Full Paper

Adhesion Improvement between Epoxy and

Stainless Steel Using a Silane Coupling Agent
in an Atmospheric Plasma Process

Gabriella Da Ponte,y Amit Kumar Ghosh,y Alexandros Kakaroglou,

Danny Van Hemelrijck, Bruno Van Mele, Bert Verheyde*

3-Aminopropyltriethoxysilane coatings have been deposited on stainless steel (SS) samples

by means of an atmospheric pressure dielectric barrier discharge as an adhesive promotion
layer in epoxy resin/SS composites. A multi-diagnostic analytical approach (FTIR, XPS) was
used for the chemical characterization of the
deposited coating with regard to improvement
of adhesively bonded joint strength. The effect
of a plasma post-treatment after the plasma
coating deposition was compared to a thermal
post-treatment. Both enhanced the siloxane
networking resulting in a significant adhesion
improvement. Fracture strength between SS
and epoxy was increased with more than
20 MPa.

1. Introduction
Dr. G. Da Ponte, Dr. B. Verheyde Stainless steel (SS) is extensively used in many technology
Vlaamse Instelling voor Technologisch Onderzoek, Boeretang
fields like construction, transportation, and process indus-
200, B-2400 Mol, Belgium
tries due to its excellent mechanical properties, corrosion
E-mail: [Link]@[Link]
resistance, and recyclability.[1] Recently, it gained a lot of
Dr. G. Da Ponte, A. K. Ghosh
SIM Researcher, Program NANOFORCE, SIM-Flanders vzw, interest for composite applications, either in the form of
Technologiepark 935, B-9052 Zwijnaarde, Belgium fiber reinforced composite[2–6] or in the form of sandwich
A. K. Ghosh, Prof. B. Van Mele panel (laminated steel plate) applications.[7,8] Polymer-steel
Research Group of Physical Chemistry and Polymer Science, Vrije hybrids offer an interesting combination: the stiffness and
Universiteit Brussel, Pleinlaan 2, B-1050 Brussels, Belgium strength of steel is combined with the low weight density
Dr. A. Kakaroglou and formability of polymers. These hybrid materials have
Research Group of Electrochemical and Surface Engineering, Vrije several advantages over the metal alone thanks to an
Universiteit Brussel, Pleinlaan 2, B-1050 Brussels, Belgium increased impact resistance, higher strength-to-weight
Prof. D. Van Hemelrijck
ratio, resistance to corrosion, better dimensional stability,
Department of Mechanics of Materials and Constructions, Vrije
and more design freedom.[8,9] However the lack in adhesion
Universiteit Brussel, Pleinlaan 2, B-1050 Brussels, Belgium
at the SS/polymer interface is one of the main drawbacks
y
These two authors contributed equally to this work of the hybrid combination.[10]

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] DOI: 10.1002/ppap.201400106 1
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
 G. Da Ponte et al.

Therefore it is important to improve the interfacial requires long time (about 2 d) for the hydrolysis of the
strength between SS and polymer to obtain better perform- coating solution to occur.[25] As a consequence, it might
ances and durability of the hybrid composite during actual be possible that some water or solvent remains in the
use.[11] To do that, different theories have been proposed siloxane film after condensation, decreasing the perfor-
in literature,[11–13] mechanical alteration of the substrate mance of the siloxane film, like for corrosion protection.[24]
(facilitates mechanical interlocking) based on grit-blasting, Deposition of silane coupling agents using atmospheric
sand blasting[14,15] or chemical etching,[16] and the polar plasma chemical vapor deposition could be an efficient
interactions with a bonding agent or with a chemical and innovative alternative to wet deposition with the
bonding facilitated by a coupling agent.[11,17–19] Indeed, a advantage of combining plasma cleaning a priori to the
coupling agent acts as an adhesion promoter being capable deposition in the same reactor. Atmospheric plasmas (AP)
of reacting with the metal substrate and also with the are nowadays well known in academics and industries
polymer material. Thanks to this chemical bonding, it is for surface engineering with a dedicated purpose.[26]
firmly anchored into the substrate and dissipates much Among different AP devices, as corona, torch, jets, dielectric
energy when loaded. Most adhesion promoters used to barrier discharges (DBDs) offer attractive perspectives as a
improve the interfacial strength of SS are based on silane versatile and easily implementable system in today’s
chemistry.[20,21] Silane based coupling agents have evolved industrial processes for coating deposition and surface
recently as a promising alternative for toxic chromate based functionalization.[27–30]
treatments offering several advantages as low cost, Atmospheric plasma deposition of siloxane films has
excellent corrosion protection, good adhesion properties already been described in literature where most of the
to organic coatings (i.e., epoxies, polyurethanes, polyesters, studies deal with the chemical characterization, the
and acrylics) and an overall improvement of the composite structure, and the functional properties of the deposited
properties like thermal durability, chemical or moisture siloxane film.[31–35] Some studies are also carried out to
resistance, mechanical strength, durability, and electrical investigate the plasma polymerization mechanisms of the
performance.[22] organosilicon compounds.[36–39] Generally, these deposited
The typical chemical structure of functional organosilane films are described as branched, highly cross-linked,
coupling agents is R-(CH2)n-Si-X3 where X is a hydrolysable insoluble in nature, pinhole free, and highly adhesive to
group (e.g., alkoxy, chlorine), R is an organic functionality most of the substrates.[40–42] A plasma deposited siloxane
(e.g., amino, methacryloxy, or epoxy), and n is generally 3. layer can act as an interfacial modifier for improving
Commonly, silanes are stored in the non-hydrolyzed state adhesion and corrosion resistance creating chemical bonds
and in most cases they need to be hydrolyzed in a dilute between the siloxane and metal interface.[43] The deposi-
aqueous solution before application. During the hydrolysis, tion of polyhydrogenmethylsiloxane and tetraethyl ortho-
silanol groups (SiOH) are produced which can link silicate on SS substrates improved the adhesion strength
covalently with the available hydroxyl groups often towards silicon elastomers.[44]
present on the metal surface.[22,23] In wet deposition The main goal of this study is to deposit a siloxane layer
methods, the metal substrates are initially dipped in a on a SS surface through DBD process. 3-Aminopropyltrie-
silane/silanol solution and the formation of a covalent bond thoxysiloxane (abbreviated as APS) was chosen as chemical
takes place during the drying process from the condensa- precursor not only because it is one of the most used
tion reaction between a hydroxyl group at the treated metal coupling agents for polymeric/inorganic composite but
surface and silanols. In that case, the R group remains also because the presence of an amino group (NH2) in its
available for covalent reaction with the epoxy or other structure makes it particularly reactive in the formation of
polymeric matrix. The silanol condensation reactions inside covalent bonds with the epoxy resin.[22]
the applied coating also lead to a cross linked siloxane Various process parameters, like the effect of plasma
network. The properties and quality of siloxane layers pretreatment prior to silane deposition, the plasma power
are strongly dependent on the various parameters of the during the deposition, the degree of precursor hydro-
deposition process.[22–24] Application of silane coupling lyzation, the treatment time, and the post-treatment step
agents through wet deposition technique is a widely on deposited film were studied. It is reported that a thermal
studied method, however it has some inherent limitations. annealing after coating deposition is causing a significant
Firstly, wet deposition technique is a multistep process that change in the surface and bulk compositions and is
requires dedicated substrate pre-treatment to enhance consistently generating defect free films.[45]
the metal–film bonding and a thermal post treatment for The effect of both thermal and plasma post treatment on
condensation of siloxane film. Secondly, the wet deposition the properties of the deposited film was studied. X-ray
technique involves the use of solutions (containing organic photoelectron spectroscopy (XPS), Fourier transform infra-
solvents if not water-based, i.e., acetone, ethanol, and red spectroscopy (FTIR) measurements were conducted to
hexane) with the formation of waste flows and it often characterize the deposited film. The adhesion strength

