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Role of Hydrogen-Bonding and OH−π Interactions in the Adhesion

of Epoxy Resin on Hydrophilic Surfaces
Shin Nakamura, Yuta Tsuji, and Kazunari Yoshizawa*
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sı Supporting Information

ABSTRACT: Epoxy resin adhesives are widely used for joining metal alloys in
various industrial fields. To elucidate the adhesion mechanism microscopically, we
investigated the interfacial interactions of epoxy resin with hydroxylated silica (0 0 1)
and γ-alumina (0 0 1) surfaces using periodic density functional theory calculations as
well as density of states (DOS) and crystal orbital Hamilton population (COHP)
analyses. To better understand the interfacial interactions, we employed and analyzed
water and benzene molecules as hydrophilic and hydrophobic adsorbates,
respectively. Structural features and calculated adhesion energies reveal that these
small adsorbates have a higher affinity for the γ-alumina surface than that for the silica
surface, while a fragmentary model for the epoxy resin exhibits a strong interaction with the silica surface. This discrepancy suggests
that the structural features of the hydroxylated silica surface dictate its affinity to a specific species. Partial DOS and COHP curves
provide evidence for the presence of OH−π interactions between the OH groups on the surfaces and the benzene rings of the epoxy
resin fragments. The orbital interaction energies of the H-bonding and OH−π interactions evaluated from the integrated COHP
indicate that the OH−π interaction is a nonnegligible origin of the adhesion interaction, even when polymers with hydrophobic
benzene rings are adsorbed on hydroxylated surfaces.

■ INTRODUCTION
Adhesion between organic and inorganic materials is an
essential process in various industrial fields.1−4 Lightweight,
durable, and strong aircraft structural members are typically
made by bonding resin sheets to aluminum alloys. 5
Applications of adhesives include coatings preventing the
corrosion of various metal materials. The body of an
automobile is also a typical product, made of steel and
aluminum alloys coated with plastic paint. One notable
application of resin adhesion is fiber-reinforced plastics,
composites of glass and carbon fibers, and synthetic polymers
like epoxy resins, for use in the automotive, aerospace, and civil
engineering and construction sectors.6−12 For the development
of these adhesive and coating technologies, it is necessary to
understand the adhesion mechanism at the interface between
an adhesive and an adherend. Figure 1. Chemical structure of (a) bisphenol A-type epoxy resin and
Epoxy resin, synthesized from diglycidylether of bisphenol A (b) simplified model for the epoxy resin; the red, brown, and white
spheres are O, C, and H atoms, respectively.
(DGEBA), is one of the most frequently employed structural
adhesives (see Figure 1 for its structure), containing ether
(−O−) and hydroxyl (−OH) groups, which can act as an of graphite, while only dispersion interactions are substantially
acceptor and a donor−acceptor of H-bond, respectively. active on the hydrophobic surfaces of the basal face and the H-
Previous theoretical and experimental works have shown that
H-bonding interactions originating from these groups provide
a clue to the mechanism of adhesion under atmospheric Received: August 7, 2020
conditions, in which water molecules are adsorbed on Accepted: September 22, 2020
adherend surfaces.13−24 Published: October 1, 2020
Energy decomposition calculations have demonstrated that
both electrostatic and dispersion interactions are significant in
the OH-functionalized surfaces of silica and the armchair edge

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsomega.0c03798

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Figure 2. Optimized geometries of (A) water molecule, (B) benzene molecule, and (C) epoxy fragment on (top) the silica and (bottom) alumina
(0 0 1) surfaces (red, oxygen; cyan, hydrogen; gray, carbon; yellow, silicon, and purple, aluminum atoms). Selected distances are shown in Å.
terminated armchair edge of graphite.16 The epoxy resin also
has hydrophobic aromatic rings, which provide the resin with
good thermal property and corrosion resistance. A recent
computational study has proposed that the benzene rings in
the epoxy resin interact with hydrophobic surfaces like the
basal planes of hexagonal boron nitride and graphite, via the
π−π stacking.25 However, due to the lack of analysis of these
behaviors and their interactions on hydrophilic surfaces, the
functional role of benzene rings in atmospheric adhesion
remains to be elucidated.
Hydrophilic surfaces can essentially be characterized by the
concentration of hydroxyl groups on the surface. McCafferty
and Wightman used X-ray photoelectron spectroscopy to
experimentally determine the densities of hydroxyl groups on
several oxide films.26 Their results show that aluminum and
chromium covered with oxides exhibit relatively high hydroxyl
densities (>13 nm−2), while tantalum and silicon oxide films
exhibit low densities (∼8 nm−2). The hydroxyl density should
affect the affinity of the adherend to the epoxy adhesive, but
the effect of different concentrations on adhesion has not been
adequately estimated.
We have reported on the estimated adhesion strength of
epoxy resins adsorbed on hydrophilic silica and γ-alumina
surfaces.14,27,28 The importance of the H-bonding interaction
between the resin and the surfaces was revealed, but how the
hydrophobic benzene ring is involved in the adhesion process
under atmospheric conditions remains to be clarified. Epoxy
resins contain a large number of benzene rings, seen from a
microscopic perspective, leading to hints for designing
innovative adhesive polymers. Also, there have been a few
systematic, comparative studies focusing on differences in
molecular sizes and kinds of slab surfaces. Since the affinity of
each surface for various molecules is important when selecting
an adherend, these aspects not only provide a complete picture
of the adhesion mechanism but also facilitate the development
of the adherend in the industrial sector. Therefore, for starters
in this study, a comparative study of adhesion interactions
brought about by small simple molecules on two surfaces with
different hydrophilic properties was carried out. Then, we
moved on to the scrutiny of the adhesion interaction of a
fragmentary model for the bisphenol A-type epoxy resin with
the surfaces.
