Theor Chem Acc (2017) 136:24
DOI 10.1007/s00214-017-2050-x
REGULAR ARTICLE
Effect of cobalt additives and mixed metal sulfides at rubber–
brass interface on rubber adhesion: a computational study
Chian Ye Ling1 · Janne T. Hirvi1 · Mika Suvanto1 · Andrey S. Bazhenov1,2 ·
Katriina Markkula3 · Leo Hillman3 · Tapani A. Pakkanen1 
Received: 13 December 2016 / Accepted: 5 January 2017
© Springer-Verlag Berlin Heidelberg 2017
Abstract  Interaction of rubber models with dopant atoms
on ZnS(110) and Cu2S(111) surfaces, present in rub-
ber–brass adhesive interlayer, has been studied via com-
putational approach using density functional theory. Car-
bon–carbon double bonds and thiol groups in rubber are
generally responsible of the interaction with metal atoms
of ZnS(110) and Cu2S(111) surfaces. Inclusion of a cop-
per atom into a zinc sulfide environment weakens the inter-
action with rubber. The incorporation of cobalt atoms as
additives on ZnS(110) and Cu2S(111) surfaces enhances
the adsorption strength with rubber. The cobalt dopant
increases the adsorption strength of all functional groups of
rubber with zinc sulfide, while in doped copper sulfide only
the carbon–carbon double bond interaction with rubber is
enhanced. It is noteworthy that also the adsorption of satu-
rated hydrocarbons on zinc sulfide is improved by cobalt
doping indicating enhanced carbon–hydrogen bond interac-
tion with the sulfide surface.
Keywords  Density functional · Adhesive interlayer ·
Dopant atom · Zinc sulfide · Copper sulfide · Adsorption
Electronic supplementary material  The online version of this
article (doi:10.1007/s00214-017-2050-x) contains supplementary
material, which is available to authorized users.
* Tapani A. Pakkanen
tapani.pakkanen@uef.fi
1
Department of Chemistry, University of Eastern Finland,
P.O. Box 111, 80101 Joensuu, Finland
2
Nanoscience Center, Department of Chemistry, University
of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland
3
R & D, Car Tyres, Nokian Tyres plc., P.O. Box 20,
37101 Nokia, Finland
1 Introduction
Brass-plated steel cords are used as a reinforcing material
in rubber tires, hydraulic hoses, and conveyor belts. Their
function is to provide stiffness and sufficient mechanical
strength to rubber–steel cord products. During the curing
process of manufacturing, a rubber–brass adhesion inter-
face is formed. The adhesion interface is very complex in
terms of its structure and composition, because in addition
to copper and zinc sulfides [1–5], copper and zinc oxides
and hydroxides are also formed simultaneously due to the
presence of oxygen and water in rubber [6, 7]. Therefore,
in order to realize a strong adhesion between rubber and
brass, a stable interfacial structure with adequate thickness
is necessary for the adhesion interface.
A good adhesion between rubber and brass requires
optimal growth of interfacial sulfides. Insufficient growth
of copper sulfide weakens the adhesion, while an excessive
growth leads to cohesive failures [6, 8]. Additives are gen-
erally required to improve the adhesion between rubber and
brass. Commercially available additives include cobalt salts
[9–11], zinc borate [12], resorcinol–formaldehyde resin
[13, 14], and methylene donors [15]. The additives enhance
migration of copper in order to form the essential amount
of copper sulfide needed in the adhesive interlayer [10, 15].
Addition of cobalt salts as additives affect not only the
formation of an adequate copper sulfide layer but also the
durability of rubber–metal bonds. It has been reported that
cobalt provides protection during aging, for example at
high humidity and temperatures [16]. The aging properties
are improved due to the formation of cobalt oxide which
slows the dezincification, thus hindering the debonding
process. Even though the influence of cobalt as an addi-
tive on rubber–brass adhesion has been extensively stud-
ied, it is an active research area due to the complexity of
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the bonding mechanism. However, there is only limited

atomic-level information on the effect of cobalt on rubber–
brass adhesion.
A detailed understanding of the rubber–brass adhesion
for improvement and control of rubber adherence to brass-
plated steel cords is of great importance. We have recently
reported an atomic-level study on interaction between
rubber adsorbate models and metal sulfide surfaces at the
adhesive interlayer. We demonstrated that functional groups
of rubber give rise to different interaction strength order on
zinc and copper sulfide surfaces [17]. In the present study,
we investigate rubber–brass adhesion, taking into account
mixed copper–zinc sulfides and the effect of cobalt addi-
tives in zinc and copper sulfide surfaces. Our aim is to
rationalize the effect of dopants on the rubber–metal sulfide
interaction at atomic level.