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

2 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201400106
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Adhesion Improvement between Epoxy and Stainless Steel . . .

evaluation of different samples was done by using pull-off dielectric glass plate (Figure 1). The system is described more in
testing (dolly testing). Fracture surface of the different dolly details in a previous article.[46] The two high voltage (HV) electrodes
samples were recorded and analyzed also to study the consist of metallic plates of 9 cm  34 cm each. The substrates
were fixed on the bottom grounded electrode. The top HV electrode
failure mode of the different samples.
was moving with a speed of 4 m  min1 above the ground electrode
to achieve homogeneous plasma treatments and thin films
deposition. An inter-electrode gap fixed at 2 mm and a frequency
2. Experimental Section constant at 1.5 kHz have been chosen to ensure stable plasma
operation in N2 atmosphere. The applied power was provided by a
2.1. Materials
high voltage generator (AFS G10S-V) and has been varied in
Bright annealed 304 SS (mirror polished) 0.8 mm thick was the range of 200–450 W, corresponding to a dissipated power of
provided by OCAS (Belgium) and used as substrates for plasma 0.6–1.5 W  cm2.
thin film deposition and dolly testing. For these purposes, the SS Two different N2 flows were used, controlled by software-
plates were cut in 30 mm  30 mm samples and sonicated in an managed (Aplaus) MKS mass flow controllers. N2 gas of 20 slm
isopropanol bath (3510 BRANSON ultrasonicator, 70 W) for 15 min. (later referred to as plasma gas, Fplasma gas) was used to ignite and
Mono/bi-sided lapped silicon and glass substrates were used for sustain the discharge. To this flow, APS was added as an aerosol
contact angle, FTIR, and thickness measurements, respectively, with a droplet size distribution between 10 and 300 nm which
after a proper cleaning in isopropanol ultrasonic bath. were generated by applying a N2 flow of 3 slm (later referred to as
3-Aminopropyltriethoxysiloxane (APS, 99% purity, CAS no: aerosol flow, Faerosol) to an in-house fabricated atomizer. Precursor
919-30-2) provided by Sigma–Aldrich (Belgium) was selected as consumption under these conditions is 9.9 g  min1.
organic precursor for the plasma deposition. One percent weight of Prior to the plasma deposition, a plasma pre-treatment in
bi-distilled water was added to pure APS to induce a pre-hydrolysis N2 þ O2 atmosphere was performed to remove impurities and to
of the precursor. Diglycidyl ether of bisphenol A, DGEBA with an enhance the amount of hydroxyl groups on the surface able to
equivalent weight of 185 g  mol1 (EPIKOTE 828 LVEL), supplied by link covalently to the siloxane film.[47,48]
Momentive Specialty chemicals (The Netherland) was chosen as Several experimental conditions were investigated to vary the
epoxy resin and 1,2 diamino cyclohexane (DAC, CAS no: 694-83-7) chemical composition of the deposited coating in order to enhance
with an equivalent weight of 28.5 g  mol1, supplied by Sigma– the adhesion toward the epoxy resin, as listed in Table 1.
Aldrich (Belgium) was chosen as curing agent. The final resin The power, related to the precursor structure retention in the
mixture was prepared by mixing the two phases in a stoichiometric discharge, the coating thickness, related to the deposition time, and
ratio by a mechanical mixer (Heidolph RZR 2041) at 2 400 rpm the effect of a pre-hydrolysis step of the APS were the main
for few minutes and by degassing it in a vacuum oven (15 min parameters under investigation. After the plasma deposition, a
in ambient temperature) before using it for the dolly sample post-treatment step was performed to build the siloxane network
preparation. formation either by thermal (conventional oven for 4 h at 100 8C)
Aluminum dollies (20 mm in diameter), previously sandblasted or plasma treatment. Note that this step is essential for the
and cleaned ultrasonically in acetone for 1 h, were used for pull-off adhesion improvement: adhesion tests performed on plasma
testing. coatings without post-treatment step showed an opposite effect
with a fracture strength lower than the untreated SS. In a
conventional wet deposition technique, the thermal treatment
2.2. Plasma Setup and Deposition Parameters leads to condensation of hydroxyl groups at the metal surface with
silanol groups and condensation of silanol groups mutually with
The experimental deposition system is a typical parallel plate DBD siloxane networking.
reactor, PlasmaZone1, where the plasma discharge is generated The plasma post treatment was optimized by changing the
between two metallic SS electrodes both covered with 3.5 mm thick parameters reported in Table 2 using both the FTIR spectra of the

Figure 1. Picture of PlasmaZone1 mounted on a X-moving table (left) and sketch of the DBD plasma setup (right).

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 3
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
 G. Da Ponte et al.

Table 1. Experimental conditions for plasma deposited thin coating (f ¼ 1.5 kHz, N2 Faerosol ¼ 3 slm, N2 Fplasma gas ¼ 20 slm).

Power [W] Precursor Deposition time [s]

Effect of power in pure APS 200, 450 Pure APS 48

Effect of power in APS þ 1% H2O 200, 450 APS þ 1% H2O 48
Effect of thickness 200 APS þ 1% H2O 16, 32, 48, 80

coating as deposited and after thermal treatment as a reference. electron flood gun was used to compensate the built up charge
The effect of the power, of the oxygen amount and of the treatment on the material surface. Spectra were charge-referenced to the
time was evaluated using FTIR spectroscopy. hydrocarbon component set at 285 eV. The spectral background
To prepare the pull-off samples, all the plasma treatments were was removed using the Shirley algorithm.[49] The spectral envelope
repeated for both sides of the SS plates consecutively. of the C1s peak was decomposed into the lowest number of
components that have physical meaning.[50,51]