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We employed water and benzene molecules as a hydrophilic
molecule and a hydrophobic ring, respectively; functional
groups analogous to them are contained in the epoxy resin. A
silica adherend with a low concentration of hydroxyl groups
and a γ-alumina surface with a high concentration of hydroxyl
groups were used. Their surface structures are well
established.29−33 Each of these molecules and the epoxy
resin fragment were placed on the surface separately, and
periodic density functional theory (DFT) calculation, the
density of states (DOS) analysis, and crystal orbital Hamilton
population (COHP) analysis34−37 were performed. Based on
the optimized geometries and calculated adhesion energies,
one can observe that the small moleculeswater and
benzeneare adsorbed in a recess surrounded by hydroxyl
groups on hydrophilic surfaces, indicating an energetic
preference to the adhesion with the γ-alumina surface, while
the epoxy resin fragment would prefer the silica surface. The
DOS and COHP curves reveal that despite the hydrophobic
nature of the benzene rings of the epoxy resin fragment,
OH−π interactions between the epoxy resin fragment and the
hydroxyl protons on the surfaces stabilize the π-electrons on
the aromatic ring.
■ RESULTS AND DISCUSSION
Adhesion Structures and Interactions. The stable
structures of a water molecule, benzene molecule, and the
epoxy fragment on the silica (0 0 1) and γ-alumina (0 0 1)
surfaces were determined from geometry optimization at the
level of periodic DFT with plane-wave basis, as shown in
Figure 2. The details of the calculation setup and the
construction of the surface slab models are given in the
Computational Procedures section. The structure of the epoxy
fragment remains almost unchanged upon adsorption onto the
surfaces (see Figure S1 in the Supporting Information). The
water molecule in both slab models forms four H-bonds with
hydroxyl groups and coordinatively unsaturated oxygen atoms
in the surface, lying close to a surface recess. Strong H-bonds
with a very short O−H distance of 1.66 Å are spotted. The
other H-bond distances are within the typical O−H distance
range (1.8−2.0 Å). The average H-bond distances are 1.84 and
1.83 Å for the silica and alumina surfaces, respectively; no
significant difference can be found.
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A previous study using a cluster model reported how a water
molecule is bound via two H-bonds by an isolated silanol
group, a model for the silica surface.38 Mian et al. reported a
stable structure of a water molecule adsorbed on the silica (0 0
1) and (1 1 1) surfaces.20 These structures suggest the
presence of strong H-bonds with O−H distances shorter than
1.7 Å. Our data reasonably suggest the idea that a water
molecule can penetrate the silanol layer of the silica surface and
approach the coordinatively unsaturated oxygen atoms that
cross-link subsurface silicon atoms.
After the geometry optimization, we calculated the adhesion
energy, ΔEad, which represents the net energy change upon
adhesion, expressed as
ΔEad = (Eadhesive + Eadherend) − E(adhesive + adherend)
where E(adhesive + adherend) represents the total energy of the
adhesive−adherend complex and Eadhesive and Eadherend,
respectively, represent the energies of the adhesive and
adherend calculated separately. Eadhesive and Eadherend are
obtained by performing the geometry optimizations separately.
Positive values of ΔEad indicate exothermic adhesion, with
higher values indicating a stronger interaction between the
adhesive and the adherend. The dispersion interaction upon
adhesion was also estimated. The dispersion energy ΔEdisp
working between the adhesive and the adherend is given by the
following equation
disp disp disp
ΔEdisp = (Eadhesive + Eadherend ) − E(adhesive + adherend)
disp
where Eadhesive disp
and Eadherend represent, respectively, the
dispersion energies of the adhesive and adherend calculated
separately and Edisp
(adhesive+adherend) is the total dispersion energy of
the adhesive−adherend complex. These values were calculated
using the optimized geometry for each system. The calculated
adhesion energies for the water molecule on the silica and γ-
alumina (0 0 1) surfaces are 72.6 and 82.6 kJ/mol, respectively,
as summarized in Table 1. The results suggest that the alumina
Table 1. Adhesion Energy, ΔEad (kJ/mol), Its Dispersion
Component, ΔEdisp (kJ/mol), and the Ratio between Them,
ΔEdisp/ΔEad, Calculated for the Three Molecules (Water,
Benzene, and Epoxy) on the Silica and Alumina (0 0 1)
Surfaces
silica (0 0 1) γ-alumina (0 0 1)
ratio
(ΔEdisp/
model ΔEad ΔEdisp ΔEad) ΔEad ΔEdisp
water 72.6 22.0 0.303 82.6 35.1
benzene 33.0 40.3 1.223 53.6 67.3
epoxy 145.9 108.8 0.746 117.0 89.6
model
surface has a slightly higher affinity for water than the silica
surface. The ΔEad values of the water molecule adsorbed on
the surfaces are comparable with those calculated using cluster
models.33,38−40 Mian et al. reported the water-binding energies
of 12.17 kcal/mol (50.9 kJ/mol) and 11.08 kcal/mol (46.4 kJ/
mol) for the silica (0 0 1) and (1 1 1) surfaces, respectively.20
Tielens et al. investigated the water-binding energy for various
silanols, finding that it ranges from 11.52 to 11.95 kcal/mol
(48.2−50.0 kJ/mol).33 These binding energies are slightly
lower than the water adhesion energies obtained in the present
study. However, the energies reported in the literature were
Article
calculated using structures with one to three H-bonds between
water and silanol, markedly different from the present study.
Therefore, we propose the idea that water molecules are
strongly stabilized when they penetrate the silanol layer of the
silica surface.
