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Journal of Adhesion Science and

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Adhesion Between Rubber Compounds

Containing Various Adhesion Promoters and
Brass-Plated Steel Cords. Part II. Effect of
Accelerator Loading in Rubber Compounds
a
Gyung Soo Jeon
a
Department of Fire-Safety Management, Jeonnam Provincial College,
Damyang, Jeonnam 517-802, South Korea;, Email: gjeon@dorip.ac.kr

Version of record first published: 02 Apr 2012

To cite this article: Gyung Soo Jeon (2008): Adhesion Between Rubber Compounds Containing Various
Adhesion Promoters and Brass-Plated Steel Cords. Part II. Effect of Accelerator Loading in Rubber
Compounds, Journal of Adhesion Science and Technology, 22:12, 1255-1284

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 Journal of Adhesion Science and Technology 22 (2008) 1255–1284
www.brill.nl/jast

Adhesion Between Rubber Compounds Containing Various

Adhesion Promoters and Brass-Plated Steel Cords. Part II.
Effect of Accelerator Loading in Rubber Compounds

Gyung Soo Jeon ∗

Department of Fire-Safety Management, Jeonnam Provincial College,
Damyang, Jeonnam 517-802, South Korea
Downloaded by [University of Guelph] at 01:55 18 July 2012

Received in final form 20 April 2008

Abstract
The adhesion property between rubber compounds containing different types of adhesion promoters
(resinous adhesion promoter (methylene donor/acceptor), cobalt salt and zinc borate) and loading amounts
of accelerator and brass-plated steel cord was investigated to understand the effect of accelerator loading in
rubber compounds on their adhesion characteristics to the brass-plated steel cords. The adhesion property
of the rubber compounds to brass-plated steel cord was largely dependent on the type of adhesion promoter
and the loading amount of accelerator in the rubber compounds. Among the various adhesion promoters
incorporated, zinc borate showed the largest enhancement of adhesion properties after cure. For the rubber
compounds containing zinc borate, pull-out force increased two times with increasing loading amount of
accelerator from 0.4 to 1.6 phr. But for the rubber compounds containing either resinous adhesion promoter
or cobalt salt, pull-out force decreased slightly with increasing loading amount of accelerator. For cobalt
salt incorporated, interfacial failure between adhesion interphase and rubber compound after humidity ag-
ing occurs dominantly, whereas a cohesive failure occurs dominantly in the weak boundary layer closely
adjacent to the adhesion interphase for both resinous adhesion promoter and zinc borate. Adhesion property
was interpreted in terms of the interphases between the rubber compounds and the brass-plated steel cords
studied using Auger electron spectroscopy. Suppression of dezincification was observed for a high loading
of the accelerator in the rubber compounds.
© Koninklijke Brill NV, Leiden, 2008

Keywords
Brass-plated steel cord, rubber compound, adhesion promoter, cobalt salt, zinc borate, resorcinol formalde-
hyde resin, methylene donor, accelerator, rubber-to-brass adhesion, adhesion interphase, AES, depth pro-
file, adhesion retention, dezincification

* To whom correspondence should be addressed. Tel.: +82-61-380-8671; Fax: +82-61-381-9100; e-mail:

gjeon@dorip.ac.kr

© Koninklijke Brill NV, Leiden, 2008 DOI:10.1163/156856108X319917

 1256 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284

1. Introduction
The production of tires is among the most important automotive applications where
adhesion is extremely important. A steel-belted radial tire contains several rein-
forcing materials such as brass-plated steel cords and polyester fabric cords. The
adhesion of rubber compounds to these cords is of critical importance for the per-
formance and safety of tire [1]. The steel cords in the belts of a tire consist of
a number of thin filaments that have been combined in a so-called cord construction.
Each cord is, therefore, flexible and strong. Each filament is individually coated
with a thin layer of brass, typically containing 63% Cu and the balance is zinc. For
a successful use of brass-plated steel cords in radial tires, attainment and mainte-
nance of good rubber compounds to brass-plated steel cords adhesion becomes vital
[2, 3].
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The adhesion mechanism is found to be dependent on the chemical composition

