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Applied Surface Science 419 (2017) 650669

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Applied Surface Science


journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Corrosion protection properties and interfacial adhesion mechanism


of an epoxy/polyamide coating applied on the steel surface decorated
with cerium oxide nanolm: Complementary experimental,
molecular dynamics (MD) and rst principle quantum mechanics
(QM) simulation methods
Ghasem Bahlakeh a, , Bahram Ramezanzadeh b, , Mohammad Reza Saeb c ,
Herman Terryn d , Mehdi Ghaffari e
a
Department of Engineering and Technology, Golestan University, Aliabad Katool, Iran
b
Department of Surface Coatings and Corrosion, Institute for Color Science and Technology, P.O. Box 16765-654, Tehran, Iran
c
Department of Resins and Additives, Institute for Color Science and Technology, P.O. Box 16765-654, Tehran, Iran
d
Department of Materials and Chemistry, Vrije Universiteit Brussel, Pleinlaan 2, B-1050 Brussels, Belgium
e
Polymer Group, Faculty of Technical and Engineering, Golestan University, P.O. Box 155, Gorgan, Golestan, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The effect of cerium oxide treatment on the corrosion protection properties and interfacial interaction of
Received 6 March 2017 steel/epoxy was studied by electrochemical impedance spectroscopy, (EIS) classical molecular dynamics
Received in revised form 23 April 2017 (MD) and rst principle quantum mechanics (QM) simulation methods X-ray photoelectron spectroscopy
Accepted 8 May 2017
(XPS) was used to verify the chemical composition of the Ce lm deposited on the steel. To probe the role
Available online 10 May 2017
of the curing agent in epoxy adsorption, computations were compared for an epoxy, aminoamide and
aminoamide modied epoxy. Moreover, to study the inuence of water on interfacial interactions the MD
Keywords:
simulations were executed for poly (aminoamide)-cured epoxy resin in contact with the different crystal-
Cerium oxide nanolm
Epoxy coating
lographic cerium dioxide (ceria, CeO2 ) surfaces including (100), (110), and (111) in the presence of water
Interfacial adhesion molecules. It was found that aminoamide-cured epoxy material was strongly adhered to all types of CeO2
Corrosion resistance substrates, so that binding to ceria surfaces followed the decreasing order CeO2 (111) > CeO2 (100) > CeO2
EIS (110) in both dry and wet environments. Calculation of interaction energies noticed an enhanced adhe-
X-ray photoelectron spectroscopy sion to metal surface due to aminoamide curing of epoxy resin; where facets (100) and (111) revealed
Molecular dynamics (MD) electrostatic and Lewis acid-base interactions, while an additional hydrogen bonding interaction was
Quantum mechanics (QM) identied for CeO2 (110). Overall, MD simulations suggested decrement of adhesion to CeO2 in wet envi-
ronment compared to dry conditions. Additionally, contact angle, pull-off test, cathodic delamination
and salt spray analyses were used to conrm the simulation results. The experimental results in line with
modeling results revealed that Ce layer deposited on steel enhanced substrate surface free energy, work
of adhesion, and interfacial adhesion strength of the epoxy coating. Furthermore, decrement of adhesion
of epoxy to CeO2 in presence of water was afrmed by experimental results. EIS results revealed remark-
able enhancement of the corrosion resistance of epoxy coating applied on the steel specimens treated by
cerium oxide.
2017 Elsevier B.V. All rights reserved.

1. Introduction

From an atomic standpoint, the microscopic space in between


an organic coating and a metal substrate resembles a local plaza
for exchange of electrons. Oxygen bearing functional groups, i.e.,
hydroxyl and epoxide, are sellers of electron pairs, electron donor. By
Corresponding authors.
contrast, metal ions present on the metal substrate play the role of
E-mail addresses: Gh.Bahlakeh@gu.ac.ir (G. Bahlakeh),
ramezanzadeh-bh@icrc.ac.ir, ramezanzadeh@aut.ac.ir (B. Ramezanzadeh).
clientele, electron acceptor, due to their free d orbitals [14]. In such

http://dx.doi.org/10.1016/j.apsusc.2017.05.070
0169-4332/ 2017 Elsevier B.V. All rights reserved.
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 651

a crowded market, electron donor and acceptor sites in the organic Table 1
Chemical composition of steel sheet.
coating and metal substrate are liable to formation of coordina-
tion bonds. Moreover, the adhesion strength in the metal/polymer Elements Fe C P Mn Si Cr Ni
interfacial layer depends to the dryness of interface. The presence Composition (wt%) 93.9 0.2 1.2 1.1 1 0.7 1.7
of water molecules can decrease the interfacial adhesion due to
excessive interactions with chemical, polar and hydrogen bonds;
thereby deteriorates desired contact between polymer and metal Their study proved that the degree of adhesion considerably weak-
or metal-oxide layer [5,6]. Furthermore, water molecules trapped ened with an increase in moisture content. They also found that
at the coating/metal interface produce an osmotic pressure leading substantial contribution to adhesion comes from the interaction
to disbondment of organic coating with the substrate [5]. Pretreat- between epoxide oxygen and surface Al atoms. Armed with DFT
ment of the metal substrate by inorganic coatings i.e., chromates calculations, Lee et al. [19] investigated the mechanism of DGEBA
and phosphates is the commonly used route to overcome inade- epoxy resin adhesion to iron surface, Fe (100) and reported that
quate adhesion resulting from water accumulation at the interface epoxy resin with parallel orientation was the most stable structure
[7,8]. Implementation of coatings based on rare earth elements above Fe substrate.
has recently recognized as the most promising echo-friendly tech- In experimental point of view, several techniques have been
nique. Cerium (Ce), and lanthanum (La) are some examples among utilized to study the organic coating/metal interface. X-ray pho-
this family of elements with extraordinary performance when toelectron spectroscopy (XPS) has been used to obtain quantitative
used for chemical treatment of metals before applying organic information about the adsorbates [20,21]. Furthermore, pull-
coatings [9,10]. Exceptionally, however, chemical treatment by off test can provide information about the interaction strength
cerium based elements revealed very high degree of success in between the coating and metal [22,23] as well as delamination.
improvement of metal/organic coating adhesion thanks to forma- Additionally, to obtain morphological and chemical information of
tion of Ce lm composed of cerium oxides/hydroxide, mainly in surface, SEM and contact angle have been utilized.
the form of Ce2 O3 or CeO2 [810]. Although many researchers have In a recent work, we have theoretically studied the interfacial
been attempted to explore the adhesion mechanism at the cerium bonding properties of an epoxy resin on the steel substrate by
oxideorganic coating interfacial zone to nd the interdependence means of DFT calculations together with MD simulations [11]. The
between interfacial physicochemical characteristics and adhesion results uncovered the crucial role of epoxy information of coat-
performance of metalorganic coating joints under dry and wet ing lms over the carbon steel surfaces of different oxide types.
conditions, providing a direct view of the interface considering In the current work, the impact of cerium (Ce) chemical treat-
molecular/atomic level interactions has remained as an awkward ment on the corrosion resistance and adhesion characteristics of
situation [11]. epoxy coating applied on steel surface has been studied combin-
Computational techniques involving rst principle quantum ing the theoretical calculation and experimental analyses. First,
mechanics (QM) calculations and atomistic molecular dynam- morphology and chemical structure of Ce-treated samples were
ics (MD) simulations have been proven to be powerful tools in characterized by X-ray photoelectron spectroscopy (XPS), scanning
unraveling the underlying interactions associated with the inter- electron microscopy (SEM) and contact angle measurements. Then,
face between organic coating and metal oxide substrate [11]. in order to explore the vital role of Ce lm on the polymer/steel
Through applying such computations, it is possible to nd qual- interfacial bonding, and to elucidate detailed microscopic view of
itative/quantitative outlook regarding the coating adhesion to how solvent diffused to the interface affects the strength of coating
metallic substrate. It has been shown that electronic structure cal- binding, ab initio QM calculations and atomistic MD simulations
culations based on QM methods, e.g. density functional theory were executed. Theoretical explorations allowed to get detailed
(DFT), are helpful to derive basic information about the elec- electronic/atomic-scale insights into the interface. The computa-
tronic features of adsorbing molecules[11,12]. For instance, it tions based on QM prociently uncovered through a wide-ranging
has been established that adsorption sites and electron distribu- molecular window some new and useful details on the electronic
tion within the molecule can manipulate the coating behavior properties, i.e., partial atomic charge and molecular orbital dis-
with respect to the substrate [11,13,14]. Unlike QM computations, tribution of epoxy molecules under the inuence of chemical
which consider the interactions at electronic scales and thus are interactions with oxide substrate. Comparison of the results under
restricted to smaller length scales, classical MD simulations utiliz- humid and dry circumstances delivered for the rst time molecular-
ing potential functions for inter/intra-molecular interactions could scale patterns/information on the situation of interfacial adhesion
be applied for more realistic scales of coating-metal oxide com- under the inuence of cerium oxide deposition, which is of premier
plex. Consequently, by making use of atomistic MD simulations, importance from application point of view. Moreover, experimen-
one can reliably mimic the experimental conditions, particularly tal results due to pull-off, salt spray, and cathodic delamination
the situations relevant to the humid environments [12,15,16]. MD tests were repeated for samples conditioned at different dry and
simulation approaches directed towards the coating-metal oxide wet conditions to valorization of the computational results.
interface are capable of providing valuable data on orientation and
stable conguration of the adsorbed molecules, the binding extent 2. Experimental
or equivalently the interaction energy [11,12].
Computational methods have been occasionally utilized to get 2.1. Materials and sample preparation
an in-depth understanding of polymeric coating-metallic substrate
systems [17]. Kisin et al. [18] theoretically probed the work of Cerium nitrate, hydrogen peroxide, sodium hydroxide, and
adhesion for acrylonitrile-butadiene-styrene (ABS) copolymer at its hydrochloric acid reagents used for Ce solution preparation were
interface with copper oxide, and concluded that increase of inter- all purchased from Aldrich Co. (Germany) and used without further
facial oxygen content promotes the work of adhesion. Semoto et al. purication. Steel panels (100 mm 80 mm 2 mm) with the com-
[13] reported that the hydroxyl (-OH) groups in the epoxy resin are position given in Table 1 were prepared from Foolad Mobarakeh
the main interaction sites for coating adhesion to the surface of alu- Co. (Iran). Epoxy resin (Araldite GZ 707175) with solid content
minum oxide. Moreover, Ogata and Takahashi [14] reported on the of 7476%, epoxy value of 0.14920.1666 Eq./100 g, and density of
interaction of diglycidyl ether of bisphenol A (DGEBA) epoxy resin 1.08 g cm3 was provided by Saman Co. (Iran), while aminoamide
with oxidized aluminum surface under different hydration levels. hardener (CRAYAMID 115) was provided by Arkema Co.
652 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