As shown in Figure 2, benzene weakly interacts with the
surface hydroxyl groups, taking on a conformation almost
perpendicular to the surface plane with angles of 75.0 and
88.7° on the silica and alumina surfaces, respectively. To
visualize the effects of the adsorption on the electron densities
of adsorbed molecules, we calculated the charge density
difference. For each model, the charge density difference, Δρ,
upon adhesion was calculated using
Δρ = ρ(adhesive + adherend) − (ρadhesive + ρadherend )
where ρ(adhesive+adherend), ρadhesive, and ρadherend are the charge
densities of the adhesive−adherend complex, adhesive, and
adherend, respectively. The charge densities of the adhesive
and adherend were calculated separately, but their geometries
were kept the same as those in the adhesive−adherend
complex. The isosurfaces of charge density difference show an
increase in electron density in the region between the
interacting hydroxyl H atom and the carbon atom of the
benzene molecule (see Figure 3A), while a slight decrease in
electron density on the lower H atoms of the benzene
molecule. These observations suggest that the main interaction
for benzene adsorption is the OH−π interaction rather than
the CH−O interaction. The adhesion energies of the benzene
molecule are estimated to be 33.0 and 53.6 kJ/mol for the
silica and alumina surfaces, respectively, as shown in Table 1. It
is inferred that the OH−π interaction on the alumina surface
has a greater effect on the adhesion energy. The presence of
the OH−π interaction of a benzene molecule is consistent with
the previous theoretical works by Rimola et al.41,42 The C−H
distance along the OH−π interaction in their model is in the
range of 2.2−2.6 Å, quite close to our results.
The benzene adhesion also denotes a high ratio of the
dispersion energy, indicating that dispersion contribution to
adhesion is crucial even on the hydrophilic surfaces. Our
previous study has investigated the adhesion of an epoxy
fragment with the hydrophobic surface of hexagonal boron
nitride: the interaction exerted at the interface is predom-
inantly derived from dispersion forces.25 The large contribu-
ratio tion of dispersion energy to the adhesion of benzene
(ΔEdisp/ investigated in the present study supports the idea that
ΔEad) benzene rings are adsorbed on surfaces primarily through
0.425 dispersion interactions. Compared to benzene adsorption, the
1.256 ratios of ΔEdisp to ΔEad for the adsorption of water indicate a
0.766 relatively low contribution of dispersion energy to adhesion
energy. The dispersion contribution seems less important for
the case of water adsorption.
The hydroxyl group of the epoxy resin model acts as an H-
bond donor−acceptor with the hydroxyl groups of both slab
model surfaces. These H-bond distances are within the typical
distance range. The hydroxyl groups in the epoxy model, in
contrast to the water molecule, cannot enter the surface recess
due to the steric hindrance caused by the two benzene rings.
Compared to the hydroxyl groups, the interaction of the
benzene rings of the epoxy fragment shows a different behavior
between the silica and alumina surfaces. As shown in Figure 2,
the benzene ring on the silica surface attracts hydroxyl protons
on the surface, but the benzene ring on the alumina surface
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Figure 3. Isosurfaces of charge density difference calculated for (A) benzene adsorption and (B) epoxy adhesion on (left) the silica and (right)
alumina surfaces (yellow, charge accumulation; cyan, charge depletion). The isovalue is set to 0.00275 e/Å3.

does not interact with the hydroxyl group. The results of this view of this insight, the silica surface may be more suitable than
calculation are consistent with the charge density differences of the alumina surface for the formation of OH−π interactions.
the epoxy models on the surfaces, as shown in Figure 3. The This is due to the long distance (∼4.9 Å) between the convex,
characteristic features of the charge density differences around protruding oxygen atoms on the silica surface, providing
the benzene rings of the epoxy model on the silica surface can sufficient space to interact with the adhesive, as shown in
be observed: they are similar to those for the adsorption of Figure 4. Since the distance between the convex oxygen atoms
benzene. This observation strongly suggests that the OH−π
interactions contribute not only to the small molecule
adsorption but also to the adsorption of large systems (e.g.,
polymers and proteins). It should be noted that we obtained
the several optimized geometries of the epoxy fragment on the
silica and alumina surfaces by changing the initial structures for
the geometry optimizations, and then, we chose the most
stable conformation among them (see Table S1 in the
Supporting Information). For the epoxy−alumina complex,
we were not able to obtain the structure with both H-bonding
and OH−π interactions using geometry optimization. During
this process, we found that the OH−π interaction between the
epoxy fragment and the alumina surface is relatively weak in
comparison with that on the silica surface. The epoxy fragment
on the alumina surface does not show the charge density
difference on the benzene ring (see Figure S2 in the
Supporting Information).
The interaction between the epoxy model and the alumina
surface does not seem to bring about significant changes in the
Figure 4. Surface structures of silica (A) and γ-alumina (B) are shown
charge density difference. The benzene rings of the epoxy
along with distances between the surface convex, protruding oxygens
fragment on the alumina surface appear to be unable to (red, oxygen; yellow, silicon; and purple, aluminum atoms). The
interact effectively with the protons of the hydroxyl groups on selected distances are shown in Å. Hydrogen atoms are omitted for
the surface. This is partly because there is a lack of recessed clarity.
areas of the surface, which are necessary for the benzene rings
to take a conformation essential for the OH−π interaction on
the surface. The absence of dangling protons on the alumina
surface is also a major factor, in which the dangling proton on the alumina surface is about the same or shorter than the
means a proton that can move flexibly in response to changes typical H-bond distance, many of the hydroxyl protons prefer
in the electrostatic potential and the structure of hydrogen to form H-bonds with the nearby convex oxygen atoms rather
bonds on the surface. than with the adhesive. By contrast, many hydroxyl protons on
For the interaction of the benzene ring with a hydroxyl the silica surface prefer to interact with the adhesive. This
proton on the surface, the plane of the benzene ring needs to tendency seems to be critically important for the adhesion of
be slightly perpendicular to the O−H direction of the hydroxyl large molecules with a large steric hindrance (e.g., polymers
group on the surface, as in the case of benzene adsorption. In and proteins).
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The arrangement of the convex oxygen atoms depends
predominantly on the concentration of hydroxyl groups on the
surface. Differences in the coordination structure of silicon and
aluminum atoms in the slabs seem to be the main cause of the
difference in the concentration of surface hydroxyl groups.