2.3. Analytical Techniques

2.4. Dolly Sample Preparation and Testing
Profilometry – The coating thickness was quantified with a
Methodology
surface profile measurement performed with a WYKO NT3300
non-contact surface profiler in phase-shifting interferometry A dolly-plate-dolly (DPD) symmetric sample configuration was
(PSI). In order to perform an accurate measurement of the used (in accordance with ISO 4624:2003)[52] for the pull-off testing
thickness and of the coating growth speed, a longer deposition as showed in Figure 2, together with the testing methodology. A
time (120 s) was used to obtain an APS-plasma coating on home-made sample preparation set up (Figure 2) was designed to
ultrasonically cleaned glass with sufficient thickness. Based maintain a perfect alignment between the dollies, as strictly
on this, the plasma deposited APS_coating has a measured required for the DPD. The dolly sample preparation consists in the
growth speed of 1.1 nm  s1. application of a thin epoxy resin layers on the surface of both Al
FTIR – A commercial Thermo Nicolet Nexus 6700 FT-IR dollies and in the placing of a double side plasma treated SS sample
spectrometer run by Omnic1 software was used for the acquisition in between them. The joints were then hold together in the set-up
of the FTIR spectra of the plasma coatings in transmission (purging and a dead weight (500 g for each sample) in combination with
time of 15 min in N2). However to follow the hydrolysis path of the glass-beads placed in between each dolly and the SS plate was used
APS with 1 wt.-% of water, the Attenuated Total Reflectance (ATR)- to maintain the uniform thickness of the adhesive coating. The
FTIR (with 458 Ge crystal, single reflection) mode was used instead. excess resin was always scraped away from the DPD sample to
In both cases, the wave number range was at 4 000–800 cm1, minimize the unavoidable meniscus of the epoxy on the side of the
with 64 scans and 4 cm1 resolution. joint and to make its shape as reproducible as possible between
XPS were collected on a Perkin-Elmer Physical Electronics 5600 samples. The first step of the resin curing was performed by keeping
X-ray spectrometer, using a monochromatic Al X-ray source the dolly samples set up at ambient temperature for 12 h. The final
operating at 200 W. Measurements were done in fixed analyzer curing required two stages in a heated oven: I. 80 8C – 2 h and II.
transmission mode using pass energy of 93.9 eV for the survey 180 8C – 1 h. The thickness of the adhesive layers after curing
spectra and 23.5 eV for the high energy resolution spectra. An was approximately 0.2 mm.
The pull off adhesion tests were performed with an Instron test
bench (Instron 5885H, capacity 250 kN) in accordance with ISO
Table 2. Experimental condition for plasma post treatment 4624:2002[52] at room temperature. In order to achieve perfect
(f ¼ 1.5 kHz, N2 Faerosol ¼ N2 Fplasma gas ¼ 20 slm). alignment and to apply only normal forces, long and thin
connecting bars were introduced in between the jaws and DPD
Power O2 amount Treatment samples. The dollies were pulled vertically away from the SS
[W] [%] time [s] substrate with a jaw speed of 0.5 mm  min1 by means of a
threaded steel screw with a fix lower jaw (Figure 2). During testing,
Effect of 200 0 16, 48, 160 the maximum force needed to break the dolly sample was recorded
and at least six measurements were performed for each type of
treatment time 200 0.1 16, 48, 160
sample for an average value and standard deviation calculation.
200 20 16, 48, 160 The fracture strength (S, MPa) was calculated by using the
450 0 16, 48, 160 Equation (1), where L is the load at break (in N) and D is the
450 0.1 16, 48, 160 diameter of the dolly in mm:

450 20 16, 48, 160 S ¼ ðL4Þ=ðpD2 Þ ð1Þ

Effect of O2 200 0.1, 5, 10, 20 48 A digital image of the fractured dolly sample surface was
450 0.1, 5, 10, 20 48 recorded by an eight mega pixel digital camera.

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

4 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201400106
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Adhesion Improvement between Epoxy and Stainless Steel . . .

Figure 2. Schematic representation of dolly sample preparation and dolly testing methodology.

3. Results and Discussion the effect of the applied power on the chemical structure of
the deposited film (Table 1).
The majority of the work was carried out with a pre- FTIR spectra of plasma APS coatings deposited at two
hydrolyzed APS precursor because not only a better different powers, 200 and 450 W are reported in Figure 3,
improvement in the adhesion strength is expected based where the most interesting peaks are highlighted.
on literature,[53,54] but also first tests with pure APS resulted A detailed summary of FTIR peak assignment is reported
in lower adhesion values. in Table 3.
However, before using the partially hydrolyzed solution The absorption of C—N stretching in amine/amide
for the deposition, ATR-FTIR measurements were per- functionalities is present at 1 390 cm1 as well as the
formed on liquid drops to follow the hydrolysis path and the typical band at 3 370–3 230 cm1 due to asymmetric/
solution stability in time. The APS þ 1 weight% H2O was symmetric N—H stretching in primary amine for the
stable 5 min after the water addition and remained stable plasma deposited APS (denoted as pd_APS) at 200 W, very
for at least 24 h. The amount of water added to the pure APS likely correlated to APS precursor structure. The CH2/CH3
was intentionally very low compared to conventional wet symmetric/asymmetric stretch absorption at 2 930–
chemical approach in order to reduce the risk of plasma 2 830 cm1 is also most striking for pd_APS at 200 W. As
quenching due to the presence of a high water molecules commonly observed for plasma coatings, the chemical
concentration during the silane deposition. composition is more complex with the formation of new
functional groups not present in the precursor, as imines/
oximes with the characteristic absorption at 1 660 cm1.
3.1. Chemical Characterization
Remarkable differences between the two coatings (as
deposited and after thermal treatment) are found in the
3.1.1. Effect of Power
siloxane band between 1 200 and 1 000 cm1. Indeed, the
FTIR measurements on plasma deposited APS coatings plasma deposited coatings at 450 W showed a typical broad
have been performed prior to adhesion testing to evaluate absorption band related to Si—O—Si/Si—O—C stretching.

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 5
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
 G. Da Ponte et al.

the Si—OH bending at 955 cm1 and the vibration of full

ethoxy groups at 775 cm1.
The presence of peaks that are related to the precursor
chemistry, such as NH2 and CH2/CH3 groups, is a strong
evidence that the APS structure is more retained when a
lower power is applied.
Therefore, the lowest possible power of 200 W to
generate a plasma in nitrogen carrier gas was selected
for the further coating development and adhesion im-
provement, as well as for the post-treatment evaluation.

3.1.2. Effect of Post Treatment

In order to evaluate the effect of the post treatment, the APS
coating was deposited always in the same experimental
Figure 3. FTIR spectra of plasma deposited coating at 200 W and conditions (Table 1, f ¼ 1.5 kHz, N2 Faerosol_APS þ 1%H2O
450 W (Table 1, f ¼ 1.5 kHz, N2 Faerosol_APS þ 1%H2O ¼ 3 slm, N2 ¼ 3 slm, N2 Fplasma gas ¼ 20 slm, 48 s, 200 W) for all the
Fplasma gas ¼ 20 slm, 48 s) without post-treatment step. surface characterization performed.
The effect of the thermal post treatment was studied
for a fixed time and temperature (4 h, 100 8C), while more
By applying lower power, discrete peaks are present: (i) C—H parameters were considered in case of the plasma post
rocking in —CH3 of ethoxy groups (CH3CH2O—) at treatment (Table 2), as the influence of the plasma power
1 169 cm1, (ii) Si—O—Si/Si—O—C symmetric stretching (200 and 450 W). In fact, although the lowest possible
at 1 080 cm1 and (iii) Si—O—Si asymmetric stretching at power was chosen for the plasma coating deposition to
1 100 cm1. Below 1 000 cm1 the main difference concerns preserve the precursor chemical structure injected into

Table 3. FTIR peak assignment for APS coatings: as deposited, after thermal and plasma post treatment.