The Ce solution was composed of Ce(NO3 )2 (2 g/L), 5 mL/L (H2 O2 , monomer of poly (aminoamide) (m = 1 in Fig. 1B), was chosen for
30 wt.%) and 11.3 mL/L (HCl, 37 wt.%). The NaOH solution (5 wt.%) both QM calculations and MD simulations, inspired from a pre-
was used as in pH regulator for Ce solution. The steel panels were vious study on epoxy coating adsorption process on bare steel
immersed in the Ce solution with the pH and temperature of 3.0 substrates [11]. During the curing reaction of bisphenol A epoxy
and 25 C, respectively, for 5 min. Prior to surface treatment, steel resin substances with nitrogenous hardener compounds based on
specimens were all abraded with emery papers of 600, 800 and poly (aminoamide), active groups in epoxy resin, i.e., two epox-
1200 followed by degreasing with acetone and rinsed with distilled ide rings and backbone hydroxyl (OH) groups shown in Fig. 1A,
water. The Ce treated samples were then rinsed with deionized could react with both amide and amine functional groups in the
water and dried before applying epoxy coating. curing agent ( NH and NH2 in Fig. 1B, respectively). As a result,
Epoxy/polyamide coating with mixing ratio of 1.3:1 w/w was there were different states for the curing reactions. Our previous
prepared and applied on the bare steel and Ce-treated panels. The computational investigations have proven that the type of cova-
coated samples were kept in room temperature for 24 h and sub- lent linkages (curing bonds) created between epoxy resin and its
stantially transferred into an oven at temperature of 100 C for full curing agent affects the potential interfacial interactions of the
curing. The thickness of the coatings after drying was ca. 70 m. cured epoxy compound with carbon steel (represented by iron
oxides) substrates [11]. Hence, in order to examine the effects
2.2. Characterization contributed from epoxy-hardener bonding type on its strength of
adhesion to Ce treated carbon steel, we considered three kinds of
The surface morphology and composition of the Ce lm precip- covalent bonding between the aminoamide hardener and epoxy
itated on the steel panels were studied by the XPS and SEM/EDS resin. First, the amide N atom was bonded to the end C atom in
analyses. Elemental surface analysis by XPS was performed on an epoxide ring shown in Fig. 1C (denoted as linkage 1). In the sec-
8025-BecTec (AlK radiation source) to probe the composition of ond case, the aminoamide monomer was linked to epoxide C atom
various Ce oxide/hydroxide layers deposited on the steel substrate. from its amine N atom (linkage 2 in Fig. 1D). Third, as in Fig. 1E,
In addition, the morphology and microstructure of the Ce layer the amine N atom of the hardener was connected to hydroxyl
was investigated by LEO 1455VP Zeiss model SEM equipped with O atom in the backbone of epoxy resin (linkage 3). Furthermore,
EDS analyzer. The surface roughness was measured through AFM to comprehensively assess the crucial role played by aminoamide
analysis, Dualscope DS 95-200, DME, Denmark. hardener in aminoamide-modied epoxy coating adhesion onto
The sensitivity of interfacial adhesion between epoxy coating cerium covered carbon steel adsorbents, atomistic MD simulations
and steel to Ce treatment was evaluated before and after expo- were executed for aminoamide fragment, and unmodied epoxy
sure to corrosive electrolytes. Cathodic delamination, salt spray resin (i.e., bisphenol A epoxy without aminoamide moiety) as well.
and pull-off tests were carried out in this regard. The adhesion In an experimental effort, Wielant et al. employed a similar proce-
properties of the coatings were carried out by Posi test-pull off dure to study the function of alcohol groups in adsorption of epoxy
adhesion tester (DEFELSKO, USA). The effect of Ce lm on the adhe- compounds on iron oxide surfaces [24].
sion strength loss of epoxy coating was studied in a corrosive media
by salt spray test. For this purpose, an articial scratch was pro- 2.3.2. QM optimization of adsorbate structures
duced on the coated samples followed by transferring them into a Before performing MD simulations, the molecular structures of
salt spray chamber. The atomized 5.0 wt.% NaCl solution was con- the aminoamide monomer and uncured epoxy resin as well as all
tinuously sprayed on the samples for 600 h to analyze at the end three differently cured epoxy resins were optimized using rst
of test the corrosion products deposited nearby the scratch and principle electronic structure calculations. These electronic scale
their development beneath the coating. The effect of Ce layer on computations based on ab initio quantum mechanics were specif-
the resistance of epoxy coating against cathodic delamination was ically carried out to predict the active sites in both epoxy and
also probed experimentally. To this end, an articial defect (5 mm hardener molecules, and to attain fundamental insights regarding
in diameter) was produced on the coated samples. Then samples the role of hardener agents in adsorption characteristics of DGEBA
immersed in 3.5 wt.% NaCl solution (25 C) and a constant polariza- coatings. To this purpose, the geometries of aminoamide fragment
tion potential of 2.5 V (with respect to a saturated Calomel reference and the uncured/cured epoxy resins were rst optimized using
electrode) was applied (by a power DC (direct current) supplier) to Hartree-Fock (HF) theory employing 6-31G** split valence basis
the samples for 24 h. All the experiments were repeated three times sets [25]. The structures obtained from HF calculations were fur-
for the sake of reliability of measurements. An Ivium Compactstat ther optimized by using density functional theory (DFT) [26,27]
(Netherlands) was utilized to evaluate the inuence of steel surface using B3LYP hybrid functional initially with the use of 6-31G**
decoration with cerium oxide on the corrosion protection proper- basis set and then with larger basis functions of 6-311G** [2830].
ties of an epoxy coating. The test was carried out at open circuit All these geometry optimizations were done in gas phase with-
potential in a three electrode cell consisting of Ag/AgCl as reference, out applying any restrictions. These successive electronic structure
platinum as counter and coated sample as working electrodes. The computations were carried out with the objective of fully equi-
measurements were done in the frequency range of 10 kHz10 mHz librating the investigated compounds. The nal global minimum
choosing a 10 mV perturbation. energy structures derived from DFT calculations at B3LYP/6-311G**
level were used to determine the partial atomic charges by making
2.3. Computational details use of ChelpG method [31], and natural bond orbital (NBO) theory
[32]. All QM calculations were executed by the use of Gaussian 09
2.3.1. Adsorbate molecules software [33].
In this work, the poly (diglycidyl ether of bisphenol A) (DGEBA)
epoxy resin was selected as organic coating materials for theo- 2.3.3. Building cerium dioxide (CeO2 ) surfaces
retical investigations. In addition, as mentioned before, the curing As mentioned before, in the second part of this paper, it was
agent used for epoxy resin was poly (aminoamide) molecule. The intended to theoretically examine the adhesion and protective
chemical structures of the epoxy resin and hardener are illustrated layer formation properties of epoxy resin on the Ce covered carbon
in Fig. 1. To determine how the hardened epoxy resin behaves on steel substrates. Consequently, it is essential to evaluate the adsorp-
cerium treated carbon steel substrates, a single epoxy resin chain tion phenomenon of epoxy compound on the cerium conversion
with one repeating unit (n = 1 in Fig. 1A), which was cured by one layer. According to our experimental characterizations (which will
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 653