Aluminum atoms in alumina basically take an octahedral
geometry consisting of six ligand oxygen atoms, whereas silicon
atoms in silica take a tetrahedral geometry consisting of four
ligand oxygen atoms. The combination of the octahedral
geometry and the (0 0 1) facet induces a flat surface and many
surface aluminum atoms are left coordinatively unsaturated
immediately after cleavage (before passivation). This view is
consistent with the fact that the distances between the convex
oxygen atoms on the alumina surface are almost the same as
the nearest Al−Al distance, which ranges from 2.8 to 2.9 Å as
measured for the optimized bulk structure of alumina. For
example, chromium in chromium(III) oxide (i.e., Cr2O3),
which has a six-coordinated structure similar to alumina, also
has a high concentration of hydroxyl groups on its surface.26
Owing to the tetrahedral geometry of silicon, concave and
convex silicon sites are generated on the silica surface: the
former are hydroxylated, while the latter are not. This leads to
a reduced number of hydration sites. Since a relatively low
density of hydroxyl groups is reported for the silica (0 0 1) and
(1 1 1) surfaces, which are derived respectively from α- and β-
cristobalites,20 the choice of lattice planes to be cleaved may
not significantly affect the hydration concentration of the
surface at least as far as silica goes. This suggests that the
coordination structure of the cationic element in the bulk may
have a significant effect on the concentration and structure of
surface hydroxyl groups.
Adhesion energies calculated for the epoxy fragment on the
silica and alumina surfaces are 145.9 and 117.0 kJ/mol,
respectively, as shown in Table 1. This result seems consistent
with the absence of the OH−π interaction on the alumina
surface. The dispersion contribution to the adhesion energy is
estimated to be 108.8 and 89.6 kJ/mol on the silica and
alumina surfaces, respectively. The ratio of ΔEdisp to ΔEad in
epoxy adhesion lies between those for water and benzene
adsorption. This suggests that the epoxy fragment adheres to
the hydrophilic surfaces through the H-bonding interaction
due to the hydroxyl group and the dispersion interaction due
to the benzene rings.
We have previously reported that the adhesion energies of
an epoxy resin fragment on the silica (0 0 1) surface and the γ-
alumina (0 0 1) surface are 145.727 and 64.7−65.8 kJ/mol,13
respectively. The value of ΔEad calculated for the silica surface
in this study is close to that of the previous study, while the
value of ΔEad for the γ-alumina surface in this study is
significantly larger than those calculated in the previous
studies. However, the previous studies on the alumina surface
did not apply dispersion correction to the periodic DFT
calculations. The mismatch in the adhesion energy of the
epoxy fragment to the alumina surface may be due to the lack
of dispersion correction in the previous studies, as dispersion
interactions contribute significantly to adhesion.
Effects on Electronic Structures and Orbital Inter-
actions. To estimate the effect of adhesion on the electronic
structure, we calculated the partial DOS (PDOS) for the 2p
orbitals of the carbon atoms of the benzene molecule and the
benzene rings in the epoxy model, as shown in Figure 5. Most
peaks of the PDOS are found downshifted by 0.34−0.39 eV
when benzene is adsorbed on the alumina surface, while its
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Figure 5. Partial density of states (PDOS) for the 2p orbitals of the C
atoms in (A) benzene and the aromatic rings of the epoxy fragment
(B) adsorbed on the surface (red lines) and isolated from the surface
(blue lines). The dashed line indicates the Fermi level. In the
calculation of the isolated epoxy molecule, the slab surface remains in
the periodic boundary box but they are separated so far that the
surface−molecule interaction can be negligible. Therefore, the Fermi
energy of the system including the isolated molecule matches that of
the surface.
adsorption on the silica surface does not appear to affect the
peak positions. The larger adhesion energy of benzene on the
alumina surface than on the silica surface (see Table 1) looks
consistent with the occurrence of the downward peak shift in
the PDOS for the alumina system and its absence in the silica
system.
The PDOS spectrum for the carbon 2p orbitals of the
benzene rings of the epoxy fragment on the alumina surface
looks almost identical to that calculated for the isolated epoxy
fragment. On the silica surface, the PDOS peaks for the carbon
2p orbitals of one of the benzene rings are downshifted by
about 0.08 eV after the adsorption of the epoxy fragment on
the surface. This suggests that the electrons on the benzene
ring are somewhat stabilized by the OH−π interaction, which
may be one of the important interactions for the adhesion of
polymers including benzene rings.
As shown in Figure 6, in contrast to the OH−π interaction,
the H-bonding interaction leads to the broadening of the
PDOS peaks for the hydroxyl O atom of the epoxy fragment
and those for the oxygen atom of the adsorbed water molecule.
Also, the H-bonding interaction lowers the energy levels of the
PDOS peaks. These features are indicative of electronic
interactions induced by H-bonds between the adherend and
the adhesive.
In addition to the PDOS calculations, we also performed
COHP analyses based on the wave function obtained from the
periodic DFT calculations. The wave function is expanded
using plane waves, so a projection scheme is required for
moving from the plane-wave to a local atomic-orbital basis set.
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Figure 6. Partial density of states (PDOS) for the O atom of the

water molecule and that for the O atom of the hydroxyl group in the
epoxy fragment. They were calculated for the state of adsorption on
the silica and γ-alumina surfaces (red) and the state in which the
adsorbate is separated from the surface (blue). The dashed line
indicates the Fermi level.

The LOBSTER program allows us to do this. The COHP Figure 7. Negative of projected crystal orbital Hamilton population
(−pCOHP) calculated for the interactions found to be related to the
analysis is a method of the decomposition of the DOS into the
OH−π interactions between the aromatic rings of the epoxy fragment
bonding and antibonding interactions for a specific pair of and the hydroxyl protons on the silica surface (A). −pCOHP curves
atoms using the corresponding Hamiltonian matrix element for the H-bonding interactions between the hydroxyl group of the
and the crystal orbital expansion coefficients. Since the epoxy fragment and the hydroxyl groups on the silica and γ-alumina
projection is done, one may call the COHP generated from surfaces (B). The dashed line indicates the Fermi level. (C) Top: the
LOBSTER the projected COHP (pCOHP). Bonding inter- atomic pairs associated with the OH−π interactions at the silica−
actions are concomitant with negative Hamiltonian matrix epoxy interface are indicated by colored lines. Bottom: the interface
elements, so negative pCOHP values ensue. The values of structure between silica/alumina and epoxy are shown in an
pCOHP plots to be presented below have already been abstracted fashion, where the atomic pairs associated with the H-
multiplied by −1 such that positive −pCOHP values bonding interactions are indicated by colored lines. The interaction
lines are color-coded with the colors of the lines in the −pCOHP
correspond to bonding interactions.
plots.