and the surface characteristics of the brass plating [4] and the composition of cure
system (sulfur and accelerator) [5], type and loading of adhesion promoter [6–20]
in rubber compounds, and cure conditions (cure temperature and time) [21, 22].
Brass plating on the surface of steel cords reacts with sulfur in the rubber com-
pound during the curing process of tire manufacturing, forming an adhesion inter-
phase between the rubber compound and the steel cord. Copper and zinc also react
with oxygen and water in the rubber, forming oxides and hydroxides of both copper
and zinc.
The major components of the adhesion interphase are sulfides, oxides and hy-
droxides of copper and zinc [23–25]. Adhesion becomes weak when copper sulfide
is not sufficiently grown in the interphase, but an excessive growth of copper sulfide
or zinc oxide brings about their own cohesive failures [26–28]. Failure rarely occurs
between the rubber compounds and the copper sulfide layer. It generally occurs co-
hesively within the copper sulfide layer or within an interphase of zinc oxide below
the copper sulfide layer. Thus the optimum growth of copper sulfide is essential
to form an adequately thick adhesion interphase between the rubber and the brass,
resulting in good adhesion [29, 30]. Good adhesion generally requires the use of
several groups of adhesion promoters. Several compounds such as cobalt salt [6–9,
12], zinc borate [16], resorcinol-formaldehyde resin [13, 31], and methylene donors
[10, 11] are commercially used as adhesion promoters to enhance the migration of
copper, forming the necessary amount of copper sulfide in the adhesion interphase.
They are used either individually or simultaneously in the rubber compounds.
During vulcanization of adhesion samples, a lack of sulfur in a thin rubber layer
closely adjacent to adhesion interphase occurs due to the large consumption of
sulfur in the formation of adhesion interphase instead of vulcanization [21, 22]. Un-
fortunately, the diffusion of sulfur from rubber bulk to the thin rubber layer closely
adjacent to adhesion interphase may be effectively hindered by the sulfur cross-
linked network formed in the bulk rubber at initial vulcanization stage. As the cure
of adhesion samples proceeds, the bulk rubber is completely cured whereas the thin
rubber layer adjacent to the adhesion interphase does not cure sufficiently. Thus the
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1257

thin rubber layer adjacent to the adhesion interphase of brass-plated steel cord has
low sulfur crosslink density compared to rubber bulk [32].
Cobalt salt has been used as an adhesion promoter in the rubber compounds
to accelerate the activation of sulfur in the interphase by inducing formation of
an adequate copper sulfide layer, thus making better adhesion possible [6–9, 12].
However, an adverse effect is observed for rubber compounds with high levels of
cobalt salt, or after humidity aging, due to the formation of an excessive copper
sulfide layer which is prone to cohesive failure [33].
Zinc borate has also been used as an adhesion promoter in rubber compounds to
retain stable adhesion by inhibiting corrosion of the adhesion interphase by virtue
of boron [16, 34].
Resorcinol-formaldehyde resin has been employed in rubber compounds to en-
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hance adhesion retention under hostile environments by suppressing the growth of

copper sulfide in the adhesion interphase [31]. A methylene acceptor (Cyrez-964,
see Section 2.1) has been used together with a methylene donor such as resorcinol-
formaldehyde resin and it was capable of adsorbing the amine generated, which
is the principal cause of corrosion in the adhesion interphase, on the silica surface
during vulcanization of rubber compounds [10, 11]. Also, it reacted with methylene
donor and subsequently formed an interpenetrating network near the adhesion in-
terphase during vulcanization. The interpenetrating network formed is responsible
for the reinforcement of weak boundary layer adjacent to adhesion interphase.
Sulfidation of brass surface is not due to its interaction with elemental sulfur, but
it is the result of the interaction between the brass surface and accelerator-sulfur
reaction products which can be represented by the general structure, Ac-Sy -Ac and
Ac-Sy -H, where Ac is an accelerator-derived moiety. The value of subscript, y,
increases with the ratio of the concentration of sulfur to the concentration of accel-
erator used in the cure system [35]. It is known that high sulfur system in rubber
compounds is beneficial to good adhesion to brass-plated steel cord. According
to recent results reported by Jeon [34], adhesion property of rubber compound to
brass-plated steel cord was found to be largely dependent on the type of adhesion
promoter incorporated in the study of the effect of sulfur loading on the adhesion
property.
The accelerator should not form a stable copper complex which dissolves in
the rubber compounds. This would be quite corrosive to the brass plating. In this
respect, benzothiazole and their sulfenamides are much better than dithiocarbamate.
Since adhesion between two phases implies that some kind of chemical or phys-
ical interaction has taken place, much attention has been paid to characterize the
adhesion interphase formed between the two phases (rubber compound and brass-
plated steel cord). Samples of adhesion interphases were prepared by inserting
a filter paper between the rubber compound and the brass-plated steel cord [36–40]
and they were analyzed by Auger electron spectroscopy (AES) in order to interpret
the adhesion properties.
 1258 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284