Fig. 1. Molecular structures of (A) poly (diglycidyl ether of bisphenol A) (DGEBA) epoxy resin, (B) poly (aminoamide), and (C)-(E) different aminoamide-cured epoxy resin.

Fig. 2. Unit cell of cerium dioxide CeO2 crystal, and constructed simulation surfaces.

be discussed later), it was observed that the Ce lm precipitated been extensively investigated in prior experimental and theoret-
on the steel sheets mostly consisted of Ce (IV) cations. Hence, the ical studies of adsorption of various small molecules onto ceria,
dioxide type of cerium, CeO2 (called ceria), was chosen to be repre- as they are the low energy surfaces of ceria [3439]. It has been
sentative of the Ce conversion coating. In order to comprehensively demonstrated that the stability of these ceria surfaces decreases
assess the adsorption ability of aminoamide-hardened bisphenol in the order of (111) > (110) > (100) [34,40]. These surfaces were
A epoxy resin materials, three different crystallographic planes of created by cleaving the unit cell of CeO2 along the corresponding
CeO2 crystals including (100), (110) and (111) were chosen for MD facets using Surface builder module available in Materials Stu-
simulations. These oxide surfaces, in particular the (111) one, have dio software (version 6) [41]. The molecular structure for CeO2
654 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

unit cell is displayed in Fig. 2. The unit cell for crystalline CeO2 integration algorithm was applied to solve the Newtons equa-
materials has face-centered cubic (uorite) structure with space tion of motion with integration time step of 1 fs (1015 s) [46]. The
group of FM3 M, and lattice constants of a = b = c = 5.411 , and operational temperature was monitored via Andersen thermostat.
= = = 90 . The thickness of all three CeO2 surfaces was set to be During simulations, all Ce and O atoms in cerium dioxide substrates,
greater than 13 . Then, the constructed surfaces of cerium oxide and water molecules in upper solvent layer constructed for aqueous
were replicated in x and y directions so as to increase the surface phase simulations were kept frozen.
area of ceria substrates. Afterwards, a large vacuum space of 50
was placed along z direction perpendicular to each CeO2 surface. 2.3.5. Adsorbate interaction energy
The presence of vacuum space limits epoxy coating molecules to In order to quantitatively evaluate the adhesion strength
be able to interact with only one side of considered cerium oxide of aminoamide-cured epoxy resin materials on cerium oxide
substrates. The dimension of constructed simulation cells for CeO2 substrates, their binding afnities towards chosen CeO2 sur-
(100), (110), and (111) substrates were as 49.74 49.74 64.88 faces were quantied via parameter of interaction (or binding)
()3 , 48.70 49.74 63.40 ()3 , and 49.74 49.74 63.27 ()3 , energy Ebinding . This is a valuable quantity to examine how the
respectively. aminoamide hardening of epoxy resin inuences its adsorption
extent compared to unmodied state. For this purpose, nal struc-
2.3.4. Molecular dynamics simulations tures obtained from MD simulation of each adsorbing molecules
For MD simulations, the geometry-optimized structures of each were used to compute the interfacial Ebinding between adhesives
adsorbate molecule resulted from DFT studies (i.e., aminoamide, and different crystallographic surfaces of cerium dioxide according
uncured epoxy resin, and aminoamide-cured epoxy resin contain- to the following formula:
ing amide N-epoxide C covalent bonding) were placed above all
three crystallographic CeO2 surfaces of (100), (110) and (111) with- Ebinding = Eadsorbate/surface (Eadsorbate + Esurface ) (1)
out introducing any water molecules into simulation cells. Such
Where Eadsorbate/surface represents the potential energy of whole
setup represents the simulations of interfacial system under dry
simulation cell (i.e., adsorbate molecule plus CeO2 surface), and
conditions (i.e. gas phase). The adsorbate molecules were initially
Eadsorbate and Esurface are the potential energy of the isolated
positioned on cerium oxide substrates so that their initial distance
adsorbate, and the CeO2 surface without adsorbate molecule,
with respect to the highest atomic layer of substrate was set to
respectively.
be higher than 15 . Additionally, in order to get fully equilibrated
CeO2 -adsorbate interface independent of initial molecular orien-
tation, all adsorbing molecules were put with parallel orientation 3. Results and discussion
relative to all cerium dioxide surfaces.
It is well known that the existence of water above the metal 3.1. Surface characterization of Ce treated samples
surface can decreases the adhesion strength of coating materials.
To mimic these conditions and to shed light on how the adsorbed The chemical composition and microstructure of the Ce lm
water weakens the interfacial adhesion between metal substrate deposited on the steel sheets were evaluated by XPS (Fig. 3) and
and coating, MD simulations were also conducted under wet condi- SEM (Fig. 4) analyses. The XPS survey spectrum (Fig. 3) shows that
tions (i.e. aqueous phase) for aminoamide-cured epoxy resin. In this the Ce layer is composed of the species containing C, O, Ce and
case, the nal ceria-modied epoxy snapshot elucidated from sim- Fe. The type and intensity of various components existed in the Ce
ulations in dry environment was used as input structure. A solvent layer can be understood from deconvolution of the Ce 3d 3/2 sig-
slab of thickness about 10 , which contains 800 H2 O molecules, nal into four Gaussiane Lorentzian peaks at binding energy range
was rst built using Amorphous cell module, and then placed over of 897910 eV [51,52]. From the results the Ce layer is composed
each nal structure by means of Layer builder module in Materials of the two forms of Ce(IV) and Ce(III). However, the intensity of
Studio software [41]. These solvent molecules inserted into the cell the Ce(IV) is more intensive that Ce(III). This is an indicative of the
were considered as two layers: a lower layer with dissolved epoxy presence of CeO2 on the steel surface more than other forms of Ce
resin adjacent to CeO2 substrates, and an upper layer which con- hydroxide/oxide. From the SEM micrographs (Fig. 4) it is obvious
tains only water molecules (about 350 H2 O). The pure liquid layer that a crack free Ce lm, composed of the Ce oxide/hydroxide, uni-
was employed to act as a wall to solvent/epoxy layer. formly covered the steel surface and provided a rough surface with
Among the studied cerium oxide surfaces the surface that nano-metric scale roughness.
yielded the strongest interaction with epoxy resin cured via amide
N-epoxide C bonding (linkage 1) was recognized. This surface was 3.2. MD and QM simulation results
subsequently utilized to probe the adhesion behavior of hardened
epoxy resin modied by amine N-epoxide C and amine N-hydroxyl Here, we initially present the simulation results related to
O linkages. MD simulations of this epoxy resin with other curing MD simulations performed under dry conditions. Fig. 5 indicates
bonds were also carried out in both dry and wet environments. the initial input cells and the corresponding nal congurations
All prepared interface systems made from crystalline CeO2 obtained at the end of 500 ps MD simulations for aminoamide
adsorbents and adsorbate molecules were minimized with the use curing agent (a, a ), and untreated epoxy resin (b, b ) as well as
of Smart minimizer, implemented in Materials Studio software aminoamide-treated epoxy resin molecules (c, c ) on the CeO2
[41]. Subsequently, the minimized simulation cells were subjected (100) substrate. On comparing the nal structures with respective
to a 500 ps MD simulation, which was executed in NVT ensemble at prepared initial ones, it is apparent that all adsorbate molecules
room temperature to bring the simulation cells to the equilibrium approached the surface of CeO2 (100) adsorbent, and nally equi-
condition. The potential energy of simulation system was expressed librated in vicinity of CeO2 (100) metal oxide layer. It is worth to
by making use of COMPASS (condensed-phase optimized molecu- mention that when MD simulations for each adsorbate-CeO2 (100)
lar potentials for atomistic simulation studies) force eld [42,43], interface system were continued for longer simulation times, the
as successfully employed in previous studies polymer-metal oxide adsorbed compounds remained attached to surface, and their rel-
interactions [44,45]. The van der Waals (vdW) and electrostatic ative distance with respect to surface showed no variation. This
non-bonded interactions were computed with the use of atom- suggests the stabilized adsorption of aminoamide fragment, and
based cutoff and Ewald methods, respectively. The velocity Verlet unmodied and modied epoxy resin on the crystallographic facet
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 655