Figure 7A shows the −pCOHP curves calculated for the
atomic pairs found to be related to the OH−π interaction at
Table 2. Distances (Å) and Integrated pCOHP (ICOHP)
the silica−epoxy interface. In these spectra, a manifold of
Values for the Atomic Pairs Shown in Figure 7C
positive peaks are observed below the Fermi level, a relatively
large positive peak at around 4 eV, and a couple of negative silica (0 0 1) γ-alumina (0 0 1)
peaks way above the Fermi level (>5 eV). Although the large distance (Å) ICOHP (eV) distance (Å) ICOHP (eV)
positive band around 4 eV contains no electrons and does not
Hslab−Oa 1.85 −0.78 1.97 −0.64
contribute to bonding, the peaks below the Fermi level indicate
Ha−Oslab 1.86 −0.67 1.79 −0.95
that the OH−π interactions between the aromatic ring and the
Hslab−Oc 1.93 −0.53
hydroxyl groups of the silica surface can be characterized by
Hslab−C1f 2.34 −0.16
the presence of bonding-type orbital interactions between
Hslab−C2b 2.08 −0.32
them over a relatively wide energy range.
Hslab−C2d 2.45 −0.14
Figure 7B shows the −pCOHP curves calculated for the
atomic pairs found to be related to the H-bonding interactions
at the silica−epoxy and alumina−epoxy interfaces. The the atomic pairs. Note that the unit of ICOHP is eV. This
calculated O−H pairs with H-bonding interactions are found value can be read as bonding energy of a certain kind.
to be characterized by bonding-type orbital interactions, The ICOHP value for the H-bonding interaction falls in the
although one can see a few negative peaks (antibonding range from −0.53 to −0.95 eV, while that for the OH−π
interactions) at around −20 and −3 eV for the alumina interaction falls in the range from −0.14 to −0.32 eV. These
interface and in the range of −20 to −18 eV and at around −6 computed values imply that the H-bonding interactions are
eV for the silica interface. We visualized the OH−π orbital stronger than the OH−π interactions. Thus, the H-bonding
interactions and the H-bonding orbital interactions by interaction is likely to have a dominant effect on adhesion as
calculating the partial charge density maps, as shown in Figure expected and as reported in the preceding studies. On top of
S2 in the Supporting Information. that, since epoxy resins have more benzene rings than hydroxyl
To compare the orbital interaction energies between the H- groups, the interaction energy due to the OH−π interaction
bonding and OH−π interactions, the pCOHP values were cannot be regarded as low as a whole. This suggests that the
integrated up to the Fermi level for each atomic pair. They are OH−π interaction should not be ignored even though
called ICOHP, as summarized in Table 2. A negative ICOHP polymers containing hydrophobic benzene rings are used for
value suggests that there is a net bonding interaction between adhesion to hydrophilic surfaces.
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Figure 8. Periodic slab models of (A) 2 × 3 supercell of the hydroxylated silica (0 0 1) surface and (B) 3 × 1 supercell of the hydroxylated γ-
alumina (0 0 1) surface (red, oxygen; cyan, hydrogen; yellow, silicon; and purple, aluminum atoms).
■ CONCLUSIONS
To elucidate the adhesion mechanism of the DGEBA epoxy
resin to the hydrophilic surfaces of alumina and silica from a
microscopic point of view, periodic DFT calculations and
orbital analysis have been used to explore the interactions at
the interfaces. Water and benzene molecules were selected as a
simple model for the hydroxyl group and the benzene ring in
the epoxy resin. A fragmentary molecular structure of the
epoxy resin was also used to study the adhesion mechanism,
including the effects of resin-specific steric hindrances.
The alumina and silica slab surfaces were modeled on
hydroxylated γ-alumina (0 0 1) and silica (0 0 1) surfaces. The
water molecule was found adsorbed into a recess surrounded
by hydroxyl groups on both surfaces to form four H-bonds,
while the benzene molecule stands almost perpendicular to the
surface in the recess, and their carbon atoms attract hydroxyl
protons through OH−π interactions.
In contrast to the small adsorbates, the optimized geometry
of the epoxy resin fragment differs from surface to surface. The
hydroxyl group in the epoxy fragment forms H-bonds with
both silica and alumina surfaces, whereas the resin’s benzene
rings interact only with the silica surface by attracting the
protons of surface hydroxyl groups thereon. Calculated
adhesion energies indicate that the alumina surface has a
higher affinity for water and benzene molecules than the silica
surface. By contrast, the epoxy fragment shows a stronger
interaction with the silica surface than with the alumina
surface.
Although this contrast seems to be a contradiction, this may
be because of the steric hindrance of the epoxy fragment. The
interactions of the fragment with protons wobbling on the
alumina surface and limited recessed space available for
interaction may also be responsible for the difference. This
indicates that by controlling the size of the recess on the
surface, which is derived from surface hydroxyl groups, one can
ameliorate the adhesion affinity of the surface to the polymer.
Orbital interactions responsible for the H-bonding and
OH−π interactions at the adhesion interfaces were also
investigated using PDOS and COHP analyses. The results
show that the benzene molecule on the alumina surface and
one of the benzene rings of the epoxy fragment on the silica
surface cause a downshift of the PDOS peaks corresponding to
the 2p orbitals of the carbon atoms therein when the adhesion
interaction sets in. This suggests that the OH−π interaction
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with the benzene ring stabilizes the π-electrons on the ring.