In this study, the adhesion properties between rubber compounds with different
loading amounts of accelerator loading and brass-plated steel cords were investi-
gated to explain the effect of the accelerator in rubber compounds containing cobalt
salt, zinc borate and resinous adhesion promoter (methylene donor/methylene ac-
ceptor) individually on the formation, growth and deterioration of adhesion inter-
phase from the depth profiles obtained by AES. Also, the adhesion property was
studied to understand the effect of loading amount of accelerator in rubber com-
pounds on the adhesion to brass-plated steel cords.

2. Experimental
2.1. Preparation of Rubber Compounds
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Six kinds of rubber compounds having different loading amounts of accelerator and
types of adhesion promoters were prepared as follows. Compositions of the mas-
terbatch and final mixed compound are given in Table 1. On the basis of Table 1,
two kinds of rubber compounds containing 1 phr of cobalt salt were prepared at
low loading of accelerator (0.4 phr) as well as high loading of accelerator (1.6 phr).
Other two kinds of rubber compounds containing 1 phr of zinc borate were pre-
pared at low loading of accelerator (0.4 phr) as well as high loading of accelerator
(1.6 phr). The other two kinds of rubber compounds containing 2 phr of methylene

Table 1.
Composition of rubber compounds used

Component Chemical or trade name Manufacturer Content (phr)

Masterbatch
Natural rubber SMR-20 Lee Rubber Co., Malaysia 100
Carbon black N330 Lucky Co., Korea 50
Processing oil A#2 Michang Co., Korea 4
Activator ZnO Hanil Co., Korea 10
Adhesion promoter Manobond 680Ca Rhone Poulenc Co., France varied
Adhesion promoter B-18Sb Indspec Co., USA varied
Adhesion promoter RP15929c Borax Co., USA varied
Final mixing
Activator Stearic acid Pyungwha Co., Korea 0.5
Accelerator Santocure MORd Monsanto Co., USA varied
Adhesion promoter Cyrez-964e Cytec Co., USA varied
Sulfur Crystex HS OT 20 Akzo Nobel Co., 4
The Netherlands
a Cobalt boroacylate (Co 23 wt%).
b Resorcinol-formaldehyde resin.
c Zinc borate (2ZnO B O · 3.5H O).
3 2 3 2
d 2-(morpholinothio)-benzothiazole sulfenamide.
e Hexamethoxymethylmelamine with 35 wt% silica.
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1259

donor/4 phr of methylene acceptor were prepared at low loading of accelerator

(0.4 phr) as well as high loading of accelerator (1.6 phr). The cobalt salt used was
Manobond 680C (Cobalt boroacylate, Co 23 wt%, Rhone Poulenc Co., France). The
zinc borate incorporated was zinc borate hydrate (Borax Co., USA). The methylene
acceptor used was B-18S (resorcinol-formaldehyde resin, Indspec Co., USA) and
methylene acceptor was Cyrez-964 (Hexamethoxymethylmelamine with 35 wt%
silica, Cytec Co., USA).
The rubber compounds were mixed as described in ASTM D-3184 using an in-
ternal mixer (Banbury Mixer model 82, Farrel Co., USA). The ingredients for the
masterbatch were mixed for 10 min at a rotor speed of 40 rpm and the dump tem-
perature was found to be around 150◦ C. After the masterbatch had cooled down to
room temperature, the final mixing components were mixed for 5 min at 30 rpm and
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the dump temperature was found to be around 90◦ C. After mixing, the compounds
were carefully re-milled into flat sheets on a two-roll mill (model MKIII, Farrel Co,
USA).
Rheocurves of the rubber compounds were recorded using a Monsanto Rheome-
ter 100 at 160◦ C. The t90 time, i.e. the time required to achieve 90% cure, and
maximum torque were determined from the rheogram. Mooney viscosity of the
rubber compounds at 100◦ C was also obtained using a Monsanto MV-2000 instru-
ment according to ASTM D-1646.
The hardness of vulcanizates was measured using a Shore A durometer according
to ASTM D-2240, and tensile properties were measured with a tensile tester (model
6021, Instron, USA) according to ASTM D-412. After vulcanizates were thermally
aged for 24 h at 100◦ C, mechanical tensile properties such as modulus and tensile
strength were also measured.
2.2. Adhesion Test
Based on the procedure described in ASTM D-2229, T-test specimens with
12.7 mm cord embedment in the rubber block were cured at 160◦ C on a hot cure
press. A construction structure of 3 × 0.35 in which 3 steel filaments having the
same diameter of 0.35 mm were twisted together was used. The copper content in
brass plating was 63.7 wt%.
Curing was continued for 5 min longer than the t90 time. For humidity aging,
specimens were placed in a humidity chamber at 83◦ C/95% relative humidity for
5, 10 and 15 days. Also, the adhesion samples were aged thermally at 100◦ C for 5,
10 and 15 days.
Pull-out force was determined as the maximum force exerted by the tensile tester
on the T-test adhesion sample during the pull-out test, at a crosshead speed of
10 mm/min. Rubber coverage, defined as the percentage of rubber-covered area
on the cord surface, was also noted. The relative extent of rubber coverage on the
pulled-out cord as determined visually was expressed as: bare steel cord as 0% to
steel cord completely covered with rubber as 100%. Both pull-out force and rub-
ber coverage reported were the averages from six specimens. The morphology of
 1260 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284