Fig. 3. (a) XPS overall survey, (b) high resolution deconvoluted Ce 3 d3/2 signal and (c) EDS results from Ce treated sample.

Fig. 4. SEM micrographs and contact angle measurement results for the bare steel and Ce treated samples.
656 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

Fig. 5. The initial and nal structure of CeO2 (100) surface interacting with (a, a ) aminoamide group, (b, b ) untreated epoxy resin, and (c, c ) aminoamide-treated epoxy
resin molecules.

(100) in cerium oxide materials. Such a stable localization of hard- the aminoamide hardener agent and both unmodied and modi-
ener molecule as well as pristine and hardened epoxy coating ed bisphenol A epoxy resin are strongly attracted by facet (110) in
compounds adjacent to cerium oxide surface is reective of their crystalline cerium dioxide molecules. It is also found that similar to
strong afnity to adsorb on CeO2 (100) substrate. In addition, as the facet (100), the skeleton of adhered molecules is almost parallel rel-
ultimate snapshots show, all three considered adsorbates adhered ative to oxide slab (110). The magnitude of molecular attachment
to substrate with their molecular plane parallel to surface. The level to CeO2 (110) substrate was quantied by assessing the energy of
of adhesion of the investigated adhesives was analyzed by calculat- binding for each of the studied adhesives. The interaction energies
ing the interaction energy between each adsorbate molecule and are predicted as 129.82, 152.50, and 203.28 kcal/mol, respec-
the plane (100) in CeO2 oxide. The simulated interaction energy tively, for aminoamide, and uncured and aminoamide-cured epoxy
values for attached aminoamide, DGEBA epoxy and aminoamide- resin. Further, the computed Ebinding of negative value quantita-
treated DGEBA epoxy resin with CeO2 (100) adsorbent amount to tively verify that hardener group and uncured/cured epoxy have
208.10, 249.97, and 400.52 kcal/mol, respectively. The calcu- strong afnity to tightly bound to oxide slab of (110) in inorganic
lated negative Ebinding values quantitatively conrm the binding cerium oxide adsorbents. The enhanced binding energy of function-
capability of aminoamide and uncured/cured epoxy to oxide slab alized epoxy resin in comparison with untreated sample reveals
of CeO2 (100). that aminoamide addition to epoxy resin favored its adsorption
Existence of a signicant Ebinding for aminoamide based adsor- over surface of CeO2 (110). According to these results, it may be
bate declares its potentiality to be applied as a hardener, and to deduced that further curing of epoxy resin via covalent linking
improve the interfacial bonding properties of cured epoxy coat- of aminoamide groups to the other active sites (i.e., the epoxide
ings. From the binding energy results for the uncured bisphenol A ring and hydroxyl group) could signicantly increase the intensity
epoxy resin and the aminoamide-hardened one, it can be seen that of adhesion to metallic surface. Additionally, when the difference
the Ebinding for aminoamide-treated epoxy resin is considerably between the estimated Ebinding for neat and treated epoxy are
higher than that for untreated one. Such an observation implies the compared in two CeO2 (100) and (110) surfaces, it is noticed that
fact that modication of epoxy resin via aminoamide curing group the aminoamide curing enhanced the Ebinding of cured epoxy with
intensies the adhesion degree of epoxy resin based coating, which CeO2 (100) to a larger extent than with CeO2 (110). One reason for
itself enhances the interaction energy for cured epoxy/CeO2 (100) such an observation may be the stronger interaction of aminoamide
complex. with layer (100) compared to layer (110).
The prepared input cells along with respective equilibrated For the CeO2 (111) substrate, the snapshots before and after
snapshots derived from NVT MD simulations of adsorption exper- molecular dynamics simulations are depicted in Fig. 7 for each
iments on cerium oxide surface (110) are illustrated in Fig. 6 for organic adsorbate. As shown, analogous to ultimate cells for the
aminoamide functionality as well as unmodied/modied epoxy cases of (100) and (110) planes, all three adsorbates moved towards
resin. The simulation cells achieved after MD simulations demon- the cerium dioxide surface (111), and eventually localized proxim-
strate that selected organic adsorbates attached to topmost layer of ity to cerium oxide slab. This visual nding proposes the ability
the CeO2 (110) substrate, and the adsorbate-adsorbent distance sig- of aminoamide and uncured/cured DGEBA epoxy resin to strongly
nicantly decreased. The observation of reduced distance suggests bind to facet (111) of cerium dioxide. The extent of adhesion was
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 657

Fig. 6. The initial and nal structure of CeO2 (110) surface interacting with (a, a ) aminoamide group, (b, b ) untreated epoxy resin, and (c, c ) aminoamide-treated epoxy
resin molecules.

Fig. 7. The initial and nal structure of CeO2 (111) surface interacting with (a, a ) aminoamide group, (b, b ) untreated epoxy resin, and (c, c ) aminoamide-treated epoxy
resin molecules.

probed through calculating the interaction energy. The Ebinding resin, and hardened epoxy resin. The predicted data demonstrate
for adsorbed molecules are computed as 397.92, 614.00, and that the functionalizing the epoxy resin by aminoamide resulted
868.76 kcal/mol, respectively, for aminoamide, pristine epoxy in substantially strengthened adsorption onto CeO2 (111) adsor-
658 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