Wavelength [cm1]

Thermal post Plasma post

As deposited treatment treatment Peak assignment

– 3 600–3 000 3 600–3 000 O—H stretch/N—H stretch[53,55,56]

3 370–3 230 – – NH2 asymmetric/symmetric stretch[53,55]
2 930–2 830 2 930–2 830 2 930–2 830 CH2/CH3 symmetric and asymmetric stretch[53,55]
– 1 720 1 720 5O stretch (aldehyde, ketones, carboxylic acid)[55]
C5
– 1 680 1 680 5O stretch (amides)[54,55]
C5
1 660 1 660 1 660 5N stretch (imines, oximes)[55,57]
C5
1 440 – – CH3 umbrella bending mode[55]
1 390 – – C—N stretch (amines, amides)[55]
1 295 – – Si—CH2 wag, C—C—O stretch (carboxylic acids, alcohols,
silanols)[55]
– 1 470–1 260 1 470–1 260 Discrete absorption for as deposited at 1 440, 1 390, 1 295 cm1,
N—O asymmetric/symmetric stretch (nitro compounds)[58]
1 169 – – C—H rocking in CH3 in CH3CH2O—[53]
1 080 1 040 1 040 Si—O—Si/Si—O—C symmetric stretch[55,56]
1 100 1 120 1 120 Si—O—Si asymmetric stretch[53–55,57]
955 – 955 O2-deficient Si—O—H bending[55–57]
– – 910 O2-excess O—H bending/N—H wagging[54]
775 775 775 Vibration of full CH3CH2O— group[53]

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

6 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201400106
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Adhesion Improvement between Epoxy and Stainless Steel . . .

the discharge, in the case of the post treatment where only

N2 and O2 gases are involved without any additional
chemistry, an increase in the power level may generate
more reactive gas species resulting in a more efficient
interaction with the deposited APS film.
A deeper investigation of the coating chemical changes
were performed both for the thermal and plasma post
treatment. In the case of plasma, the effect of different
parameters as gas feed (i.e., amount of oxygen from 0 to
20%), treatment time and applied power was evaluated
(Table 2). In Figure 4, FTIR spectra of coatings deposited
using the same plasma condition, before and after thermal
post treatment were compared.
The chemical composition of these films is strongly
influenced by the extra thermal treatment that is probably
enhancing the carbon oxidation state as indicated by the
absorptions between 1 720 and 1 660 cm1, and surely the
siloxane networking as clearly observed in the broadening
of the characteristic siloxane band between 1 200 and
1 000 cm1.
Regarding the plasma post treatment, the role of the
treatment time on the further siloxane networking is
reported in Figure 5 for three different gas mixture
compositions, pure N2, N2 þ 0.1% O2 and N2 þ 20% O2.
This study was performed at 200 and 450 W, but since the
power appeared to be a negligible parameter in case of
the plasma post treatment, the FTIR spectra of pd_APS
coatings with a plasma post treatment at 450 W were
shown. All the FTIR spectra for pd_APS with plasma post
treatment are compared to the spectra of the film as
deposited and after thermal post treatment, both used as
references.
As reported before, the spectral region of main interest is
related to the siloxane band (1 200–1 000 cm1), focusing on
the typical broadening of the absorption band correlated
to the Si—O—Si networking improvement, on the Si—OH

Figure 5. Effect of plasma post treatment: FTIR spectra of plasma

deposited APS coating (Table 1, f ¼ 1.5 kHz, N2 Faerosol_APS þ 1%
H2O ¼ 3 slm, N2 Fplasma gas ¼ 20 slm, 48 s, 200 W) subjected to a
plasma post treatment at 450 W for different time (16 s, 48 s,
160 s) and 3 gas mixtures: i) pure N2, ii) N2þ 1% O2 and
iii) N2 þ 20% O2.

and ethoxy stretching at 955 and 775 cm1. The plasma

post-treatment step performed in pure N2 resulted in a
minor variation of the chemical structure of the deposited
Figure 4. FTIR spectra of plasma deposited APS coating (Table 1,
coating. Indeed, irrespective the treatment time, the FTIR
f ¼ 1.5 kHz, N2 Faerosol_APS þ 1%H2O ¼ 3 slm, N2 Fplasma gas ¼ 20 spectra after plasma treatment are rather comparable to
slm, 48 s, 200 W) with and without thermal post treatment. the FTIR spectrum of the as deposited coating. The addition

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 7
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
 G. Da Ponte et al.

of 0.1% of oxygen had a slight effect on the chemical

composition of the deposited coatings with a low
pronounced broadening of the siloxane band and a partial
oxidation of the coatings indicated by the presence of —NOx
groups at 1 470–1 260 cm1 mainly observed for long
treatments (160 s). The oxidative effect of the plasma post
treatment is clear by increasing the oxygen amount of the
feed gas to air level (Figure 7, iii), where the absorption of
—NOx groups and O—H bending/N—H wagging at
910 cm1 is strongly enhanced, coherently with the
hydrophilic behavior already observed for SE measure-
ments. Besides that, the main effect of the oxygen addition
is the promotion of the siloxane networking formation
regardless the treatment time. Therefore, the O2 amount of
the feed gas has been investigated more in details to
Figure 6. Effect of oxygen amount in the feed gas: FTIR spectra
of plasma deposited APS coating (Table 1, f ¼ 1.5 kHz, N2 understand deeply its effect on the plasma post treatment.
Faerosol_APS þ 1%H2O ¼ 3 slm, N2 Fplasma gas ¼ 20 slm, 48 s, An intermediate treatment time (48 s) and two different
200 W) subjected to a plasma post treatment of 48s for power levels, 200 and 450 W, were chosen for the process.
different amount of oxygen (0.1%, 5%, 10%, 20%) at 450 W. Figure 6 reports the FTIR spectra at 450 W because a similar
trend was observed at 200 W.

Figure 7. XPS results: C1s, N1s, O1s and Si2p best fitting spectra for (a) as deposited, (b) thermal post treatment, (c) plasma post
treatment_10% O2, 450 W, 48 s.

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

8 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201400106
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Adhesion Improvement between Epoxy and Stainless Steel . . .

By increasing the O2 from 0.1 to 20%, the chemical peak fitting of C1s, O1s, N1s, and Si2p high resolution
composition of the films is strongly oxidized by reactive O2 spectra for plasma deposited films,[55,59] with minor
species generated in the plasma phase. Main experimental changes due to the formation of new functional groups,
observations are: (i) strong absorption band at 3 600– as amide and nitro-groups during the plasma process as
3 000 cm1 due to O—H/N—H stretching, (ii) presence of observed from FTIR spectra.
aldehyde and ketones at 1 720–1 680 cm1 as for thermal As extensively reported in Table 4, the C1s has been
post treatment, (iii) increase of absorption band at 1 470– best-fitted in six peak components. The full width in half
1 260 cm1 and (iv) presence of OH bending/N—H wagging maximum (FWHM) was taken the same for all fitting
at 910 cm1. Moreover, an addition of 5% O2 in the N2 gas components and fitted between 1.1 and 1.3.
flow is already enough to obtain a siloxane band (1 200– Table 5 shows the comparison of the elemental
1 000 cm1) comparable to the pd_APS with thermal post composition (%) together with the elemental ratio of the
treatment. pd_APS coatings and sol–gel deposited APS coating.[55]
XPS measurements have been performed on selected The C/Si ratio (Table 5) decrease from 7.2 for the as
coatings for a complementary understanding of the chemi- deposited coating to 5.1 after a thermal post treatment and
cal changes experienced after thermal and plasma post 2.9 after plasma post treatment. The C/Si ratio for the as
treatment. The coating deposition was performed in the deposited coating resembles most to 9 which corresponds
same conditions (Table 1, f ¼ 1.5 kHz, N2 Faerosol_APS þ 1% to unreacted APS (C9H17O3NSi.). Once the polycondensation
H2O ¼ 3 slm, N2 Fplasmagas ¼ 20 slm, 48 s, 200 W). The survey reaction has taken place ethoxy functions are removed
XPS spectra show no lines of Fe of the substrates. and the C/Si is dropping to theoretically 3 in case of full
Figure 7 and Table 4 report on the elemental chemical condensation with remain of the aminopropyl group.
environments with the best fitting spectra for C1s, N1s, The coating after plasma treatment tends most to the C/Si
O1s, and Si2p. ratio of such condensated APS. Note that the N/Si ratio
The data in literature regarding sol–gel APS conventional for all coatings is approximately 1.0 as expected for the
films (wet chemistry deposition approach) were used for APS precursor. The O/Si and O/N ratios (Table 5) confirm

Table 4. Peak components and attribution for C1s, O1s, N1s and Si2p regions for APS coatings: as deposited, after thermal and plasma post
treatment.