2 Models and methods

Based on our previous study [17], Cu2S(111) surface

exhibits stronger interaction with rubber than CuS(001)
surface. Therefore, in the present adsorption study, we
are focusing only on ZnS and Cu2S surface models. The
construction of surface models is based on our previously
reported study [17]. The optimized bulk structures of zinc
sulfide (cubic zinc blende [18]) and copper sulfide (cubic
antifluorite [19]) were used for cleavage of the ZnS(110)
[20, 21] and Cu2S(111) [22] surfaces. The optimized lat-
tice parameters for bulk zinc and copper sulfides are 5.474
and 5.652 Å; being slightly larger than the experimen-
tal values of 5.400 Å [23] and 5.629 Å [24]. The (2 × 2)
supercell surfaces were employed, where the thicknesses
of ZnS(110) and Cu2S(111) slabs were chosen to be four
and six atomic layers, respectively. The bottom half of the
layers were fixed at equilibrium bulk environment for the
adsorption studies.
Doping is realized by substituting one metal atom on the
unconstrained side of sulfide surfaces (Fig. 1). To study the
influence of mixed metal sulfide surface, we chose the sim-
plest case, which is the ZnS(110) surface doped with a cop-
per atom, denoted as Cu/ZnS(110). On the other hand, both
ZnS(110) and Cu2S(111) are doped with a cobalt atom,
Fig. 1  Top and side views of doped a ZnS(110) and b Cu2S(111)
denoted as Co/ZnS(110) and Co/Cu2S(111), in order to surface models. Blue, yellow, red, and black spheres represent zinc,
predict the effect of cobalt as an additive. Adsorbate mod- sulfur, copper, and dopant atoms, respectively
els, shown in Fig. 2, are constructed from rubber structure
and allowed to relax freely on the doped sulfide surfaces.
They represent elementary functional groups of vulcanized However, spin-unpaired methodology is employed as
rubber such as saturated hydrocarbons (methane, ethane, unpaired electrons are introduced due to doping by copper
and propane), ethene, and hydrogen sulfide. Larger models or cobalt atom. We have also verified our previous results
such as methyl- and thiol-substituted ethenes are also used. with spin-unpaired calculations, and the adsorption ener-
The choice of the computational method and the basis gies are very close to those of the spin-paired calculations.
sets is based on the previously reported evaluation [17]. All calculations were done using the Crystal09 program

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Theor Chem Acc (2017) 136:24 Page 3 of 7  24

Fig. 2  Adsorbate models
derived from rubber structure

Table 1  Calculated adsorption Adsorbate ZnS(110) Cu2S(111) Cu/ZnS(110) Co/Cu2S(111) Co/ZnS(110)

energies (in kJ mol−1) on [17] [17]
undoped and doped metal
sulfide surfaces Methane −3.0 −0.5 −2.0 −0.9 −27.0
Ethane −4.3 −0.8 −2.4 −1.0 −30.1
Propane −3.0 −1.0 −2.7 −1.2 −29.6
Ethene −29.8 −48.2 −15.5 −79.1 −71.5
Hydrogen sulfide −61.4 −39.3 −36.8 −43.8 −98.8
Methyl-substituted ethene −39.8 −53.7 −24.2 −79.7 −78.5
Thiol-substituted ethene −50.5 −41.5 −33.9 −69.7 −89.1