bent, an observation due to the strong intermolecular interactions as well (denoted as Oi and Ni). Fig. 8 gives the results for pro-
present between aminoamide hardener and slab (111) of cerium les of concentration. From this gure, it is clear that compared
dioxide. to initial concentrations appeared at a distance of approximately
In summary, the visualized nal snapshots and the calculated 20 from surface, both of the Of and Nf concentrations in equili-
Ebinding for uncured as well as aminoamide-cured epoxy resin brated congurations of cured epoxy resin occurred at much closer
materials cooperatively suggest that both the neat and the hard- distances from all ceria substrates. This observation again demon-
ened epoxy resins are capable of binding to all three investigated strates that the cured epoxy resin tightly attached to characterized
CeO2 (100), (110), and (111) surfaces. This feature allows the adsor- cerium oxide planes. These atomic scale insights evidence the fact
bates to form coating on cerium oxide conversion layer. Moreover, the poly (aminoamide)-cured epoxy resin networks could adsorb
on the basis of the aforementioned Ebinding values, conjugat- on different CeO2 surfaces, enabling them to form effective coating
ing aminoamide fragment to epoxy resin brings about stronger layers over crystalline CeO2 metal oxide.
adhesion to all three crystallographic facets of cerium dioxide, It is well known that the strength of adhesion and the adsorbed
because of the involvement of hardener molecules in interfacial geometry of all adsorbates on cerium oxides are correlated with the
interactions with substrate. The Ebinding of aminoamide as well as intermolecular interactions present at the interface between the
pristine and hardened epoxy resin followed the decreasing order of surface atoms and the active sites in cured epoxy chains. Such inter-
CeO2 (111) > CeO2 (100) > CeO2 (110), revealing that the adhesives facial forces manipulate the phenomenon of DGEBA-based epoxy
are most strongly pulled by (111) plane in CeO2 conversion layer resin adsorption onto the substrate of CeO2 . Therefore, in order
precipitated on steel surface. Such an observed trend in binding to get deeper insights into the molecular interactions governing
energy of adsorbates is assigned to the existence of higher num- the adhesion behavior of epoxy resin above cerium dioxide layers,
ber of Ce atoms in top layers of cerium dioxide (111) structure, the nal congurations of cured epoxy resin adhered to considered
which induces greater surface charges. This characteristic in turn metallic surfaces were further examined. Fig. 9 provides the pic-
enhances the electrostatic interactions between negatively charged tures related to side and top view of the aminoamide-cured epoxy
centers in adsorbing molecules and surface cerium atoms. This will resin equilibrated close to all three metal oxide surfaces of CeO2
be discussed in more details later. (100), (110), and (111). Panels (a)-(c) indicate that treated epoxy
In a recent computational QM/MD work, we have studied the resin adsorbed to surfaces with its skeleton parallel to oxide slabs.
intermolecular interactions between the poly (aminoamide)-cured This preferred at orientation against the surface, which happens as
DGEBA epoxy resin and carbon steel surfaces. The steel layers a result of presence of active centers along the epoxy chain, allows
were represented by three iron oxides, FeO (100), Fe2 O3 (110), the epoxy molecules to maximize their surface coverage properties.
and Fe3 O4 (100). The aminoamide-cured epoxy resin showed the This describes best the enhanced coating lm formation ability of
Ebinding values of 113.6, 1035.9, and 304.4 kcal/mol with epoxy compounds over protective layers of ceria on carbon steel. In
FeO (100), Fe2 O3 (110), and Fe3 O4 (100) surfaces, respectively. addition, from the side view it can be seen that O and N heteroatoms
When the interaction energies of cured epoxy with selected sur- pointed downward, particularly, in cases of CeO2 (100) and (111),
faces of CeO2 are compared with the corresponding data for iron an observation due to the electrostatic interactions of these reactive
oxide surfaces, it can be found that Ebinding of cured epoxy resin centers with positively charged surface Ce sites. As shown, in con-
with two CeO2 surfaces (i.e. (100) and (111)) are higher than that trast to planes of (100) and (111) which are only Ce-terminated, the
of two iron oxide substrates (i.e. FeO (100) and Fe3 O4 (100)). uppermost atomic layer in (110) facet of ceria is ended with O sites
Interestingly, the most stable surface of ceria, CeO2 (111), with as well, allowing the cured epoxy resin to participate in hydrogen
Ebinding of 868.76 kcal/mol yielded signicantly stronger inter- bonding interactions with surface. In this case, the backbone OH
actions towards epoxy compound compared to FeO (100) and Fe3 O4 as well as amine fragments formed hydrogen bonds with surface
(100) surfaces, and also its interactions were comparable to Fe2 O3 O atoms via donating their H atoms. Consequently, another inter-
(110) surface. facial bonding mechanism (i.e., hydrogen bonding) exists between
As the CeO2 (111) surface yielded the strongest interactions the epoxy resin and the CeO2 (110) molecule. The fact that NH2
towards the aminoamide-cured epoxy resin (linkage 1), it was moiety emerged as hydrogen-bonded with surface again empha-
adopted to assess the binding of cured epoxy resin containing the sizes the critical role of aminoamide hardener in strengthening the
other types of aminoamide-epoxy covalent bonding (i.e., linkages epoxy attachment to ceria lms covered the carbon steel. Also, the
2 & 3 in Fig. 1D and E). The Ebinding for the nal adsorbed epoxy panel (c) in this gure displays that all hydrogen atoms of epoxy
resin over CeO2 (111) adsorbent (not shown here) was calculated attached to CeO2 (111) adsorbent pointed away from the surface.
as 739.04 and 813.85 kcal/mol, revealing the weaker interfacial Such an observations is rationalized by the higher surface charges
binding of epoxy resin cured with amine N-epoxide C or amine N- induced by cerium atoms. It may be noted that the repetition unit
hydroxyl O in comparison with epoxy resin with amide N-epoxide for CeO2 (100) substrate is an oxygen layer followed by a cerium
C curing bond. As shown in Fig. 1C, in modied epoxy of linkage 1 one, whereas the CeO2 (111) surface is the stack of a Ce layer sand-
both NH2 groups are free, while in the other modications, one wiched between two rows of O sites (that is, three atomic O/Ce/O
of the two active amine groups are free and the other is bonded layers) [35]. As a consequence, although the highest atomic row in
to either epoxide carbon or hydroxyl oxygen. As a result, the free both the crystallographic facets of (100) and (111) is terminated
amine groups could more efciently interact with surface atoms with cerium atoms, presence of single O row in topmost unit for
compared to the amide and bonded amine groups, and thus leading plane (111) produces higher surface charges than the plane (100).
to the strongest adhesion to surface. In our previous work, it has been demonstrated that besides
The adhesion features of single molecule of aminoamide- the oxygen as well as nitrogen atoms in hardened epoxy resin, the
modied epoxy resin over CeO2 oxide layers was further benzene rings in bisphenol A moieties of epoxy behaved as reac-
quantitatively inspected through analysis of concentration proles tive sites in epoxy bonding to different iron oxide substrates [11].
along direction perpendicular to surface (i.e., z-direction). This was Further examination of adsorbed geometry of aminoamide-cured
done for oxygen and nitrogen heteroatoms in modied epoxy. The epoxy resin (Fig. 9) exhibits that the aromatic benzene rings in
proles of atomic concentration were predicted as time-averaged two bisphenol A parts of epoxy adopted parallel orientation with
values from the dynamic trajectories within the last 100 ps MD sim- respect to chosen cerium dioxide surfaces, in particular, for CeO2
ulations (denoted as Of and Nf). To better analyze the results, the O (111) surface. This kind of cured epoxy resin adhesion is attributed
as well as N concentration proles in initial cells were assessed to the Lewis acid-base (or electronic donor-acceptor) interactions
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 659

Fig. 8. Concentration proles for oxygen and nitrogen atoms in aminoamide-modied epoxy resin over (a) CeO2 (100), (b) CeO2 (110), and (c) CeO2 (111) surfaces in initial
cells (Oi and Ni) and during the last 100 ps simulations (Of and Nf).

Fig. 9. The side and top view of nal structure of aminoamide-modied epoxy resin on (a, a ) CeO2 (100), (b, b ) CeO2 (110), and (c, c ) CeO2 (111) surfaces. The intermolecular
hydrogen bonds are shown as dashed green line. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

between benzene rings in epoxy and Ce atoms in ceria. In such The empty f orbitals in Ce atoms could accept the lone pair of elec-
intermolecular interactions, electron-rich sites in adsorbate such as trons in electronegative O and N centers, and also the delocalized
nitrogen, phosphorus, oxygen, and sulfur atoms as well as aromatic electrons in benzene rings, leading to an improvement in extent
rings give their electrons to unoccupied orbitals of metallic cations of epoxy binding to different cerium dioxide substrates. From the
in oxide adsorbents [4750]. Thus, in modied epoxy-CeO2 system, closer inspection of adsorbed epoxy conguration in Fig. 9, it can
the N as well as O atoms and the benzene fragments in epoxy resin be seen that contrary to epoxy-CeO2 (111) interface where all aro-
act as Lewis bases and the Ce sites in ceria behave as Lewis acid [11]. matic rings in cured epoxy were wholly parallel relative to surface,
660 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