As Thermal post Plasma post

Peak assignments deposited treatment treatment

Element Region Peak BE [eV] Attribution Area [%] Area [%] Area [%]

C C1s C0 284.4  0.2 C—Si[55,60] 23  2 22  2 23  2

C1 285.0  0.2 C—C/C—R (H)[55,60] 31  2 37  2 25  2
C2 286.0  0.2 C—N [55,60]
13  2 21  2 15  2
C3 286.6  0.2 5C—O—C ,
C—O—R(H)/O5 28  2 92 18  2
5N
C5 [55,60]

C4 287.9  0.2 5O/N—C5

C5 5O[55,60] 41 91 10  1
C5 288.9  0.2 C OOH(R)[55,60] <1 21 91
O O1s O1 530.8  0.2 —O (oxide) [21]
42 42 21
O2 532.1  0.2 —OH[21] 81  2 60  2 55  2
O3 532.7  0.2 —O—Si[21,61] 15  2 36  2 43  2

N N1s N1 398.8  0.2 5C[60,62]

N5 23  2 42 _
N2 399.7  0.2 C—N[60] 45  2 29  2 18  2
N3 400.5  0.2 5O[60]
NC5 21  2 43  2 23  2
N4 401.7  0.2 NH2 =NHþ3
[60,62]
21 91 26  1
N5 406.3  0.2 NOx[63,64]
92 15  2 33  2
Si Si2p Si1 102.1–102.4  0.2 Si—(O)2[65] 75  2 74  2 72  2
Si2 102.7–103.0  0.2 Si—(O)3/4[65] 25  2 26  2 29  2

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 9
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
 G. Da Ponte et al.

Table 5. Elemental composition (%) and C/Si, O/Si, O/N, and N/Si ratio for pd_APS coatings compared with sol-gel values.[55]

C O N Si C/Si O/Si O/N N/Si

As deposited 57.5 26.4 8.2 7.9 7.2 3.3 3.2 1.04

Thermal post treatment 49.4 31.7 9.3 9.6 5.1 3.3 3.4 0.97
Plasma post treatment 32.6 45.2 10.8 11.3 2.9 4 4.2 0.96
Sol-gel APS[55] 52 21 14 13 4 1.6 1.5 1.07

the higher oxygen content of the coatings subjected to related fracture strength combined with their correspond-
a plasma post treatment, with an increase from 3.3 to 4 ing standard deviation are reported in Table 6. It is crucial
and 3.2 to 4.2, respectively. Comparing those values with to highlight that for all plasma coatings without further
conventionally polymerized films (wet chemistry) that treatment step, either thermal or plasma, the fracture
show values of around 1.5, the effect of oxygen content strength was lower or comparable to untreated SS samples
during plasma deposition and post treatment is clear. (data not shown).
The main effect of the post-treatment results in an For the thermal post treatment, the process improve-
expected decrease of the ether/alcoholic component ment was mainly oriented in the tuning of the chemical
C—O—R (H) (C3) via the elimination of ethanol molecules coating composition, monitored by FTIR and XPS, varying
belonging to the precursor in favor of an improvement of the APS precursor (with or without water addition), the
siloxane networking. power and treatment time related to the coating thickness.
This decrease in the C—O—R (H) is more pronounced for A significant improvement of the fracture strength was
the thermal than for the plasma treatment, most likely due achieved by using the pre-hydrolyzed APS solution with
to the oxidative N2 þ O2 plasma effect, consistent with the the lowest applied power of 200 W. In these conditions,
growth of O-functionalities as chetonic/amides and car- an increase of the fracture strength from 9  4 MPa for
boxylic groups for the plasma post treatment (C4, C5). The untreated SS to 28  5 MPa and 37  9 MPa was obtained
decrease of the oxygen component at 532.1 eV for hydroxyl for a deposition time of 48 and 32 s, corresponding to a
groups (O2) is in line with the C1s best fitting: the post thickness of 53 and 35 nm, respectively. Shorter (16 s) and
treatment, both thermal or plasma, is linked to siloxane longer (80 s) treatments resulted in a decrease in the
networking via ethanol consumption. The Si—O—Si fracture strength, most likely due to a not homogeneous
networking is further attested by the increase of the coating in the first case and to a possible internal break of
O—Si component at 532.7 eV (O3). a too thick soft coating for the longest deposition.
In addition, the plasma post treatment is promoting the In order to perform the plasma post treatment, the APS
formation of (protonated) amines and nitro groups (N4, N5). film was deposited always at fixed experimental plasma
In either case, these results are coherent with the previous conditions with APS þ 1%water, 200 W for 48 s. In this
observation based on FTIR. case, the parameters under investigation are the oxygen
The Si2p spectra (Figure 7) are subjected to a shift toward concentration in the plasma gas, the power and the post
higher binding energy, compared with the as deposited film, treatment time. The best adhesion improvements have
of 0.3 eV for the thermal post treatment and 0.4 eV in case of been reached for an O2 addition of either 5% (450 W, 48 s)
the plasma post-treatment attesting for a more pronounced or 10% (450 W, 16 and 48 s), as reported in Table 6. However,
oxidation environment experienced by the Si. Indeed, the the effect of power and treatment time is less conclusive.
Si2p binding energies for the silicon chemical environments Both thermal and plasma post treatment promoted a
Si(—O)2, Si(—O)3, Si(—O)4 are 102.1, 102.8, and 103.4 eV, significant improvement of fracture strength of around
respectively.[65] After the post treatment the silicon chemi- 20 MPa with respect to native SS, as showed in Figure 8.
cal environments in the pd_APS coatings become thus The adhesion failure passed from a purely adhesive one
more oxidised with a shift toward higher binding energy, in the case of native SS (or equally for plasma coatings
mainly for the plasma post treatment where and interme- without post treatment) to an adhesive–cohesive mixed
diate value for Si(—O)3 and Si(—O)4 is observed probably failure mode after post treatment (Figure 8).
indicating the co-existence of both species.

4. Discussion
3.2. Adhesion Strength Measurement
Adhesion strength measurements have been carried out on As observed in the previous section, the principal effect of the
selected samples; an overview of the adhesion tests and post treatment is an improvement of the siloxane network

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

10 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201400106
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Adhesion Improvement between Epoxy and Stainless Steel . . .

Table 6. Overview of adhesion strength measurements on plasma APS coatings with thermal and plasma post treatment.