[25] at DFT level using the PBE0 hybrid exchange–corre-
lation functional [26–28]. The optimized def-TZVP basis
sets were used for copper, zinc (available in supplemen-
tary data of Ref. [17]), and cobalt atoms (available in sup-
plementary data Appendix A), and the standard def-TZVP
basis set was used for carbon, sulfur, and hydrogen atoms
[29]. The k-point densities for the calculations are about
4.5 Å−1 for zinc sulfide and 11.0 Å−1 for copper sulfide in
each periodic direction. The counterpoise method has been
used to correct the basis set superposition error (BSSE) in
the calculated adsorption energies [30].
3 Results and discussion
3.1 Adsorption on Cu/ZnS(110) surface
Our focus is on the interaction of adsorbate models with
the surface metal atoms since they play the main role in the
interfacial adhesion [17]. The adsorption energies on top of
dopant atom on doped surfaces are presented in Table 1 and
compared with those of undoped reference surfaces [17].
The adsorption energies for functional group models on the
mixed Cu/ZnS(110) surface are smaller than on undoped
ZnS(110) surface, but follow the same trend. Saturated
hydrocarbons exhibit only weak interactions with adsorp-
tion energies less than −5 kJ mol−1. Adsorption energy of
hydrogen sulfide is about twice as large as that of ethene.
The same qualitative observation can also be made for the
larger adsorbate models as thiol-substituted ethene adsorbs
stronger than methyl-substituted ethene.
The optimized adsorption geometries on top of copper
dopant atom on Cu/ZnS(110) surface are shown in Fig. 3a–
g. The ethene interacts via the carbon–carbon double bond
and hydrogen sulfide through the lone electron pairs of sul-
fur. Outward relaxation of the copper atom interacting with
either ethene or hydrogen sulfide indicates stronger inter-
action compared to saturated hydrocarbons. On the other
hand, the distortion of adsorbate from the free geometry is
smaller on Cu/ZnS(110) surface than on ZnS(110) surface.
The elongation of ethene double bond and bending of its
end groups is given in Table 2. The larger adsorbate mod-
els confirm the adsorption preference of functional groups
as methyl-substituted ethene adsorbs from the double bond
and thiol-substituted ethene from the thiol group.
Adsorption on top of zinc atom next to the dopant on
Cu/ZnS(110) surface was also investigated. However, the
copper doping seems to have only a local effect on the sur-
face and was not found to influence the adsorption proper-
ties of neighboring zinc atoms.

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 24   Page 4 of 7 Theor Chem Acc (2017) 136:24

Fig. 3  Side views of optimized adsorption geometries of a methane, atom on Cu/ZnS(110) surface. Blue, yellow, red, gray, and white
b ethane, c propane, d ethene, e hydrogen sulfide, f methyl-substi- spheres represent zinc, sulfur, copper, carbon, and hydrogen atoms,
tuted ethene, and g thiol-substituted ethene on top of copper dopant respectively

Table 2  Adsorption energies (ΔEads) and geometrical parameters of ethene bound to metal (M) sulfide surfaces

Free ZnS(110) Cu2S(111) Cu/ZnS(110) Co/Cu2S(111) Co/ZnS(110)

ethene [17] [17]

ΔEads (kJ mol‒1) – −29.8 −48.2 −15.5 −79.1 −71.5

C–M distance (Å) – 2.57 2.21 2.65 2.08 2.39
C=C bond length (Å) 1.32 1.34 1.35 1.33 1.38 1.34
Bending of CH2 groups (°) 0.0 3.5 7.3 2.8 17.0 5.5