The COHP values were integrated up to the Fermi level to
obtain the ICOHP, which is a good measure of the bonding
energy due to orbital interactions. Calculated ICOHP values
indicate that the H-bonding interaction is stronger than the
OH−π interaction. However, considering that the number of
the benzene rings in epoxy resins is greater than that of the
hydroxyl groups, it can be concluded that OH−π interactions
cannot be ignored as one of the origins of the adhesion force.
■
COMPUTATIONAL PROCEDURES
We performed all of the ab initio periodic calculations using
VASP program package version 5.4.4.43−46 We carried out
geometry optimizations using DFT with the Perdew−Burke−
Ernzerhof functional47 with a dispersion correction of the
DFT-D2 method by Grimme.48 The plane-wave basis set
cutoff and self-consistent field tolerance were set to 500 and
10−5 eV, respectively. The threshold of atomic forces for the
convergence of the geometry optimization was set to 0.03 eV/
Å. We employed a mesh of k-points of 2 × 2 × 1 for sampling
the Brillouin zone. We calculated DOS and COHP using
LOBSTER software version 3.1.0,34−36 utilizing the wave
functions generated from the VASP periodic DFT calculations.
Structures were visualized using the VESTA software pack-
age.49
A periodic silica (0 0 1) surface was created by cleaving the
bulk structure of α-cristobalite obtained from the Materials
Studio 6.1 database.50 The unit cell of silica contains four
silicon and eight oxygen atoms with lattice constants of a =
4.931 Å, b = 4.931 Å, c = 6.802 Å, and β = 90.00°, as
determined from DFT calculations. By repeating the unit cell
twice in the direction of the c-axis, a supercell containing eight
atomic layers was constructed, and an empty space with a
thickness of 20 Å was added as a vacuum layer on the surface.
Two water molecules were dissociatively adsorbed to passivate
coordinatively unsaturated silicon atoms on the surface. The
hydroxylated surface thus generated was optimized using the
periodic DFT method with the atomic positions in the middle
layers (i.e., the fourth and fifth layers) kept fixed. The slab
model obtained was virtually identical to the one investigated
in our previous study,27 as shown in Figure 8A.
A periodic γ-alumina (0 0 1) surface slab model was
constructed in the same way as used for the construction of the
silica (0 0 1) surface model. The bulk structure of γ-alumina
https://dx.doi.org/10.1021/acsomega.0c03798
ACS Omega 2020, 5, 26211−26219
ACS Omega http://pubs.acs.org/journal/acsodf
was obtained from the literature, where a model based on DFT
calculations by Toulhoat et al. is reported.51,52 The unit cell of
γ-alumina contains 16 aluminum atoms and 24 oxygen atoms
with lattice constants of a = 5.528 Å, b = 8.333 Å, c = 8.022 Å,
and β = 90.68°, as determined from DFT calculations. A 20 Å
thick empty space was placed on the surface as a vacuum layer
and eight water molecules were dissociatively adsorbed on the
surface to passivate coordinatively unsaturated aluminum
atoms on the surface. The surface structure created was
optimized with the atomic positions of the middle layers (i.e.,
the second and third layers of the four layers) kept fixed. As
can be seen from Figure 8B, the optimized surface structure for
γ-alumina is in good agreement with what was calculated in
previous studies.13,28
Owing to the different molecular sizes of the three adhesive
molecules, a 2 × 2 supercell of the silica slab was used for the
calculations of water and benzene adsorption and a 2 × 3
supercell for epoxy adhesion. A 2 × 1 supercell of the γ-
alumina slab was used for the calculations of benzene
adsorption and a 3 × 1 supercell for epoxy adhesion. The
longer dimensions of the a- and b-directions of the periodic
boundary box are ∼15 and ∼17 Å for the silica and γ-alumina
surfaces, respectively, both of which are longer than the end-to-
end distance of the epoxy fragment (∼13 Å). The unit cell of
the γ-alumina slab was used for the calculations of water
adsorption. In the optimizations of the slab structures with the
addition of each adhesive model, the atomic positions of the
lower half of the silica and alumina slabs were fixed and those
of the upper half were fully relaxed. Each of the adsorbate
molecules was placed randomly on the surface and geometry
optimization was carried out several times to determine a
stable interfacial structure.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.0c03798.
Relative energies for the optimized geometries of the
epoxy fragment on the hydroxylated surfaces, structural
changes of the epoxy fragments upon adsorption,
isosurfaces of charge density difference calculated for
epoxy adhesion on the alumina surface without H-
bonding interactions, and partial charge density maps for
the epoxy fragment adsorbed onto the hydroxylated
surfaces (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Kazunari Yoshizawa − Institute for Materials Chemistry and
Engineering and IRCCS, Kyushu University, Fukuoka 819-
0395, Japan; orcid.org/0000-0002-6279-9722;
Email: kazunari@ms.ifoc.kyushu-u.ac.jp
Authors
Shin Nakamura − Institute for Materials Chemistry and
Engineering and IRCCS, Kyushu University, Fukuoka 819-
0395, Japan; orcid.org/0000-0001-6223-2323
Yuta Tsuji − Institute for Materials Chemistry and Engineering
and IRCCS, Kyushu University, Fukuoka 819-0395, Japan;
orcid.org/0000-0003-4224-4532
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.0c03798
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Article
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by KAKENHI grants (numbers
JP17K14440 and JP17H03117) from the Japan Society for the
Promotion of Science (JSPS) and the Ministry of Education,
Culture, Sports, Science and Technology of Japan (MEXT)
through the MEXT projects Integrated Research Consortium
on Chemical Sciences (IRCCS), Cooperative Research
Program of Network Joint Research Center for Materials and
Devices, and Elements Strategy Initiative to Form Core
Research Center and by JST-CREST JPMJCR15P5 and JST-
Mirai JPMJMI18A2. The computations in this work were
primarily performed using the computer facilities at the
Research Institute for Information Technology, Kyushu
University. Y.T. is grateful for a JSPS Grant-in-Aid for
Scientific Research on Innovative Areas (Discrete Geometric
Analysis for Materials Design, grant number JP20H04643, and
Mixed Anion, grant number JP19H04700).