Coating deposition Post treatment

Fracture
Thermal Plasma strength

Studied Power Deposition Temperature Time Power O2 Treatment

effect Precursor [W] time [s] [8C] [h] [W] [%] time [s] [MPa]

Native SS No treatment – – – – – – – 94

Thermal post Effect of Pure APS 450 48 100 4 75
treatment the power Pure APS 350 48 100 4 83
Pure APS 200 48 100 4 13  2
APS þ 1%water 350 48 100 4 14  4
APS þ 1%water 200 48 100 4 28  5
Effect APS þ 1%water 200 16 100 4 17  8
deposition APS þ 1%water 200 32 100 4 37  9
time APS þ 1%water 200 80 100 4 23  3
Plasma post Effect of APS þ 1%water 200 48 450 5 48 29  8
treatment O2 amount APS þ 1%water 200 48 450 10 48 30  4
APS þ 1%water 200 48 450 20 48 24  4
Effect of APS þ 1%water 200 48 200 10 16 24  4
power and APS þ 1%water 200 48 200 10 48 20  5
treatment APS þ 1%water 200 48 450 10 16 28  5
time APS þ 1%water 200 48 450 5 16 20  4

via the ethanol consumption and an increase in the oxidation Si covalent bonds. Furthermore, it is assumed that Si—O—Me
of the coatings mainly after the plasma treatment. Both the covalent bonds are generated in a similar way, which is
temperature and the plasma conditions are enhancing the indirectly supported by the observed adhesion strength
reactions between vicinal silanols groups to generate Si—O— improvement (for additional support, see ref.[43]).

Figure 8. Improvement of the fracture strength for thermal and plasma post treatment (left). Images of adhesive failure for native SS,
best condition for thermal and plasma post treatment (right).

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 11
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
 G. Da Ponte et al.

The conventional mechanism for a sol–gel siloxane film final effect of both processes on the deposited film is
formation (wet chemistry approach) is well known and comparable.
reported in several papers.[66,67] Three main steps are As main outcome from the previous section, the O2 key
involved: (i) partial hydrolysis of the precursor with silanol role was proven in promoting the further development of
formation, (ii) condensation between two silanol groups the pd_coatings. It is known that the addition of O2 to the
with water elimination, and (iii) further condensation plasma during atmospheric plasma deposition of silanes
between silanols and siloxane networking with the is strongly influencing the amount of carbon left in the
elongation of the Si—O—Si chain by elimination of ethanol deposited coating. O2 creates excited species of dissociated
in the case of the APS. molecular O2 as well as several radicals. The interaction of
The deposition of siloxane coatings via plasma followed these energized oxygen species with the plasma deposited
by a thermal or plasma post treatment leads to a layer with coatings may lead to several processes as C—C bonds
a similar chemical structure attested by several experi- rupture and hydrocarbon oxidation.[68] In the specific case
mental evidences as the reduction of ethoxy groups in favor of pd_APS films with a thickness around 30–40 nm, the
of the increase of Si—O—Si networking. However, the coating may undergo a strong oxidative effect during
intrinsic reactive nature of the plasma during the coating the plasma post-treatment step that may be described as
deposition and the oxidative post-treatment step generates a combustion process when performed in O2-excess. Indeed
new chemical groups in the coatings. FTIR and XPS data typical functional groups of the APS precursor as —Si
revealed the presence of other functionalities, not expected (OC2H5) present in the coating after the plasma coating
in conventional wet chemistry APS polymerization, as deposition (Table 3 and 4, Figure 3) may interact with
amide, imine and nitro-groups. The following discussion reactive O-species to produce silicon-oxygen species and
is dedicated to the understanding of the mechanism of CO2 and H2O coming from the hydrocarbons part combus-
formation of these chemical groups. Imine groups are tion. This mechanism for the Si—O—Si network formation
formed during the plasma deposition from the APS after plasma post treatment, is supported by different
precursor aerosol. A possible explanation is reported in experimental evidences: (i) decrease of ethoxy component
literature where the formation of imine in oxygen at 1 169 and 775 cm1 (Table 3, Figure 4 and 5), (ii) increase
atmosphere and in presence of a reactive source (heating of Si—O—Si groups (Table 3, Figure 4 and 5, O3 component
or plasma) is described as in Scheme 1. due to Si—O in Table 4), (iii) decrease of C/Si observed
Moreover by following the reaction Scheme 1 the only after plasma post treatment related to a possible
hydrolysis of the imine promotes aldehyde formation with carbon loss as CO2(g) (Table 5).
elimination of NH3. The presence of these successive Both in the case of thermal and plasma post treatment,
reactions could explain the formation and co-existence of an increase of the (H)R—C5 5O/N—C5 5O component at
these species in the plasma deposited coatings, as attested 1 680 cm1 is observed with FTIR (Table 3), confirmed by
by XPS (Table 4). This could also justify the O/N ratio XPS with the increase in the N3 component of N1s
increase observed for all the plasma deposited coatings (Table 4), mainly for the thermal post treatment.
compared to sol-gel, with a loss in N-functionalities in Moreover the main variation observed after post treat-
favor of O-functionalities. ment compared to the as deposited coating is specifically
A further complication of the chemical composition of related to two IR frequency regions, 3 600–3 000 cm1
the coatings is obtained after the post treatment. Both and 1 450–1 250 cm1. The region at 3 600–3 000 cm1 is
the thermal and the plasma post treatment, if performed generally assigned to —OH groups, but besides hydroxyl
with a certain level of O2 in the plasma gas mixture, groups, amines are found in that region. Therefore by
enhanced the siloxane networking, as clearly observed in analyzing the XPS spectra in combination with the FTIR
the previous section. However, besides the Si—O—Si data, it is important to highlight the decrease of the O1s
formation and polymer chain elongation, other reactions component related to —OH groups (O2, Table 4) after
take place during the post treatment encouraged either post treatment despite a significant increase of the N4
by the heating or the plasma. A general finding is that the component due to R—NH2, mainly in the case of the
plasma post treatment.
In Figure 9, the evolution of the FTIR spectrum of the
plasma deposited and plasma post-treated APS coating is
shown upon storing a sample in a desiccator. A decrease of
the silanol peak around 910 cm1 was noticed which is
explained by a further condensation taking place during the
first day after coating deposition. Although less clear, it is
Scheme 1. Formation and Hydrolysis of Imine in Aminosilane confirmed by the slight decrease of the broad band above
Films.[57] 3 000 cm1.

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

12 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201400106
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Adhesion Improvement between Epoxy and Stainless Steel . . .