the pulled-out steel cord surface after measuring the pull-out force was investigated
using an image analyzer.
2.3. Analysis of the Adhesion Interphase
Brass-plated steel cord was covered with a filter paper (pore size: 5 µm; catalog
no 142 50, Millipore Co., USA), sandwiched between two uncured pads of rubber
compound, and then placed in a pad mold [36–41]. Curing and aging conditions for
forming the adhesion interphase of rubber compound/brass-plated steel cord were
the same as in the preparation of the T-test specimens. After the various treatments
such as vulcanization and/or aging, samples for analysis of the adhesion interphase
were obtained by peeling away the filter paper placed on the steel cord. Sulfur from
the rubber compound migrated through the pores of the filter paper and reacted
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with brass plating on brass-plated steel cord, forming an adhesion interphase. After
removing the rubber and filter paper from the brass-plated steel cord, the adhesion
interphase, which contained copper sulfide and zinc oxide, remained on the brass-
plated steel cord.
The depth profiles from the interphase in contact with the rubber compound to
the bulk of the brass-plated steel cord were recorded on a Perkin-Elmer Auger
spectrometer (model Phi 670, Perkin-Elmer Co., USA). A 10 × 10 µm2 area was
examined using an ion beam with an acceleration voltage of 5.0 kV, a current of
0.03 µA, and an incident angle to the specimen of 60◦ . Surface concentrations
were determined every 0.5 min from the Auger peaks of detected elements with
compensation for their sensitivity factors. A sputter gun with an argon ion beam
rastered a 2 × 2 mm2 area for depth profiling. The sputter rate was determined to
be 4.4 nm/min using tantalum pentoxide. It was difficult, however, to determine the
sputter rate precisely for the adhesion interphase because it included various chem-
ical components with varying concentrations. Therefore, the sputter time instead of
the absolute depth was used to indicate the depth of the adhesion interphase in this
paper.

3. Results and Discussion

3.1. Physical Properties of Rubber Compound
The cure and viscoelastic properties of green rubber compounds are summarized in
Table 2. In the rubber compounds containing resinous adhesion promoter, cure rate
of rubber compound is very small compared to those containing either cobalt salt
or zinc borate. This may stem from the adsorption of accelerator on silica surface
in methylene acceptor incorporated. Regardless of the type of adhesion promoter
incorporated, cure rate of rubber compounds increased with loading amount of ac-
celerator. Especially, cure rate of rubber compound containing resinous adhesion
promoter increased as much as five times with increasing loading amount of accel-
erator from 0.4 to 1.6 phr.
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1261

Table 2.
Cure propertiesa determined by oscillating disc type rheometera and Mooney viscoelastic properties
by Mooney viscometer testb for green rubber compounds with different loadings of accelerator and
types of adhesion promoters

Co Zn Resin Accelerator Time (min) CRIh Torque (J) Mooney

salt borate (phrc / (phr) (min−1 ) viscosityi
(phr) (phr) phrd ) t2 e t40 f t90 g min max

