesive pull-off from PA; instead, bonding strength of CA, PU and PU-hybrid adhesives.
they are the breaking forces of adhesives exclusively. Thus, it can be
concluded that the adhesion strength of CA and PU-hybrid adhesives
3.6. Numerical simulation results
after APPT treatment increased. On the other hand, the unchanged
failure mode of PU specifies no effect of APPT.
3.6.1. CZM parameters obtained from pull-off tests
Following the procedure indicated in Section 2.8, the following

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 13. FTIR spectra of hot-pressed PAs before and after treatment: a,b) PA11, c,d) PA12.

Table 7
Thermal properties of studied Pas by DSC measurements.
PA11 PA12
Untreated APPT Untreated APPT
Tg ± 2 ( ◦ C) 44 42 43 46
Tm ± 3 ( ◦ C) 193 190 179 181
ΔH ± 2 (J/g) 52 50 47 45
χc ± 2(%) 23 22 49 47

parameters were extracted for a bilinear CZM law: the corrected

strength, the contact stiffness for the simulations, and the maximum
crack separation. These parameters can also be used to obtain the critical
fracture energy (area under the CZM curve) and compare it with the
experimental value. The summarized results are shown in Table 10.
It should be noted that there is a great dispersion of the data results,
particularly in the maximum crack separation results. Thus, the averages
are shown and used for the simulations.

3.6.2. CZM parameters obtained

Based on the experimental and numerical results, meaningful results
could be obtained. It is noted that the substrate (whether PA11 or PA12)
has little or no influence on the shape of the CZM law; however, the
adhesive and the surface treatment do have a significant influence, as
detailed below.
For the case of the epoxy adhesive, the bilinear CZM law worked
adequately for both substrates, mainly due to the brittle nature of the
epoxy, as shown in Fig. 19. Not only the adhesive strength increased
with the APPT, but so did the fracture energy and, more importantly, the Fig. 14. DSC thermograms of PAs before and after treatment (heating rate: 20
stiffness. The most significant increase was seen with the PA11, where ◦
C /min): a) PA11, b) PA12.
the adhesive could partially hold the load after reaching the load peak.
The results in Fig. 19 also show that the epoxy adhesives greatly benefit difference comes from the higher surface roughness present in the un­
from the APPT treatment, as the peak load is significantly increased. treated PA12, as shown in Table 9. It can also be deduced that the epoxy
Unlike other adhesives, the PA12 showed a significant reduction in the adhesives are far more sensitive to changes in the surface roughness than
maximum displacement during the pull-off test. It is theorized that this other adhesives, which do not show this change. This behavior is