Therefore, both thermal and plasma post treatment are

decisive for the adhesion improvement (Table 6) by the
silanol condensation with Si—O—Si bonds formation prior
to the interaction of the plasma films with the epoxy/amine
mixture and the thermal curing process of the thermoset. It
is assumed that the post treatment prior to epoxy/amine
cure not only enhances the siloxane networking and the
coating strength, but also favors the formation of Si—O—
Me covalent bonds at the metal surface, improving the
pd_APS coating/SS adhesion. The thermal and plasma post
treatments clearly induce chemical changes, such as
silanol/ethoxy reduction and formation of new (different)
chemical functionalities or the presence of reactive groups
in a different ratio. As an example, especially coatings
subjected to a plasma post treatment, contain nitro
Figure 9. Effect of aging (drying) up to one month in a desiccator:
FTIR spectra of plasma deposited APS coating (Table 1, f ¼ 1.5 kHz, compounds, and a significant amount of amines (Table 4,
N2 aerosol_APSþ1%H2O ¼ 3 slm, N2 plasma gas ¼ 20 slm, 48 s, 200 W) Figure 9); the latter are important in the reaction of the
subjected to a plasma post treatment performed at 10% O2, at epoxy/amine thermosetting system. Although chemical
450 W for 48 s. differences exist between thermal and plasma post treat-
ments, the final effect in both cases is a significant increase
in the adhesion strength of more than 20 MPa in SS/epoxy
The strong oxidative effect of the post treatment is composites (Figure 8). Post treatment of this adhesion
evident in the absorption peaks in the IR region between promotion layer can improve mechanical properties of
1 450 and 1 250 cm1, correlated to the presence of several the layer by increasing Si—O—Si networking and/or can
functional groups as stated in Table 3. However mainly in contribute to the creation of stronger interfaces (interphases)
the case of plasma post treatment, the presence of nitro between coupling layer and metal substrate (Si—O—Me
compounds is strongly increased as confirmed by the bond formation) and between coupling layer and the cured
component N5 of N1s (Table 4, Figure 6) justifying the organic epoxy matrix. This leads to a remarkable increase
increase of the O/N ratio compared to as deposited and of adhesion strength in epoxy/SS hybrids.
thermally treated coatings as observed in Table 5.
As a main achievement of this study, it has been proven
that the thermal or plasma post treatments are strongly 5. Conclusion
improving the adhesion strength in epoxy/SS hybrids
(Section 3.2). Indeed, the pd_APS coating without any post In the present paper, atmospheric pressure plasma deposi-
treatment shows a very low adhesion strength in SS tion of siloxane coatings is presented as a feasible and
composites. The chemistry of the as deposited APS coating is convenient alternative to conventional wet chemistry in
quite different compared to its chemical composition after terms of a sensible reduction of the overall process time and
the post treatment. Clear evidences of the precursor liquid waste as well as a versatile technology easy to be
structure are still present after plasma deposition, as implemented in an existing production line. The chemical
shown by discrete IR peaks related to ethoxy and silanol composition of the thin Si—O—Si plasma deposited film
groups and the XPS C/Si ratio of 7.2 close to the APS was optimized by a multi diagnostic approach by evaluat-
precursor value of 9.0. The highly retained APS structure in ing the effect of the main external plasma parameters
as deposited coatings may undergo a condensation step (power, precursor, thickness, and post treatment) in
during the thermal epoxy curing reaction. As a result, the relation to the improved adhesion property. As main
Si—O—Si networking would be improved, but in combina- outcome, the positive effect of the post-treatment step,
tion with water release. It is known that the presence of either thermal or plasma, on the adhesion strength increase
minor amounts of water is interfering with the epoxy/ has been found. In both cases, an improvement of more
amine curing step: water will affect the epoxy cure rate and than 20 MPa in fracture strength was reached when an
also decrease the final crosslink density and glass transition applied power of 200 W and pre-hydrolyzed APS were used
temperature, leading to worse mechanical properties of for the coating deposition.
the epoxy thermoset.[69–71] These effects are important for Moreover, it is clear from this work that the post
the development of the coupling agent/epoxy interface treatment after plasma deposition is a valuable alternative
(interphase) and might lead, as a consequence, to an to conventional thermal (sol–gel) wet chemistry deposi-
inferior epoxy/SS adhesion. tion. It leads to undoubted advantages over wet processes

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 13
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
 G. Da Ponte et al.

from the technological and industrial point of view. Indeed, [20] M. Honkanen, M. Hoikkanen, M. Vippola, J. Vuorinen, T.
the proposed plasma approach offers a versatile technology €ytty, M. Lampima
Lepisto, P. Jussila, H. Ali-Lo €ki, Appl. Surf. Sci.
2011, 257, 9335.
all-in-one combining the surface treatment with the post-
€ytty, K. Lahtonen, M. Hirsimaki, M. Valden,
[21] P. Jussila, H. Ali-Lo
treatment step with a potential enormous impact in the Surf. Interface Anal. 2010, 42, 157.
silane based coupling agent sector. The main advantage of [22] E. P. Plueddemann, In Siloxane Coupling Agents, 2nd edition,
plasma post treatment over thermal is the overall speed of Plenum Press, New York, USA 1991.
the process. Indeed the plasma post treatment is performed [23] M. L. Abel, R. D. Allington, R. P. Digby, N. Porritt, S. J. Shaw, J. F.
in line directly after the coating deposition and requires Watts, Int. J. Adhes. Adhes. 2006, 26, 2.
[24] A. Batan, F. Brusciotti, I. De Graeve, J. Vereecken, M. Wenkin,
only few minutes, while the thermal post treatment is a M. Piens, J. J. Pireaux, F. Reniers, H. Terryn, Prog. Org. Coat.
separate 2–4 h batch process. 2010, 69, 126.
[25] D. Zhu, W. J. Van Ooij, Prog. Org. Coat. 2004, 49, 42.
[26] D. Merche, N. Vandencasteele, F. Reniers, Thin Solid Films
Acknowledgments: This research was done in the framework of 2012, 520, 4219.
the SIM-Nanoforce program (Next generation nano-engineered [27] P. Heyse, R. Dams, S. Paulussen, K. Houthoofd, K. Janssen, P. A.
polymer-steel/CNT hybrids) and SIM is gratefully acknowledged Jacobs, B. F. Sels, Plasma Process. Polym. 2007, 4, 145.
[28] G. Da Ponte, E. Sardella, F. Fanelli, R. d’Agostino, R. Gristina, P.
for its financial support. ArcelorMittal Global R&D Gent – OCAS
NV is acknowledged for providing SS samples. Favia, Plasma Process. Polym. 2012, 9, 1176.
[29] G. Da Ponte, E. Sardella, F. Fanelli, S. Paulussen, P. Favia,
Plasma Process. Polym. 2014, 11, 345.
[30] S. Put, C. Bertels, A. Vanhulsel, Surf. Coat. Technol. 2013,
234, 76.
Received: August 5, 2014; Revised: September 14, 2014; Accepted: [31] A. Sabata, W. J. Van Ooij, H. K. Yasuda, Surf. Interface Anal.
September 22, 2014;DOI: 10.1002/ppap.201400106 1993, 20, 845.
Keywords: composites; dielectric barrier discharges (DBD); plasma [32] I. Tajima, M. Yamamoto, J. Polym. Sci. Part A: Polym. Chem.
post treatment; silane; stainless steel 1987, 25, 1737.
[33] R. Foest, F. Adler, F. Sigeneger, M. Schmidt, Surf. Coat. Technol.
2003, 163, 323.
[34] B. Verheyde, D. Havermans, A. Vanhulsel, Plasma Process.
[1] J. R. Davis, Stainless Steels, ASM International, Ohio, USA 1999. Polym. 2011, 8, 755.
[2] R. Karakuzu, C. Atas, H. Akbulut, Compos. Sci. Technol. 2001, [35] V. Danilov, H.-E. Wagner, J. Meichsner, Plasma Process. Polym.
61, 1475. 2011, 8, 1059.
[3] C. Sabino-Netto, G. V. Salmoria, C. H. Ahrens, A. S. Pouzada, [36] U. Lommatzsch, J. Ihde, Plasma Process. Polym. 2009, 6, 642.
Mater. Sci. Forum. 2008, 587–588, 222. [37] C. P. Klages, M. Eichler, R. Thyen, New Diam. Fronti. C Technol.
[4] W. Hufenbach, M. Gude, O. Helms, A. Ulbricht, Proceedings in 2003, 13, 175.
1st EUCOMAS conference. 2008, 1st EUCOMAS, 131. [38] J. H. Lee, T. T. T. Pham, Y. S. Kim, J. T. Lim, S. J. Kyung, G. Y.
[5] T. J. Ahmed, PhD Thesis TU Delft (Delft, Netherland), April, Yeom, J. Electrochem. Soc. 2008, 155, D163.
2009. [39] F. Massines, N. Gherardi, F. Sommer, Plasmas Polym. 2000, 5,
[6] M. G. Callens, L. Gorbatikh, I. Verpoest, Compos. Part A 2014, 151.
61, 235. [40] P. Supiot, C. Vivien, A. Granier, A. Bousquet, A. Mackova, D.
[7] X. Zhao, L. Zhang, Eng. Struct. 2007, 29, 1808. Escaich, R. Clergereaux, P. Raynaud, Z. Stryhal, J. Pavlik,
[8] M. Honkanen, M. Hoikkanen, M. Vippola, J. Vuorinen, T. Plasma Process. Polym. 2006, 3, 100.
Lepisto€, J. Adhes. Sci. Technol. 2009, 23, 1747. [41] T. Hiraide, H. Yamada, O. Tsuji, J. Photopolym. Sci. Technol.
[9] M. Grujicic, V. Sellappan, M. A. Omar, N. Seyr, A. Obieglo, M. 1994, 7, 345.
Erdmann, J. Holzleitner, J. Mater. Process. Technol. 2008, 197, [42] A. Meiners, G. Ohms, M. Leck, U. Vetter, B. Abel, J. Adhes. Sci.
363. Technol. 2012, 26, 1611.
[10] B. Morais, A. B. Pereira, J. P. Teixeira, N. C. Cavaleiro, Int. J. [43] A. Batan, N. Mine, B. Douhard, F. Brusciotti, I. De Graeve, J.
Adhes. Adhes. 2007, 27, 679. Vereecken, M. Wenkin, M. Piens, H. Terryn, J. J. Pireaux, F.
€
[11] L. F. M. da Silva, A. Ochsner, R. D. Adams, Eds., Handbook of Reniers, Chem. Phys. Lett. 2010, 493, 107.
Adhesion Technology, Springer, Heidelberg 2011. [44] E. Nwankire, M. Ardhaoui, D. P. Dowling, Polym. Int. 2009, 58,
[12] D. E. Packham, J. Adhes. 2008, 84, 240. 996.
[13] A. Baldan, Int. J. Adhes. Adhes. 2012, 38, 95. [45] K. G. Sachdev, H. S. Sachdev, Thin Solid Films 1983, 107, 245.
[14] F. Harris, A. Beevers, Int. J. Adhes. Adhes. 1999, 19, 445. [46] J. Bour, J. Bardon, H. Aubriet, D. Del Frari, B. Verheyde, R.
[15] S. Y. Park, W. J. Choi, H. S. Choi, H. Kwon, S. H. Kim, J. Adhes. Dams, D. Vangeneugden, D. Ruch, Plasma Process. Polym.
2010, 86, 192. 2008, 5, 788.
[16] F. Bouquet, J. M. Cuntz, C. Coddet, J. Adhes. Sci. Technol. 1992, [47] F. O’Kane, K. L. Mittal, J. Vac. Sci. Technol. 1974, 11, 567.
6, 233. [48] T. S. Williams, H. Yu, P. C. Yeh, J. M. Yang, R. F. Hicks, J. Compos.
[17] P. Puomi, H. M. Fagerholm, J. Adhes. Sci. Technol. 2001, 15, 509. Mater. 2014, 48, 219.
[18] F. Awaja, M. Gilbert, G. Kelly, B. Fox, P. J. Pigram, Prog. Polym. [49] A. Shirley, Phys. Rev. B 1972, 5, 4709.
Sci. 2009, 34, 948. [50] A. Batan, B. Nisol, A. Kakaroglou, I. De Graeve, G. Van Assche,
[19] M. N. Sathyanarayana, M. Yaseen, Prog. Org. Coat. 1995, 26, B. Van Mele, H. Terryn, F. Reniers, Plasma Process. Polym.
275. 2013, 10, 857.