■ REFERENCES
(1) Kinloch, A. J. The science of adhesion. J. Mater. Sci. 1980, 15,
2141−2166.
(2) Edward, P. Epoxy Adhesive Formulations; McGraw-Hill
Professional, 2005.
(3) Fourche, G. An overview of the basic aspects of polymer
adhesion. Part II: Application to surface treatments. Polym. Eng. Sci.
1995, 35, 968−975.
(4) Fourche, G. An overview of the basic aspects of polymer
adhesion. Part I: Fundamentals. Polym. Eng. Sci. 1995, 35, 957−967.
(5) Brockmann, W.; Hennemann, O. D.; Kollek, H.; Matz, C.
Adhesion in bonded aluminium joints for aircraft construction. Int. J.
Adhes. Adhes. 1986, 6, 115−143.
(6) Simon, R.; Prosen, S. P.; Duffy, J. Carbon fibre composites.
Nature 1967, 213, 1113−1114.
(7) Ishida, H.; Koenig, J. L. The reinforcement mechanism of fiber-
glass reinforced plastics under wet conditions: a review. Polym. Eng.
Sci. 1978, 18, 128−145.
(8) Fitzer, E.; Geigl, K. H.; Hüttner, W.; Weiss, R. Chemical
interactions between the carbon fibre surface and epoxy resins.
Carbon 1980, 18, 389−393.
(9) Park, S. J.; Kim, B. J. Roles of acidic functional groups of carbon
fiber surfaces in enhancing interfacial adhesion behavior. Mater. Sci.
Eng., A 2005, 408, 269−273.
(10) Dai, Z.; Shi, F.; Zhang, B.; Li, M.; Zhang, Z. Effect of sizing on
carbon fiber surface properties and fibers/epoxy interfacial adhesion.
Appl. Surf. Sci. 2011, 257, 6980−6985.
(11) Deng, S. H.; Zhou, X. D.; Fan, C. J.; Lin, Q. F.; Zhou, X. G.
Release of interfacial thermal stress and accompanying improvement
of interfacial adhesion in carbon fiber reinforced epoxy resin
composites: induced by diblock copolymers. Composites, Part A
2012, 43, 990−996.
(12) Sathishkumar, T. P.; Satheeshkumar, S.; Naveen, J. Glass fiber-
reinforced polymer composites - a review. J. Reinf. Plast. Compos.
2014, 33, 1258−1275.
(13) Semoto, T.; Tsuji, Y.; Yoshizawa, K. Molecular understanding
of the adhesive force between a metal oxide surface and an epoxy
resin. J. Phys. Chem. C 2011, 115, 11701−11708.
(14) Semoto, T.; Tsuji, Y.; Yoshizawa, K. Molecular understanding
of the adhesive force between a metal oxide surface and an epoxy
resin: effects of surface water. Bull. Chem. Soc. Jpn. 2012, 85, 672−
678.
(15) Semoto, T.; Tsuji, Y.; Tanaka, H.; Yoshizawa, K. Role of edge
oxygen atoms on the adhesive interaction between carbon fiber and
epoxy resin. J. Phys. Chem. C 2013, 117, 24830−24835.
https://dx.doi.org/10.1021/acsomega.0c03798
ACS Omega 2020, 5, 26211−26219
ACS Omega http://pubs.acs.org/journal/acsodf
(16) Yoshizawa, K.; Semoto, T.; Hitaoka, S.; Higuchi, C.; Shiota, Y.;
Tanaka, H. Synergy of electrostatic and van der Waals interactions in
the adhesion of epoxy resin with carbon-fiber and glass surfaces. Bull.
Chem. Soc. Jpn. 2017, 90, 500−505.
(17) Henry, D. J.; Yiapanis, G.; Evans, E.; Yarovsky, I. Adhesion
between graphite and modified polyester surfaces: a theoretical study.
J. Phys. Chem. B 2005, 109, 17224−17231.
(18) Köppen, S.; Bronkalla, O.; Langel, W. Adsorption config-
urations and energies of amino acids on anatase and rutile surfaces. J.
Phys. Chem. C 2008, 112, 13600−13606.
(19) Koppen, S.; Langel, W. Simulation of adhesion forces and
energies of peptides on titanium dioxide surfaces. Langmuir 2010, 26,
15248−15256.
(20) Mian, S. A.; Saha, L. C.; Jang, J.; Wang, L.; Gao, X.; Nagase, S.
Density functional theory study of catechol adhesion on silica
surfaces. J. Phys. Chem. C 2010, 114, 20793−20800.
(21) Mian, S. A.; Yang, L. M.; Saha, L. C.; Ahmed, E.; Ajmal, M.;
Ganz, E. A fundamental understanding of catechol and water
adsorption on a hydrophilic silica surface: exploring the underwater
adhesion mechanism of mussels on an atomic scale. Langmuir 2014,
30, 6906−6914.
(22) Bahlakeh, G.; Ghaffari, M.; Saeb, M. R.; Ramezanzadeh, B.; De
Proft, F.; Terryn, H. A close-up of the effect of iron oxide type on the
interfacial interaction between epoxy and carbon steel: combined
molecular dynamics simulations and quantum mechanics. J. Phys.
Chem. C 2016, 120, 11014−11026.
(23) Ogata, S.; Takahashi, Y. Moisture-induced reduction of
adhesion strength between surface oxidized Al and epoxy resin:
dynamics simulation with electronic structure calculation. J. Phys.
Chem. C 2016, 120, 13630−13637.
(24) Ogata, S.; Uranagase, M. Unveiling the chemical reactions
involved in moisture-induced weakening of adhesion between
aluminum and epoxy resin. J. Phys. Chem. C 2018, 122, 17748−17755.
(25) Tsuji, Y.; Kitamura, Y.; Someya, M.; Takano, T.; Yaginuma, M.;
Nakanishi, K.; Yoshizawa, K. Adhesion of epoxy resin with hexagonal
boron nitride and graphite. ACS Omega 2019, 4, 4491−4504.