– – 2/4 0.4 3.2 6.5 27.1 4.2 2.03 4.44 80

– – 2/4 1.6 3.2 6.0 8.2 20.1 1.93 5.33 79
1 – – 0.4 2.4 4.0 6.2 26.5 1.63 4.52 60
1 – – 1.6 3.1 4.2 5.3 45.7 1.57 6.07 62
– 1 – 0.4 3.2 4.4 7.6 22.9 1.63 4.00 74
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– 1 – 1.6 3.0 4.1 6.2 32.1 1.46 4.84 70

a Rubber compounds were sheared to ±1◦ and 1.67 Hz at 160◦ C.
b Rubber compounds were sheared to 2 rpm at 100◦ C.
c Loading amount of B-18S as methylene donor.
d Loading amount of Cyrez-964 as methylene acceptor.
e Time required to attain 2% cure.
f Time required to attain 40% cure.
g Time required to attain 90% cure.
h CRI (Cure Rate Index) = 100/(t − t ).
90 2
i Torque, ML
1+4,100◦ C .

Regardless of the type of adhesion promoter, the mechanical crosslink density,

which is traditionally defined as the difference between the maximum torque and
the minimum torque of the rubber compound in the rubber industry, increased with
increasing loading amount of accelerator into rubber compounds. The increase in
the mechanical crosslink density of rubber compound containing cobalt salt is con-
spicuous with increasing loading amount of accelerator.
The mechanical crosslink density of rubber compounds containing resinous ad-
hesion promoter is similar to that containing zinc borate. From the above result, the
good mechanical property of rubber compounds containing cobalt salt can be ex-
plained. From the results mentioned above, the loading amount of accelerator in the
rubber compounds containing different types of adhesion promoters affected both
the cure rate and crosslink density of rubber compounds. It is well known that the
increase in loading amount of accelerator produces higher crosslinked density and,
therefore, high modulus, hardness, etc. [35]. Also, it is known that the monosulfidic
crosslinks in the vulcanizates formed mainly at high loading of accelerator. High
loading of accelerator used sulfur efficiently in the production of crosslinks; there-
fore, the crosslinks are shorter than in the case of conventional vulcanization. The
efficient vulcanization produces more monosulfidic crosslinks and less polysulfidic
ones, or their average sulfur rank, which is the length of sulfur chain involved in
sulfur crosslinks, is lower.
 1262 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284

Table 3.
Mechanical properties of unaged vulcanizates with different loadings of accelerator and types of ad-
hesion promoters

Co Zn Resin Accelerator Hardness Modulus (MPa) T.S.c E.B.d

salt borate (phra / (phr) (Shore A) (MPa) (%)
100% 200% 300%
(phr) (phr) phrb )

– – 2/4 0.4 67 2.84 7.7 13.7 17.3 420

– – 2/5 1.6 70 4.80 12.4 20.0 27.5 360
1 – – 0.4 66 3.53 9.0 15.2 24.2 460
1 – – 1.6 73 5.98 14.4 22.1 26.2 370
– 1 – 0.4 67 3.23 8.5 14.7 24.0 470
– 1 – 1.6 69 3.92 10.2 17.2 27.0 460
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a Loading amount of B-18S as methylene donor.

b Loading amount of Cyrez-964 as methylene acceptor.
c Tensile strength.
d Elongation-at-break.

As shown in Table 2, the Mooney viscosity of rubber compounds varies not

only with the loading amount of accelerator but also with the type of adhesion pro-
moter. The rubber compounds containing cobalt salt showed the smallest Mooney
viscosity whereas those containing resinous adhesion promoter showed the largest
Mooney viscosity. These observations may due to the role of dissociated anion salt
in cobalt salt as a lubricant and the role of silica as filler in methylene acceptor,
respectively.
The mechanical properties of vulcanizates without any aging treatment are
shown in Table 3. Regardless of the type of adhesion promoter incorporated, hard-
ness and modulus of vulcanizates increased with increasing loading amount of
accelerator but the elongation at break decreased. The tensile strength of vulcan-
izates with increasing loading amount of accelerator increased regardless of the
type of adhesion promoter incorporated. The largest increase in tensile strength in
the rubber compounds containing zinc borate was found with increasing loading
amount of accelerator.
The mechanical properties of vulcanizates with thermal aging for 24 h at 100◦ C
are presented in Table 4. Compared to the properties of unaged vulcanizates,
modulus and hardness increased with thermal aging but both tensile strength and
elongation-at-break decreased due to the chain scission in the sulfur crosslinks un-
der thermal aging treatment. Regardless of the type of adhesion promoter incorpo-
rated, tensile strength increased with increasing loading amount of accelerator. The
rubber compounds containing zinc borate showed the highest tensile strength for
the thermal aged vulcanizates with all adhesion promoters incorporated. The pres-
ence of zinc compounds can promote the reduction of the sulfur rank of crosslinks
during high temperature aging of the vulcanizate [35]. Higher loading amount of
accelerator produces a good resistance to thermal oxidative aging. The resistance
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1263