Table 2 whole adsorbate towards the oxide substrate, causing a at ori-


Partial atomic charges of aminoamide-modied epoxy resin determined at B3LYP/6-
entation above cerium dioxide layers. From the electronic charge
311G** level using ChelpG method. The charges in parentheses are based on NBO
theory. perspective, the stronger epoxy binding to CeO2 (111) compared
to the other slabs is ascribed to the stronger intermolecular inter-
Atom No. Linkage 1 Linkage 2 Linkage 3
actions occurred between the charged O as well as N centers and
1(N) 0.98 (0.84) 0.83 (0.86) 0.90 (0.83) surface Ce cations. Furthermore, the signicant charges carried by
2(N) 0.30 (0.51) 0.47 (0.64) 0.54 (0.64) aminoamide nitrogen atoms indeed evidence the fact that conju-
3(N) 0.93 (0.83) 0.45 (0.72) 0.65 (0.37)
gating the hardener molecule to the epoxy resin is a benet for
4(O) 0.54 (0.65) 0.50 (0.67) 0.55 (0.66)
5(O) 0.64 (0.75) 0.58 (0.75) 0.26 (0.52) adhesion features of epoxy materials over cerium dioxide coated
6(O) 0.50 (0.59) 0.34 (0.56) 0.38 (0.54) on carbon steel. It is also noted that in all three types of aminoamide
7(O) 0.39 (0.55) 0.41 (0.53) 0.43 (0.54) bonding to epoxy, unbounded amine N atom(s) are more nega-
8(O) 0.62 (0.74) 0.64 (0.71) 0.37 (0.47)
tively charged than the amide N or bonded amine N atom, implying
9(O) 0.45 (0.57) 0.40 (0.53) 0.47 (0.54)
10(O) 0.39 (0.53) 0.36 (0.54) 0.37 (0.54) the dominant contribution of unbounded amine functionality in
11(O) 0.27 (0.52) 0.26 (0.52) 0.26 (0.52) adsorption of modied epoxy to ceria layers. This in turn strongly
supports the highest binding energy of epoxy resin containing
uncured amine N atoms (i.e., linkage 1) among the differently cured
epoxy resins.
The theory of frontier molecular orbital (FMO) was employed to
further shed light on the adsorption centers responsible for binding
of aminoamide-modied epoxy resin via Lewis acid-base interac-
tions to oxidized cerium layers. Fig. 10 demonstrates the global
minimum energy structure of aminoamide-conjugated epoxy resin
(linkage 1), and the respective distribution of the highest occu-
pied molecular orbital (HOMO) and lowest unoccupied molecular
orbital (LUMO). A HOMO orbital is associated with active sites of the
greatest ability to interact with metal atoms by offering electrons
to vacant metallic orbitals. On the other side, a LUMO region in an
adsorbate represents active sites which accept electrons from lled
orbitals in surface atoms. It is well established that an adhesive
attaches to a metal oxide substrate principally via these reactive
sites. According to the graphical results for distribution of HOMO
and LUMO (Fig. 10b and c), it can be observed that the HOMO
orbitals are centered on the two aromatic benzene cycles of one
of the bisphenol A fragments and also on its neighboring O atoms,
while the LUMO ones are distributed over the C atoms of benzene
rings in the other bisphenol A moiety. These ndings for molecular
orbital distribution reveal that epoxy resin molecule could donate
the delocalized electrons in bisphenol A fragments to the low-
energy unoccupied orbitals of surface cerium atoms, and thereby
facilitate the epoxy adsorption through interactions based on the
acid-base mechanism. These electronic scale insights are in close
accordance with the visualized snapshots for adsorbed epoxy resin
with benzene rings parallel relative to crystallographic oxide sur-
.
faces (Fig. 9).
To further explore the local reactivity of coating molecule, the
some benzene rings in epoxy were rather tilted with respect to the Fukui indices (FI) were examined for all three types of investigated

other ceria adsorbents (i.e., one ring above CeO2 (110) and two rings aminoamide-cured epoxy resin [51]. The Fukui function (f ( r )) is
above CeO2 (100)). These results in line with calculated interac-
determined from the rst derivative of electron density (( r )) with
tion energies suggest that aminoamide-cured epoxy resin behaved
regards to the number of electrons (N) at constant potential (( r )):
differently upon adhesion to studied cerium dioxide surfaces.
 
The degree of epoxy attachment to ceria substrate through ( r )
interfacial bonding mechanisms (i.e., electrostatic and acid-base f(r ) = (2)
N
( r )
interactions) greatly relies upon the average density of elec-
trons (or partial charge) centered on active sites, especially the Using nite difference (FD) approximation and Hirshfeld
O as well as N atoms. The partial atomic charges of these atoms population analysis [52], the atom-condensed Fukui functions
in B3LYP/6-311G** optimized structures of aminoamide-treated
corresponding to electrophilic (f ( r )) and nucleophilic (f + ( r ))
epoxy resin were determined using both the ChelpG and NBO centers were estimated according to the following equations:
methods. The charges derived from DFT computations are tabu-   
lated in Table 2 for all three aminoamide-modied epoxy resins. f+ r = N+1 r N r (3)
The results obtained through both approaches manifest that both
heteroatoms, particularly the N atoms, possessed large negative
  
f r = N r N1 r (4)
charges. This observation points out the strong propensity of the O
(ether, hydroxyl, epoxide and amide O atoms) and N (amine and
amide) atoms to take part in interfacial interactions with CeO2 In these equations, N ( r ) is the electronic density of neutral

substrate. Interactions of such negatively-charged sites along the species, and N+1 ( r ) and N1 ( r ) are respectively representative of
treated epoxy monomer with Ce cations of vacant orbitals push the electronic densities of anionic and cationic species. Fukui func-
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 661

Fig. 10. The B3LYP/6-311G** optimized structure (a), HOMO (b) and LUMO (c) of aminoamide-modied epoxy resin adsorbate molecule [11].

Fig. 11. The optimized structure (a, b, and c), Fukui function for electrophilic attack f (a , b , and c ), and Fukui function for nucleophilic attack f+ (a , b , and c ) in epoxy
resin with different curing bonds: (a-a ) linkage 1, (b-b ) linkage 2 and (c-c ) linkage 3.
662 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

Fig. 12. The side view of nal structure of solvated aminoamide-cured epoxy resin on (a, a ) CeO2 (100), (b, b ) CeO2 (110), and (c, c ) CeO2 (111) surfaces (a-c: with water, and
a - c : without water molecules); Hydrogen bonds of cured epoxy resin with water molecules over (a ) CeO2 (100), (b ) CeO2 (110), and (c ) CeO2 (111) surfaces. Hydrogen
bonds are shown as dashed green line, and the atomic color code is: C gray, O red, N blue, and H white. (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)

tions were calculated by the use of DMol3 code, which is based on ment emerged as local reactive sties for electrophilic attack, which
DFT computations. The generalized-gradient approximation (GGA) further highlights their key role in surface binding of hardened
using Perdew-Burke-Ernzerhof (PBE) scheme [53] was applied epoxy coating. On the other side, the active regions for nucleophilic
to calculate electronic exchange-correlation term with double interaction (i.e., f+ ) centered on both bisphenol A moieties. Addi-
numeric polarization (DNP) basis set. Fig. 11 demonstrates the opti- tionally, it is visible that the graphical results for atom-centered FI
mized geometry along with Fukui functions for electrophilic and in epoxy resin with linkage 3 are more or less identical to those
nucleophilic attacks for aminoamide-modied epoxy resin with found in linkage 2, where the ether O atoms and some benzene
three distinct curing linkages. It can be seen from this gure that C atoms behaved as reactive zones for electrophilic attack. These
in modied epoxy with curing linkage 1, the f function appeared observations further declare the fact that the aminoamide hard-
over amine N and amide O atoms in aminoamide cuing agent, while ener, and the backbone ether oxygen as well as aromatic rings act
the f+ function distributed almost over bisphenol A aromatic rings. as reactive electrophilic centers in epoxy resin and thus are able
This graphical distribution of FI reects the electrophilic behavior to provide their electrons to surface electron-decient sites within
of aminoamide group in cured epoxy resin interaction with metallic donor-acceptor interactions.
surfaces. In epoxy resin containing linkage 2 (Fig. 11b-b ), the ether As the water solvent at the interface of epoxy and metal
oxygen sites together with benzene rings in one bisphenol A frag- substrate steadily leads to a reduction in coating attachment
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 663

Fig. 13. Comparison of the interaction energy of aminoamide-modied epoxy resin with different CeO2 surfaces under dry and wet conditions.