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

with APPT, which might occur due to the large dispersion in the results
(recall Table 8), and the average was used. This dispersion might also be
responsible for the apparent disagreement in the maximum crack
separation.
As for the PU adhesive, the bilinear law reproduced the results with
some errors, as seen in Fig. 21. The main difference is that the experi­
mental results have a non-linear hardening portion near the peak stress.
A trapezoidal or trilinear CZM law could be used to overcome these is­
sues for substrates with and without APPT. Although there was no sig­
nificant increase in the adhesive strength, the fracture energy increased
for the APPT treated PAs. It is also worth noting that the low contact
stiffness affected the stability of the numerical simulation. To obtain the
full test curve, a mesh element size lower than that of Fig. 7 was used, as
well as very low load increments, represented as a low simulation time
step. The red stars in Fig. 21 and Fig. 22 correspond to the points where
the mesh size and time step were decreased to ensure numerical
convergence; before these points, the original mesh was used for the
modeling.
Finally, the PU-hybrid adhesive case showed the most significant
change in the shape of the CZM-law (Fig. 22). In the case of untreated
PAs, the bilinear CZM law reproduced the experimental results with
acceptable accuracy. However, the specimens with APPT could hold the
peak load, which means they were able to absorb more significant
Fig. 15. Variation of adhesion strength of different adhesives for treated and fracture energy. This, in turn, means that a trapezoidal CZM law could fit
untreated PAs: a) adhesion strength of PA11, b) adhesion strength of PA12.
the data better. However, it must be noted that for both evaluated cases:
to obtain the complete curve, a simulation with a much smaller mesh
Table 8 element size and much lower solution time step was required. The mesh
ANOVA results for adhesion strength of PA11 and PA12 with different adhesives. shown in Fig. 7 could only reach the point marked in the red star in
Fig. 22 before separation/termination. However, decreasing the element
Adhesive AVG adhesion strength Mean F F
(MPa) square
size and time step can significantly increase the simulation time.
critical
The utilized bilinear CZM law proved to be adequate for simulating
PA11
brittle adhesives with and without treatment. However, it is inadequate
Epoxy-APPT 2.208 6.231 118.940 4.965
Epoxy 0.857 for the more elastic adhesives, which could be better described with a
PU-hybrid- 1.691 0.167 2.869 4.965 trapezoidal CZM-law. It is also worth noting that cases with low contact
APPT stiffness (elastic adhesives) require a very fine mesh with small time
PU-hybrid 1.455
steps (or load increments) to reproduce the whole test curve.
PU-APPT 1.084 0.006 0.595 4.965
PU 1.040
CA-APPT 0.539 0.104 2.953 5.317 4. Conclusions
CA 0.744
PA12 Surface modification of polymers by atmospheric pressure plasma is
Epoxy-APPT 2.628 11.479 305.154 4.965
a well-known technique typically performed before any bonding. This
Epoxy 0.672
PU-hybrid- 1.502 0.141 4.191 4.965 study has provided a methodology of surface improvement by employ­
APPT ing APPT treatment on the PA11 and PA12 surfaces. In this regard,
PU-hybrid 1.286 various surface characterization techniques were applied to verify the
PU-APPT 1.051 0.060 4.898 4.965
plasma effects on the surfaces. Based on the performed experiments and
PU 0.909
CA-APPT 0.577 0.043 0.442 4.965
analyses, the conclusions were obtained as follows:
CA 0.698
- The wettability of surfaces was improved significantly by reducing
the contact angles and increasing surface free energy by 40% and
consistent in all tests. 85% for PA11 and PA12, respectively.
Similarly, the bilinear CZM law also fitted the CA adhesive appro­ - Plasma-activated polyamide surfaces did not lose their high polar
priately due to its brittle nature, as shown in Fig. 20. The plasma surface energy until 11 days after treatment, showing their stable
treatment did provide a more significant maximum crack separation on functionality over time.
average. There was an apparent loss in strength for the PA11 substrate

Fig. 16. Some of the failure modes in the pull-off test.

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 17. Pulled-off samples after adhesion test for each polymer and adhesive.

Fig. 18. 3D images of polyamides surfaces by CLSM: a) PA11, b) PA11-APPT, c) PA12, d) PA12-APPT.

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Table 9 untreated surfaces. In addition, APPT treatment significantly