Table 4.
Mechanical properties of vulcanizates with different loadings of accelerator and types of adhesion
promoters after thermal aginga

Co Zn Resin Accelerator Hardness Modulus (MPa) T.S.d E.B.e

salt borate (phrb / (phr) (Shore A)
100% 200% 300%
(MPa) (%)
(phr) (phr) phrc )

– – 2/4 0.4 71 4.31 10.6 – 11.9 220

– – 2/4 1.6 76 7.25 17.0 – 21.1 250
1 – – 0.4 73 5.49 12.4 18.3 18.3 300
1 – – 1.6 78 8.62 16.9 – 19.7 210
– 1 – 0.4 69 4.90 11.9 18.3 20.6 340
– 1 – 1.6 75 5.88 14.1 21.9 23.8 330
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a Vulcanizates were thermally aged for 24 hr at 100◦ C.

b Loading amount of B-18S as methylene donor.
c Loading amount of Cyrez-964 as methylene acceptor.
d Tensile strength.
e Elongation-at-break.

to thermally induced loss of crosslinks is thought to be the result of the greater

intrinsic stability of the monosulfidic crosslinks.
3.2. Adhesion Properties of the Rubber Compounds to Brass-Plated Steel Cord
Adhesion properties of the rubber compounds to brass-plated steel cord were found
to be significantly dependent on the type of adhesion promoter and the loading
amount of accelerator in the rubber compounds as shown in Fig. 1. Figure 1 shows
the pull-out force and rubber coverage of the brass-plated steel cord to rubber com-
pounds both immediately after cure and after humidity aging treatment for 15 days.
The effect of the loading amount of accelerator in the rubber compounds on adhe-
sion properties varied with the type of adhesion promoter incorporated. Among the
various adhesion promoters incorporated, zinc borate showed the largest enhance-
ment of adhesion properties after cure.
For the rubber compounds containing zinc borate, pull-out force increased as
much as two times with increasing loading amount of accelerator from 0.4 to
1.6 phr. But for the rubber compounds containing either resinous adhesion promoter
or cobalt salt, pull-out force decreased slightly with increasing loading amount of
accelerator. Regardless of the type of adhesion promoter incorporated, cohesive
failure in the rubber layer occurred after the pull-out test, supported from the high
rubber coverage shown in Fig. 2.
The adhesion of rubber compounds containing zinc borate to brass-plated steel
cords was very sensitive to loading amount of accelerator in the rubber compound.
But the adhesion of rubber compounds containing either resinous adhesion pro-
moter or cobalt salt to brass-plated steel cords was not sensitive to loading amount
of accelerator in the rubber compounds.
 1264 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284
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Figure 1. Adhesion properties of rubber compounds with different loading amounts of accelerator
and adhesion promoters (cobalt salt/zinc borate/resin) to brass-plated steel cord both immediately
after cure and after humidity aging at 83◦ C and 95% relative humidity for 15 days; (a) pull-out force
and (b) rubber coverage.
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1265
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Figure 2. Image analyzer micrographs (magnification: ×50) of pulled-out steel cords from un-
aged adhesion samples with respect to loading amounts of both accelerator and adhesion promoters
(cobalt salt/zinc borate/(methylene donor/methylene acceptor) (phr/phr/phr/(phr/phr)): (a) 4/0/0/(2/4);
(b) 8/0/0/(2/4); (c) 4/1/0/0; (d) 8/1/0/0; (e) 4/0/1/0; (f) 8/0/1/0.