Fig. 14. Concentration proles for oxygen and nitrogen atoms in water-solvated aminoamide-modied epoxy resin over (a) CeO2 (100), (b) CeO2 (110), and (c) CeO2 (111)
surfaces during the last 100 ps simulations.

to surface, MD simulations were also executed in the presence shown in Fig. 12c, because of the electrostatic and Lewis acid-base
of water molecules. The nal snapshots for aminoamide-treated interactions with surface Ce cations, water oxygen atoms pointed
epoxy resin over each considered surface of ceria in wet environ- towards the surface of CeO2 (111).
ment are depicted in Fig. 12. In order to get better understanding Such solvent-ceria afnities inuenced the interfacial behav-
of the adsorbed epoxy conguration in aqueous solution above ior of epoxy above the cerium dioxide substrates. As displayed in
the cerium oxide, the structures without water molecules were panel (b ) in this gure, the aminoamide-conjugated epoxy resin
also visualized in this gure (parts a -c ). This gure claries that contributed in only one hydrogen bond with surface (110) in wet
the cured epoxy resin dissolved in water solvents adhered to all environment in contrast to two hydrogen bonds observed under
three CeO2 substrates under wet conditions. Water molecules also dry conditions (Fig. 9b ). The computed hydrogen bond length
demonstrated binding to ceria surfaces thanks to their interactions (2.24 ) reveals that this single hydrogen bond of dissolved epoxy
with surface Ce and O atoms. For example, water solvents emerged resin is weaker than those formed in dry medium. Furthermore, on
in interfacial hydrogen bonds by donating their H atoms to surface the basis of the ultimate conguration of solvated epoxy resin on
O atoms in CeO2 (110) (the H-bonds not shown here). In addition, as top of CeO2 (111) (shown in Fig. 12c ), it is noted that the orienta-
664 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

Fig. 15. (a) Visual performances of the aminoamide-epoxy coatings applied on the steel sample without (Blank sample) and with Ce treatment after 900 h salt spray test, (b)
the aminoamide-epoxy coating delamination rate at different exposure times and (c) pull-off test results after salt spray test.

tion of aromatic benzene rings in bisphenol A moieties considerably and solvent as revealed through hydrogen bonds of epoxy with
deviated from their planar orientation relative to surface observed surrounding H2 O molecules.
in gas phase situations. The characteristic of epoxy resin adhesion to CeO2 surface was
Owing to the presence of the hydrophilic sites in aminoamide- further quantitatively inspected by analyzing the concentration
treated epoxy resin, solvent molecules seem to have propensity for proles for O and N atoms in aqueous solution of coating. The cal-
interactions with epoxy coating. Fig. 12a c give the intermolec- culated average concentrations over each surface were provided in
ular hydrogen bonds that established between epoxy resin and its Fig. 14. Also, the concentration proles at dry conditions were pre-
surrounding water medium above each characterized ceria surface. sented for comparison. It is noted from this gure that the O and N
It is apparent from this visualization that the cured DGEBA-based concentration proles occurred at noticeably larger distances from
epoxy resin involved in hydrogen bonding interactions with neigh- the highest layer of all CeO2 surfaces in wet environment in com-
boring H2 O molecules through its hydroxyl, OH, as well as amine, parison with concentrations at dry situations. This observation once
NH2 , functionalities. This observation declares that the hardener again suggests that the presence of water molecules at the interface
agent improves the epoxy resin afnities to not only the ceria adsor- resulted in a signicant decrease in the coating attachment to Ce
bent but also the solvent molecules. lm precipitated on the carbon steel substrate.
The epoxy resin attachment to the CeO2 conversion layers in
the presence of water molecules was quantied via determining 3.3. Adhesion properties of the epoxy coating applied on the Ce
the interaction energy, Ebinding . The computed energies for dis- treated samples
solved epoxy interactions with Ce dioxide layers were plotted in
Fig. 13. The Ebinding values obtained in the absence of solvent The surface free energy is an important parameter that effec-
were also provided to simply compare the interaction levels in wet tively changes the interaction mechanisms of the epoxy coating
and dry environments. First, it can be seen that the order of for over the steel substrate. The surface free energy was evaluated
coating adhesion to three crystallographic Ce oxide surfaces under through contact angle measurements. The contact angle values of
wet conditions is the same as that found under dry situations. Sec- water on the bare and Ce treated steel samples were calculated and
ond, it is obvious that the binding energy of epoxy with all three reported in Fig. 4. In addition, the work of adhesion (Wa ) and surface
CeO2 (100), (110), and (111) surfaces decreased in wet environment free energy ( s ) values were obtained from Youngs and Neumanns
compared to dry conditions. The observation of lower Ebinding in equations (Eqs.5 and 6) [54] as dened:
the presence of water molecules implies the weakened adhesion of
solvated coating to substrate, which accords well with experimen- W a =  lv (1 + cos) (5)
tal results. The fact that solvent weakens the interfacial binding W a = 2( lv  sv ) 1/2 2
exp( lv  sv ) ] (6)
between coating molecules and substrate is assigned to two rea-
sons: (1) the coating and solvent competition to interact with metal where  is the contact angle of water,  lv and  sv are the surface ten-
oxide substrate, and (2) the afnities between epoxy resin coating sion of water and surface free energy of the substrate, respectively,
and is 0.0001247 0.000010(mJ/m2 )2 .
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 665

Fig. 16. The cathodic delamination rate after different immersion times for the aminoamide-epoxy coating applied on untreated (blank sample) and Ce treated steel samples.

Fig. 4 compares the contact angle, surface free energy and work number of physical interactions through mechanical inter-locking
of adhesion values for the bare steel and Ce treated sample. One mechanism. Second, the Ce lm noticeably increased the surface
can be observed From Fig. 4 is the noticeable increase of  s and Wa free energy and based on wetting theory the substrate wettabil-
and decrease of contact angle after Ce deposition. This is an indica- ity by the epoxy coating can be enhanced. The aminoamide-cured
tive of Ce layer capability of enhancing the surface free energy. The epoxy coating contains active adsorption sites like epoxide, ether
increase of work of adhesion reveals that Ce layer could provide and hydroxyl as well as amide and amine fragments which are
proper adhesion of epoxy coating on the substrate. To show this, able to strongly interact with surface Ce cations through electro-
the adhesion properties of epoxy coating on the bare steel and Ce static, hydrogen bonding and donor-acceptor mechanisms [11]. As
treated samples were investigated by pull-off, cathodic delamina- mentioned before, from an electronic point of view, these electron-
tion and salt spray tests. Fig. 15 compares the results obtained from rich groups can donate their electron pairs to unoccupied orbitals
these experiments. in Ce cations located at uppermost atoms layers of CeO2 surface
It is clearly observed from Fig. 15C that the pull-off strength and thereby form a coordination bond. As a result, the interfacial
of the epoxy coating applied in the Ce treated sample is notice- coordination bonds are responsible for the creation of chemical
ably higher than that of bare steel. In addition, the mechanism of interactions between the polymer coating and surface-treated steel
detachment changes from adhesive to cohesive with Ce treatment. substrate, which gives rise to an increase in adhesion strength
The observations of adhesive failure reveal that the epoxy coating [16].
interfacial adhesion was not high enough to resist against applied The dry adhesion strength values for the untreated and Ce
pull-off force. But for the Ce treated sampler the coating was not treated samples, obtained from pull-off test, were 5.8 and 6.25 MPa,
detached from the substrate and the applied pull-off forced resulted respectively. Regarding these values and the wet adhesion strength
in coating damage. These observations could clearly illustrate the values reported in Fig. 5, the adhesion loss of the epoxy coat-
role of Ce lm on the signicant improvement of epoxy coating ing applied on the untreated and Ce treated samples are 65 and
adhesion to the substrate. 25%, respectively, depicting the effectiveness of the Ce lm on
The improvement of the aminoamide-epoxy coating adhesion the prevention of epoxy coating delamination when exposed to
on the Ce treated steel can be attributed to various reasons. First, wet environment i.e., corrosive electrolyte. The signicant adhe-
deposition of Ce coating on the steel substrate increased the aver- sion loss on the untreated steel specimen clearly depicts that
age roughness (Ra ) (obtained from AFM analysis) from 65 nm for the water molecules provided stronger hydrogen bonding with poly-
untreated steel to 125 nm for the Ce treated sample. The increase of mer and surface hydroxylation of the metal oxide resulted in the
surface roughness indicates that deposition of Ce lm on the steel coating adhesion bonds destruction. However, the interactions
substrate provided greater adhesion sites and contact area for adhe- between the Ce oxides/hydroxides cannot be easily spoiled by
sion bonding with aminoamide-epoxy coating. The epoxy chains water molecules as the Ce oxides provide strong hydrogen bonds
diffuse into the nano-porosities of the substrate and provide larger with polymer which strongly supports the MD simulation ndings
666 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