(26) McCafferty, E.; Wightman, J. P. Determination of the
concentration of surface hydroxyl groups on metal oxide films by a
quantitative XPS method. Surf. Interface Anal. 1998, 26, 549−564.
(27) Higuchi, C.; Tanaka, H.; Yoshizawa, K. Molecular under-
standing of the adhesive interactions between silica surface and epoxy
resin: effects of interfacial water. J. Comput. Chem. 2019, 40, 164−171.
(28) Yoshizawa, K.; Murata, H.; Tanaka, H. Density-functional tight-
binding study on the effects of interfacial water in the adhesion force
between epoxy resin and alumina surface. Langmuir 2018, 34, 14428−
14438.
(29) Liu, Z.; Ma, L.; Junaid, A. S. M. NO and NO2 adsorption on
Al2O3 and Ga modified Al2O3 surfaces: a density functional theory
study. J. Phys. Chem. C 2010, 114, 4445−4450.
(30) Kwak, J. H.; Hu, J.; Mei, D.; Yi, C. W.; Kim, D. H.; Peden, C.
H.; Allard, L. F.; Szanyi, J. Coordinatively unsaturated Al3+ centers as
binding sites for active catalyst phases of platinum on γ-Al2O3. Science
2009, 325, 1670−1673.
(31) Peri, J. B. A model for the surface of γ-alumina1. J. Phys. Chem.
A 1965, 69, 220−230.
(32) Zhuravlev, L. T. Concentration of hydroxyl groups on the
surface of amorphous silicas. Langmuir 1987, 3, 316−318.
(33) Tielens, F.; Gervais, C.; Lambert, J. F. o.; Mauri, F.; Costa, D.
Ab initio study of the hydroxylated surface of amorphous silica: a
representative model. Chem. Mater. 2008, 20, 3336−3344.
(34) Deringer, V. L.; Tchougreeff, A. L.; Dronskowski, R. Crystal
orbital Hamilton population (COHP) analysis as projected from
plane-wave basis sets. J. Phys. Chem. A 2011, 115, 5461−5466.
(35) Maintz, S.; Deringer, V. L.; Tchougreeff, A. L.; Dronskowski, R.
Analytic projection from plane-wave and PAW wavefunctions and
application to chemical-bonding analysis in solids. J. Comput. Chem.
2013, 34, 2557−2567.
26219
Article
(36) Maintz, S.; Deringer, V. L.; Tchougreeff, A. L.; Dronskowski, R.
LOBSTER: A tool to extract chemical bonding from plane-wave
based DFT. J. Comput. Chem. 2016, 37, 1030−1035.
(37) Dronskowski, R.; Bloechl, P. E. Crystal orbital Hamilton
populations (COHP): energy-resolved visualization of chemical
bonding in solids based on density-functional calculations. J. Phys.
Chem. B 1993, 97, 8617−8624.
(38) Pelmenschikov, A. G.; Morosi, G.; Gamba, A. Adsorption of
water and methanol on silica hydroxyls: ab initio energy and
frequency calculations. J. Phys. Chem. A 1997, 101, 1178−1187.
(39) Civalleri, B.; Garrone, E.; Ugliengo, P. Cagelike clusters as
models for the isolated hydroxyls of silica: ab initio B3-LYP
calculations of the interaction with ammonia. Langmuir 1999, 15,
5829−5835.
(40) Civalleri, B.; Garrone, E.; Ugliengo, P. Cage-like clusters as
models for the hydroxyls of silica: ab initio calculation of 1H and 29Si
NMR chemical shifts. Chem. Phys. Lett. 1999, 299, 443−450.
(41) Rimola, A.; Civalleri, B.; Ugliengo, P. Physisorption of aromatic
organic contaminants at the surface of hydrophobic/hydrophilic silica
geosorbents: a B3LYP-D modeling study. Phys. Chem. Chem. Phys.
2010, 12, 6357−6366.
(42) Rimola, A.; Sodupe, M.; Ugliengo, P. Affinity Scale for the
Interaction of Amino Acids with Silica Surfaces. J. Phys. Chem. C
2009, 113, 5741−5750.
(43) Kresse, G.; Hafner, J. Ab initio molecular dynamics for liquid
metals. Phys. Rev. B 1993, 47, 558−561.
(44) Kresse, G.; Hafner, J. Ab initio molecular-dynamics simulation
of the liquid-metal-amorphous-semiconductor transition in germa-
nium. Phys. Rev. B 1994, 49, 14251−14269.
(45) Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy
calculations for metals and semiconductors using a plane-wave basis
set. Comput. Mater. Sci. 1996, 6, 15−50.
(46) Kresse, G.; Furthmuller, J. Efficient iterative schemes for ab
initio total-energy calculations using a plane-wave basis set. Phys. Rev.
B 1996, 54, 11169−11186.
(47) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient
approximation made simple. Phys. Rev. Lett. 1996, 77, 3865−3868.
(48) Grimme, S. Semiempirical GGA-type density functional
constructed with a long-range dispersion correction. J. Comput.
Chem. 2006, 27, 1787−1799.
(49) Momma, K.; Izumi, F. VESTA 3for three-dimensional
visualization of crystal, volumetric and morphology data. J. Appl.
Crystallogr. 2011, 44, 1272−1276.
(50) Materials Studio 6.1; Accelrys, Inc.: San Diego, CA, 2012.
(51) Krokidis, X.; Raybaud, P.; Gobichon, A.-E.; Rebours, B.; Euzen,
P.; Toulhoat, H. Theoretical study of the dehydration process of
boehmite to γ-alumina. J. Phys. Chem. B 2001, 105, 5121−5130.
(52) Digne, M.; Sautet, P.; Raybaud, P.; Euzen, P.; Toulhoat, H. Use
of DFT to achieve a rational understanding of acid-basic properties of
γ-alumina surfaces. J. Catal. 2004, 226, 54−68.
https://dx.doi.org/10.1021/acsomega.0c03798
ACS Omega 2020, 5, 26211−26219