A weak boundary layer in the rubber layer closely adjacent to the adhesion in-
terphase was formed due to the insufficient crosslinking in this rubber layer. The
increase in the loading amount of accelerator in the rubber compounds containing
different adhesion promoters does not cause change in the scorch time as shown
in Table 2. It is well known that the formation of adhesion interphase is completed
essentially before the scorch time of rubber compound. Therefore, a rubber com-
 1266 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284

pound with high loading amount of accelerator may be very affluent with available
accelerator which can be used to post-cure the weak boundary layer in the rubber
layer closely near the adhesion interphase. According to the mechanism mentioned
above, the pull-out force increased with loading amount of accelerator in the rubber
compound.
The resinous adhesion promoter formed an interpenetrating network closely near
the adhesion interphase during vulcanization. Both sulfur crosslinked network and
interpenetrating network retarded the diffusion of accelerator from the bulk rubber
to the rubber layer closely near the adhesion interphase. The high loading of accel-
erator in the rubber compounds containing resinous adhesion promoter reduced the
tendency for weak boundary layer formation adjacent to the adhesion interphase be-
cause of affluence of accelerator in the rubber layer closely adjacent to the adhesion
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interphase.
The cobalt salt in the rubber compounds is known to accelerate adhesion inter-
phase formation during vulcanization. As shown in Fig. 1, increasing the loading
amount of accelerator from 0.4 to 1.6 phr in the rubber compounds did not increase
adhesion properties significantly. For the rubber compounds containing cobalt salt,
rubber coverage stayed constant at 90% with increasing accelerator loading from
0.4 to 1.6 phr. Figure 2 shows pulled-out cord surfaces of unaged adhesion sam-
ples. As shown in Fig. 2, the rubber coverage of the cord surface is very high in the
rubber compounds, regardless of the type of adhesion promoter incorporated.
The humidity aging deteriorates the adhesion properties of rubber compounds
to brass-plated steel cord. After humidity aging for 15 days, the pull-out force de-
creased compared to that immediately after cure for all rubber compounds, but the
extent of decrease in pull-out force varied with the loading amount of accelerator
and the type of adhesion promoter incorporated.
For the rubber compounds containing resinous adhesion promoter, adhesion re-
tention after humidity aging increased significantly with increasing loading amount
of accelerator. As there is an excess accelerator in the rubber compound in the
case of high loading amount of accelerator, the weak boundary layer closely near
the adhesion interphase is reinforced with post-vulcanization during aging treat-
ment. Besides the crosslinks near the adhesion interphase, interpenetrating network,
produced by the reaction between methylene donor and methylene acceptor incor-
porated as resinous adhesion promoter, formed in the region of the weak boundary
layer. Also, high crosslinks arising from post-vulcanization make it difficult for hu-
midity to diffuse into the region of adhesion interphase under humidity aging.
For the rubber compounds containing cobalt salt, adhesion retention decreased
with increasing loading amount of accelerator. Cobalt salt in the rubber compounds
enhanced the formation of adhesion interphase, especially formation of copper sul-
fide. Also, the accelerator plays an important role in the formation of adhesion
interphase. For the rubber compounds containing cobalt salt, high loading of ac-
celerator in the rubber compound grew adhesion interphase excessively under the
humid hostile environment. Therefore, the adhesion retention decreased with in-
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1267
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Figure 3. Image analyzer micrographs (magnification: ×50) of pulled-out steel cords from adhesion
samples after humidity aging for 15 days with respect to loading amounts of both accelerator and adhe-
sion promoters (cobalt salt/zinc borate/(methylene donor/methylene acceptor) (phr/phr/phr/(phr/phr)):
(a) 4/0/0/(2/4); (b) 8/0/0/(2/4); (c) 4/1/0/0; (d) 8/1/0/0; (e) 4/0/1/0; (f) 8/0/1/0.

creasing loading amount of accelerator for the rubber compound containing cobalt
salt. This fact can also be supported from the low rubber coverage shown in Figs 2
and 3 for high loading amount of accelerator.
For the rubber compounds containing zinc borate, poor adhesion retention ap-
peared for high loading of accelerator. For cobalt salt incorporated, failure after
humidity aging dominantly occurs in the adhesion interphase whereas failure occurs
 1268 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284

dominantly in the weak boundary layer closely adjacent to the adhesion interphase
for both resinous adhesion promoter and zinc borate.
The rubber coverage showed similar behavior as the pull-out force. The rubber
coverage on the brass-plated steel cord by incorporating cobalt salt and high loading
of accelerator into the rubber compound was lower than samples containing either
resinous adhesion promoter or zinc borate in the rubber compounds after humidity
aging for 15 days (Fig. 3). As shown in Fig. 1, incorporating high loading amount of
accelerator and resinous adhesion promoter in the rubber compounds significantly
improves adhesion stability against humidity aging.
Figure 4 shows the pull-out force and rubber coverage of the brass-plated steel
cord after thermal aging. The adhesion property after thermal aging is different
from that after humidity aging. The extent of decrease in adhesion property under
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thermal aging is smaller than that under humidity aging.