Fig. 17. Bode diagrams of the aminoamide-epoxy coatings applied on the (a) untreated and (b) Ce treated samples after 7, 21 and 45 days immersion in 3.5 wt.% NaCl solution;
(c1 ) and (c2 ) equivalent electrical models; Solid lines and marker points represent the tted and experimental data, respectively.

of weakened coating adhesion to substrate in wet environments. ples oddly increases as the immersion time increases, but for the
The coating adhesion properties will be spoiled by the time when Ce treated sample the delamination diameter slightly increases. All
exposed to a wet media. Therefore, the adhesion properties can be observations demonstrate the effective role of Ce layer on preven-
indirectly probed by slat spray test (Fig. 15) and cathodic delam- tion of coating from losing its adhesion in harsh wet environments.
ination (Fig. 16), which give the amount of coating adhesion loss The inuence of steel surface treatment by cerium oxide lm on
after exposure to a wet condition. the corrosion protection performance of an epoxy/polyamide coat-
From Fig. 15 it can be realized that for the blank sample the ing was evaluated by EIS analysis. The test was performed on the
increase of exposure time results in the increase of coating delam- neat epoxy and Ce/Epoxy samples after 7, 21 and 45 days immer-
ination length. However, in the case of Ce treated sample, the sion in 3.5 wt.% NaCl solutions. From the results it can be seen
coating delamination during exposure time seems not reasonable. that the epoxy coating applied on the Ce treated steel substrate
These results imply that the surface treatment by cerium oxide shows only one relaxation time at all immersion times, indicating
could enhance the coating resistance against delamination in wet that the time constants related to the epoxy coating and double
environments. Fig. 16 shows that the cathodic delamination rate layer are resolved. However, for the epoxy coating applied on the
concerned with the blank sample is much higher than the one for untreated steel the Bode plots show one relaxation at 7 and 21 days
Ce treated sample. The delamination diameter of the blank sam- and two distinctive time constants at 45 days immersion. One can
G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669 667

The values of electrochemical parameters for the coatings applied on the mild steel treated by cerium oxides after 7, 21 and 45 days immersion in 3.5 wt.% NaCl solution; corresponds to the standard deviation of three replications.
be understood from these observations is that in the case of the
coating applied on the Ce treated steel the electrolyte diffusion

0.707 0.2
into the coating/metal interface did not signicantly decline the

616 15.8
3.89 1.2

4.46 1.3

10.0 2.5
8.7 3.2
coating protection performance. However, for the coating applied
fb (Hz) on the untreated steel the electrolyte diffusion into the coat-
ing/metal interface resulted in the coating delamination, leading
to the observation of the time constant related to the double layer.
Bode diagrams of these samples and the parameters extracted are
given in Fig. 17 and Table 3. The Bode diagrams were also tted
89 0.5

88 1.0

89 1.0

88 1.0

88 0.5
70 3.0
by the equivalent electrical circuits shown in Fig. 17c1 and c2 and
-10kHz
(deg)

the results extracted are reported in Table 3. Different parameters


including solution resistance (Rs ), coating resistance (Rc ), charge
transfer resistance (Rct ), constant phase element of coating (CPEc ),
constant phase element of double layer (CPEdl ), total resistance
log (|Z|10mHz

8.43 0.21

8.31 0.15

6.76 0.18

9.81 0.24

8.65 0.14

8.17 0.12
/ohm cm2 )

(Rt = Rc + Rct ) and total constant phase element (CPEt ).


It can be seen from Fig. 17 and Table 3 that the impedance values
at 10 mHz (|Z|10mHz ) and Rt of the epoxy coatings applied on the Ce
treated samples are much greater than the neat epoxy sample at all
immersion times. As the immersion time elapses the |Z|at10mHz and
(Mohm cm2 )

Rt values decrease for both samples but the decrease is more pro-
6780 234

488 43.0

156 23.0

nounced for the neat epoxy sample. The phase angle values close
213 8.0
272 12

6.2 0.8

to 90 are obtained for the sample treated by Ce, indicating lower


corrosive electrolyte diffusion into the coating/metal interface. In
Rt

addition, the breakpoint frequency (fb ) values of the Ce treated


samples are less than the neat epoxy. There is a direct correlation
between the increase of fb and the coating delamination rate. The
0.88 0.03

0.85 0.02

0.84 0.01

0.78 0.03

0.79 0.02
0.80 0.01

shift of fb by the increase of immersion time depicts the increase of


disbonded areas. The lower increase of fb for the Ce/Epoxy sample
than the neat sample clearly demonstrate the lower delamina-
n

tion of coating. In fact, deposition of Ce lm on the steel surface


(ohm1 cm2 sn )

0.0023 0.0002

0.0043 0.0003

0.0012 0.0001

0.0018 0.0003

0.0032 0.0004

could remarkably reduce the delamination rate of epoxy coating.


0.012 0.0012

Only one relaxation time can be seen in the Bode diagrams of the
CPEc , CPEt

Ce/Epoxy samples at all immersion times but two times constant


appeared after 45 days immersion on the neat epoxy sample. This
Y0

clearly shows that the electrolyte reached the epoxy/steel interface


resulted in the signicant coating delamination and corrosion prod-
ucts creation beneath the coating. All of these results conrm that
(Mohm cm2 )

deposition of Ce lm at the epoxy/steel interface could noticeably


4.35 0.35

enhance the protection performance of the epoxy coating.


The results achieved from experiments are in reasonable agree-
Rc

ment with the computational MD observation of stronger hardened


epoxy coating adhesion to Ce treated steel as compared to bare steel
substrates.
0.82 0.01

4. Conclusion
n

Results showed that the Ce lm composed of CeO2 , uniformly cov-


(ohm1 cm2 sn )

0.016 0.0015

ered the steel surface and remarkably enhanced its surface free
energy and work of adhesion and promoted the epoxy coating
adhesion on the steel substrate in both dry and wet conditions.
CPEdl

The increase in surface roughness resulted in the increase of the


Y0

number of adhesion sites and contact area between the epoxy


coating and steel substrate. The steel substrate wettability by
1.85 0.15

aminoamide-epoxy coating was noticeably enhanced after depo-


(Mohm

sition of Ce lm. The polar groups of aminoamide-epoxy coating


cm2 )

could interact with steel surface through hydrogen bonding and


Rct

chemical bonds.
Results obtained from MD simulations proved that aminoamide-
Ce treated steel/epoxy,

Ce treated steel/epoxy,

Ce treated steel/epoxy,
Untreated steel/epoxy,

Untreated steel/epoxy,

Untreated steel/epoxy,

cured epoxy resins are able to strongly bind to all three oxide
surfaces of CeO2 . The calculated interaction energies for adsorbed
epoxy resin showed that under both wet and dry conditions the
extent of epoxy binding to the selected ceria surfaces followed
21 days

45 days

21 days

45 days
Sample

the decreasing sequence: CeO2 (111) > CeO2 (100) > CeO2 (110).
7 days

7 days
Table 3

Moreover, by comparing the interaction energies for aminoamide


and uncured/cured epoxy resin, it was found that curing of epoxy
668 G. Bahlakeh et al. / Applied Surface Science 419 (2017) 650669

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