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

14 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201400106
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Adhesion Improvement between Epoxy and Stainless Steel . . .

[51] T. Van Schaftinghen, C. Le Pen, H. Terryn, F. Horzenberger, [62] E. T. Vandenberg, L. Bertilsson, B. Liedberg, K. Uvdal, R.
Electrochim. Acta 2004, 49, 2997. Erlandsson, H. Elwing, I. Lundstro €m, J. Colloid Interf. Sci. 1991,
[52] Standard NF EN ISO 4624, 2003. 147, 103.
[53] R. Pena-Alonso, J. Rubio, J. L. Oteo, J. Mater. Sci. 2007, 42, 595. [63] A. Hollander, S. Kropke, F. Pippig, Surf. Interface Anal. 2008,
[54] X. Wang, G. Li, A. Li, Z. Zhang, J. Mater. Process. Technol. 2007, 40, 379.
186, 259. [64] B. Finke, K. Schroder, A. Ohl, Plasma Process. Polym. 2008, 5,
[55] E. Lecoq, D. Duday, S. Bulou, G. Frache, F. Hilt, R. Maurau, P. 386.
Choquet, Plasma Process. Polym. 2013, 10, 250. [65] M. R. Alexander, R. D. Short, F. R. Jones, W. Michaeli, C. J.
[56] E. Vassallo, A. Cremona, L. Laguardia, E. Mesto, Surf. Coat. Blomfield, Appl. Surf. Sci. 1999, 137, 179.
Technol. 2006, 200, 3035. [66] J. Chen, M. D. Soucek, Eur. Polym. J. 2003, 39, 505.
[57] M. R. Tchoquessi Diodjo, L. Belec, E. Aragon, Y. Joliff, L. Lanarde, [67] B. Arkles, J. R. Steinmetz, J. Zazyczny, P. Mehta, In Siloxanes
F. X. Perrin, ACS Appl. Mater. Interfaces 2013, 5, 6751. and Other Coupling Agent, K. L. Mittal, Ed., VSP, Utrecht, The
[58] B. Stuart, Infrared Spectroscopy, Fundamentals and Applica- Netherland 1992, 91.
tion, John Wiley & Sons, Ltd., 2004, 71. [68] K. Ru€ gner, R. Reuter, D. Ellerweg, T. de los Arcos, A. von
[59] M. K. Harun, S. B. Lyon, J. A. Marsh, Prog. Org. Coat. 2003, 46, 21. Keudell, J. Benedikt, Plasma Process. Polym. 2013, 10, 1061.
[60] N. Graf, E. Yegen, T. Gross, A. Lippitz, W. Weigel, S. Krakert, [69] S. Choi, A. P. Janisse, C. Liu, E. P. Douglas, J. Polym. Sci., Part A:
A. Terfort, Z. E. S. Unger, Surf. Sci. 2009, 603, 2849. Polym. Chem. 2011, 49, 4650.
[61] V. H. V. Sarmento, M. G. Schiavetto, P. Hammer, A. V. [70] G. Van Assche, B. Van Mele, Polymer 2002, 43, 4605.
Benedetti, C. S. Fugivara, P. H. Suegama, S. H. Pulcinelli, C. V. [71] L. Wu, S. V. Hoa, M. Ton-That, J. Appl. Polym. Sci. 2004, 92,
Santilli, Surf. Coat. Tech. 2010, 204, 2689. 2261.

Plasma Process. Polym. 2014, DOI: 10.1002/ppap.201400106

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 15
R

Early View Publication; these are NOT the final page numbers, use DOI for citation !!