Geometrical parameters of free ethene are included as a reference

3.2 Effect of cobalt as adhesion promoter
3.2.1 Adsorption on Co/Cu2S(111) surface
The adsorption energies on top of cobalt dopant atom on
Co/Cu2S(111) surface are presented in Table 1. The general
adsorption energy trend is similar to the undoped case, but
adsorption due to the ethene functional group is enhanced.
Saturated hydrocarbons display only weak interaction with
cobalt atom on Co/Cu2S(111) surface. In the case of hydro-
gen sulfide, the adsorption energy is slightly increased. How-
ever, ethene–cobalt interaction is about 30 kJ mol−1 stronger
than the ethene–copper interaction on undoped Cu2S(111)
surface. Note that even undoped Cu2S(111) surface adsorbs
ethene stronger than hydrogen sulfide, which is opposed to
that observed on ZnS(110) surface. The same overall effect
is also found in the case of larger substituted ethene models.
The optimized adsorption geometries on top of cobalt
dopant atom on Co/Cu2S(111) are illustrated in Fig. 4a–g.
A notable outward relaxation of the cobalt atom is clearly
visible in the case of sulfur and especially carbon–car-
bon double bond containing adsorbates. The distortion of
ethene from the gas phase geometry is also larger than on
undoped Cu2S(111) surface (see Table 2). The most signifi-
cant structural difference compared to undoped and doped
ZnS(110) surfaces is found for the thiol-substituted ethene.
The coordination takes place via double bond instead of
thiol group which can be rationalized by larger adsorption
energy of ethene than hydrogen sulfide.
3.2.2 Adsorption on Co/ZnS(110) surface
The adsorption energies on top of cobalt dopant atom
on Co/ZnS(110) surface are given in Table 1. The gen-
eral trend of the adsorption energies follows again that of
the corresponding undoped surface. However, a notable
increase in the calculated adsorption energies is found
due to the cobalt doping. Saturated hydrocarbons, ethene,

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Theor Chem Acc (2017) 136:24 Page 5 of 7  24
Fig. 4  Side views of optimized adsorption geometries of a methane,
b ethane, c propane, d ethene, e hydrogen sulfide, f methyl-substi-
tuted ethene, and g thiol-substituted ethene on top of cobalt dopant
Fig. 5  Side views of optimized adsorption geometries of a methane,
b ethane, c propane, d ethene, e hydrogen sulfide, f methyl-substi-
tuted ethene, and g thiol-substituted ethene on top of cobalt atom on
and hydrogen sulfide display higher adsorption energies
on cobalt dopant atom with values of −30.0, −71.5, and
−98.8 kJ mol−1, respectively. The interaction of satu-
rated hydrocarbons is about 25.0 kJ mol−1 stronger than
on undoped ZnS(110) surface, while ethene and hydro-
gen sulfide adsorb about 40.0 kJ mol−1 stronger than on
undoped ZnS(110) surface. The stronger interactions of
ethene and hydrogen sulfide with cobalt dopant atom on
Co/ZnS(110) surface are also reflected on the adsorption of
substituted ethenes. The corresponding interactions are also
atom on Co/Cu2S(111) surface. Red, yellow, green, gray, and white
spheres represent copper, sulfur, cobalt, carbon, and hydrogen atoms,
respectively
Co/ZnS(110) surface. Blue, yellow, green, gray, and white spheres
represent zinc, sulfur, cobalt, carbon, and hydrogen atoms, respec-
tively
about 40 kJ mol−1 stronger compared to substituted ethenes
on undoped ZnS(110) surface.
The comparison of adsorption energies to those on top
of cobalt dopant atom on Co/Cu2S(111) surface highlights
the effect of surrounding matrix. Ethene adsorption energy
on Co/ZnS(110) surface is about 10 kJ mol−1 smaller
than on Co/Cu2S(111) surface. In contrast, hydrogen
sulfide adsorbs on Co/ZnS(110) surface about 50 kJ mol−1
stronger than on Co/Cu2S(111) surface. Hence, opposite
adsorption preference of ethene and hydrogen sulfide on
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Table 3  Adsorption energies (ΔEads) and geometrical parameters of methane bound to metal (M) sulfide surfaces
Free ZnS(110) [17] Cu2S(111) [17] Cu/ZnS(110) Co/Cu2S(111) Co/ZnS(110)
methane

ΔEads (kJ mol‒1) – −3.0 −0.5 −2.0 −0.9 −27.0

C–M distance (Å) – 3.25 3.36 3.59 3.41 2.63
Longest C–H bond length (Å) 1.091 1.092 1.090 1.091 1.091 1.099
Largest H–C–H angle (°) 109.5 110.8 109.6 110.2 109.7 114.9
Smallest H–C–H angle (°) 109.4 108.3 109.3 108.9 109.2 106.6