Roughness parameters of PAs before and after APPT treatment. improved the adhesive bond strength of epoxy with PA11 and PA12
Roughness parameters PA11 PA11-APPT PA12 PA12-APPT by 157% and 291%, respectively. On the one hand, the statistical
model of ANOVA showed that APPT had no positive effect on the
Sa (μm) 0.85 0.56 0.93 0.67
Spk (μm) 0.92 0.71 1.52 1.12 adhesion strength of CA, PU and PU-hybrid due to the drying effect of
Sk (μm) 2.20 1.22 3.25 1.82 plasma and low surface tension energy of PUs. On the other hand,
Svk (μm) 1.16 0.81 1.48 1.23 failure mode changing of CA and PU-hybrid from adhesive to cohe­
SMr1 (%) 10.19 12.48 11.98 13.08 sive failure exhibits a good substrate-adhesive bonding after APPT.
SMr2 (%) 89.41 89.01 88.91 89.01
- The average micro-roughness decreased by 34% and 28% for PA11
and PA12, respectively, after APPT treatment as a result of the
cleaning and ablation effect of plasma.
Table 10 - The APPT treatment has a significant influence on the shape of the
Input values for FEM-CZM simulations and resulting fracture energy. CZM-law for each case. In brittle adhesives, such as epoxy and
Adhesive Adhesive Stiffness for Max. crack Fracture cyanoacrylate, the bilinear CZM-law describes the fracture behavior
Strength σmax contact Kn separation δc energy adequately, and in both cases, it can reproduce the increase in
[MPa] [N/mm3] [mm] (bilinear CZM)
strength and fracture energy. As for the elastic adhesives, a trape­
[N/mm]
zoidal CZM-law would fit more adequately the experimental results,
PA11
since the linear CZM-law does not fit the data adequately and re­
Epoxy- 2.208 3.979 1 1.104
APPT
quires a high computational cost to fully reproduce the test. Overall,
Epoxy 0.857 2.546 0.66 0.283 the pull-off tests not only provide insights into the influence of the
PU- 1.691 1.291 6 4.530* APPT treatment on the strength but also on the fracture energy and
hybrid- shape of the CZM-law required. This proves to be a helpful tool since
APPT
the alternative tests, although standardized, require test specimens
PU-hybrid 1.455 1.212 6.8 4.658*
PU-APPT 1.084 0.546 6 2.850* with extensive preparations.
PU 1.040 0.576 5 2.320*
CA-APPT 0.539 0.764 0.65 0.137 Such results confirm the APPT treatment potential for modifying the
CA 0.744 2.760 0.45 0.179
PAs surface characterizations, which is required prior to applying ad­
PA12
Epoxy- 2.628 4.244 0.7 0.920
hesives or coatings to have a promising bonding.
APPT
Epoxy 0.672 0.318 1.75 0.417 Authors statement
PU- 1.502 1.205 6 4.230*
hybrid-
All persons who meet authorship criteria are listed as authors, and all
APPT
PU-hybrid 1.286 1.222 5 3.055 authors certify that they have participated sufficiently in the work to
PU-APPT 1.051 0.263 6.1 3.205* take public responsibility for the content, including participation in the
PU 0.909 0.455 6 2.728* concept, design, analysis, writing, or revision of the manuscript.
CA-APPT 0.577 0.637 0.85 0.203 Furthermore, each author certifies that this material or similar material
CA 0.698 1.702 0.45 0.134
has not been and will not be submitted to or published in any other
*
Approximated values using the bilinear CZM-law. publication before its appearance in the Surfaces and Interfaces.
Authorship contributions surnames, e.g., Y.L. Cheung). The name of
- The XPS and FTIR analysis results revealed that plasma generated each author must appear at least once in each of the three categories
additional oxygen-containing functional groups (C–O, C = O and O below. Category 1 Conception and design of study: M.A. Martinez, J.
= C–N) on the surface, which reduced the hydrophobicity behavior Abenojar, M. Bahrami, D. Lavayen-Farfan Acquisition of data: M. Bah­
of surfaces. rami, D. Lavayen-Farfan Analysis and/or interpretation of data: M.
- Using DSC measurements, the neutral effect of APPT treatment on Bahrami, D. Lavayen-Farfan, M.A. Martínez, J. Abenojar Category 2
PAs’ thermal properties was confirmed. Drafting the manuscript: M. Bahrami, D. Lavayen-Farfan Revising the
- The pull-off strength of adhesive joint to PAs was observed by a manuscript critically for important intellectual content: M. Bahrami, D.
sequence of epoxy >PU-hybrid >PU >CA for both treated and Lavayen-Farfan, M.A. Martínez, J. Abenojar Category 3 Approval of the

Fig. 19. Force – displacement curves comparison between the experimental and numerical results for the epoxy adhesive (only the average of the experimental
curves is plotted to avoid cluttering): a) PA11, b) PA12.

14
M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

Fig. 20. Force – displacement curves comparison between the experimental and numerical results for the CA adhesive: a) PA11, b) PA12.

Fig. 21. Force – displacement curves comparison between the experimental and numerical results for the PU adhesive: a) PA11, b) PA12.

Fig. 22. Force – displacement curves comparison between the experimental and numerical results for the PU-hybrid adhesive: a) PA11, b) PA12.

version of the manuscript to be published (the names of all authors must Funding
be listed): M. Bahrami, D. Lavayen-Farfan, M.A. Martínez, J. Abenojar
This research did not receive any specific grant from funding
Authors contributions agencies in the public, commercial, or not-for-profit sectors.

Conceptualization and methodology: M.B., J.A., and M.Á.M.; simu­ Declaration of Competing Interest
lation: D.L.F; writing-original draft preparation: M.B., D.L.F.; writing-
review and editing: M.B., J.A., D.L.F. and M.Á.M.; supervision: J.A., The authors declare that they have no known competing financial
and M.Á.M. All authors have read and agreed to the published version of interests or personal relationships that could have appeared to influence
the manuscript. the work reported in this paper.

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M. Bahrami et al. Surfaces and Interfaces 32 (2022) 102154

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