Geometrical parameters of free methane are included as a reference

Fig. 6  Effect of the dopant

atom on adsorption strength (in
kJ mol−1) of rubber adsorbate
models. Unsaturated hydrocar-
bons present the average effect
on adsorption of ethene and
methyl-substituted ethene

same dopant atom can be observed in the two matrices. The
same observation is valid also for larger rubber adsorbate
models.
The optimized adsorption geometries on top of cobalt
dopant atom on Co/ZnS(110) are shown in Fig. 5a–g.
The most notable structural difference compared to
undoped and copper-doped ZnS(110) surfaces can be
seen in the case of saturated hydrocarbons. Adsorption
energies and geometrical parameters of methane on dif-
ferent sulfide surfaces are presented in Table 3. Stronger
interaction of methane is connected to the shorter car-
bon–cobalt distance on Co/ZnS(110) surface. Actually,
transition metal surfaces are known to facilitate meth-
ane dissociation. It has been reported that cobalt sur-
face is active in dehydrogenation of methane [31, 32]
with an activation barrier of 120 kJ mol−1 [32]. Appar-
ently also cobalt dopant in ZnS(110) matrix moderately
activates the carbon–hydrogen bond which rationalizes
the increased interaction. The same phenomenon is
observed for the other saturated hydrocarbon adsorbates
as well.
3.3 Promotional impact of dopants
In general, saturated hydrocarbons show only weak interac-
tion with zinc and copper atoms on undoped ZnS(110) and
Cu2S(111) surfaces, whereas stronger interaction is real-
ized through carbon–carbon double bonds and thiol groups
of rubber. The interaction trend of the adsorbate mod-
els and doped sulfide surfaces follows those of undoped
sulfide surfaces displaying the crucial effect of the matrix
surrounding the dopant atom. However, the dopant atoms
either increase or decrease adsorption energy. The effect
of dopant atom on adsorption strengths of rubber models
is presented in Fig. 6. The copper dopant on Cu/ZnS(110)
surface weakens the interaction with carbon–carbon dou-
ble bonds and thiol groups of rubber as it displays smaller
adsorption energies than undoped ZnS(110) surface.

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Theor Chem Acc (2017) 136:24 Page 7 of 7  24
The doping by cobalt atom has a positive effect on rub-
ber–brass adhesion. The cobalt doping of Cu2S(111) sur-
face improves notably adhesion with carbon–carbon double
bonds, while there is only a slight increase in the adhesion
with thiol groups of rubber. A notable increase in adsorp-
tion energy of thiol-substituted ethene with cobalt atom
on Co/Cu2S(111) surface is due to the stronger binding
strength of the carbon–carbon double bond than the thiol
group. On the other hand, the cobalt doping of ZnS(110)
surface improves significantly the adhesion of both carbon–
carbon double bonds and thiol groups of rubber. Moreover,
saturated hydrocarbon groups of rubber are activated lead-
ing to increased adhesion of rubber on Co/ZnS(110) sur-
face. The carbon–hydrogen bond activation is not observed
on Co/Cu2S(111) surface.
4 Conclusions
In order to understand the rubber–brass adhesion at atomic
level, we have studied the process by investigating the
effect of mixed copper–zinc on ZnS(110) surface as well
as the effect of cobalt as an additive on ZnS(110) and
Cu2S(111) surfaces. Adsorption energetics of adsorbate
models on doped sulfide surfaces were examined.
The different behavior of adsorbate models derived from
natural rubber toward dopant atom on Zn and Cu sulfide
at adhesive interlayer is the key in the rubber–brass adhe-
sion. The interaction between rubber and brass is found to
be weakened when rubber adheres on mixed copper–zinc
sulfide surface. The inclusion of cobalt atom as an addi-
tive is important in rubber–brass adhesion since it enhances
the interaction between rubber and sulfide surfaces. Cobalt
dopants with ability to activate carbon–hydrogen bonds can
be useful to enhance rubber–brass adhesion. The role of
doping of zinc and copper sulfides has been shown to be
an important in the optimization of the interphase adhesion.
Acknowledgements Financial support provided by the Finnish
Funding Agency for Technology and Innovation TEKES and the
European Union/European Regional Development Fund (ERDF) for
the “Smart Active Materials” project (70058/11) and “Vauhtia Ren-
kaisiin” project (3246/31/2015) is gratefully acknowledged. The com-
putations were made possible by use of the Finnish Grid Infrastruc-
ture resources.
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