For the incorporation of either resinous adhesion promoter or cobalt salt into rub-
ber compounds, adhesion retention after thermal aging increased with increasing
loading amount of accelerator in the rubber compounds. But with the incorpora-
tion of zinc borate, adhesion retention decreased significantly. For the high loading
amount of accelerator in the rubber compounds, monosulfidic structure in sul-
fur crosslinked networks formed preferentially compared to polysulfidic structure
formation during vulcanization. Also, polysulfidic structure was transformed into
monosulfidic structure under thermal aging environments. It is known that thermal
aging causes the decline of physical properties of rubber compounds, whereas hu-
midity aging is mainly responsible for the deterioration of the adhesion interphase
between the rubber compound and brass-plated steel cord. It was found that the
highest adhesion retention after thermal aging was in the adhesion sample contain-
ing zinc borate and low loading amount of accelerator.
Figure 5 shows image analyzer micrographs of pulled-out steel cords from ad-
hesion samples thermally aged for 15 days with respect to loading amount of
accelerator in the rubber compounds containing various adhesion promoters. Re-
gardless of the type of adhesion promoter incorporated, a cohesive failure in the
rubber compound after thermal aging occurred dominantly after the pull-out test.
The effects of loading amount of accelerator in the rubber compounds on their
adhesion properties to brass-plated steel cord can be summarized as: (1) The en-
hancement in the unaged adhesion properties was significant with incorporating
high loading of accelerator in the rubber compounds containing zinc borate. (2) Un-
der humidity aging treatment, the extent of adhesion retention with respect to the
loading amount of accelerator after humidity aging depended largely on the type
of adhesion promoter incorporated. (3) For cobalt salt incorporated, interfacial fail-
ure between adhesion interphase and rubber compound after humidity aging occurs
dominantly, whereas a cohesive failure predominantly occurs in the weak boundary
layer closely adjacent to adhesion interphase for both resinous adhesion promoter
and zinc borate. (4) Under thermal aging, for the incorporation of either resinous
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1269
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Figure 4. Adhesion properties of rubber compounds with different loading amounts of both accelera-
tor and adhesion promoters (cobalt salt/zinc borate/resin) to brass-plated steel cord after thermal aging
at 100◦ C for 15 days: (a) pull-out force and (b) rubber coverage.
 1270 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284
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Figure 5. Image analyzer micrographs (magnification: ×50) of pulled-out steel cords from ad-
hesion samples after thermally aging for 15 days with respect to loading amounts of both ac-
celerator and adhesion promoters (cobalt salt/zinc borate/(methylene donor/methylene acceptor)
(phr/phr/phr/(phr/phr)): (a) 4/0/0/(2/4); (b) 8/0/0/(2/4); (c) 4/1/0/0; (d) 8/1/0/0; (e) 4/0/1/0; (f) 8/0/1/0.

adhesion promoter or cobalt salt into the rubber compound, the extent of adhesion
retention after thermal aging increased with increasing loading amount of accel-
erator in rubber compounds. But with the incorporation of zinc borate, adhesion
retention decreased significantly. (5) Regardless of the type of adhesion promoter
incorporated, a cohesive failure of rubber layer in thermally aged adhesion samples
is dominant after the pull-out test.
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1271
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Figure 6. AES depth profiles of C, O, S, Fe, Cu and Zn for the adhesion interphase of unaged adhesion
samples between the rubber compound with 0.4 phr of accelerator and brass-plated steel cord.

This summary suggests that maintaining adhesion durability against various hos-
tile aging environments depends on the loading amount of accelerator incorporated
into the rubber compounds.
3.3. Examination of the Adhesion Interphase
Figure 6 shows AES depth profiles of the unaged adhesion interphase formed be-
tween the brass-plated steel cord and the rubber compound containing 0.4 phr of
accelerator and resinous adhesion promoter. On the outermost surface of the brass-
plated steel cord which was in contact with the rubber compound, carbon, copper
and sulfur were detected. Beneath these elements, zinc, oxygen and iron were
detected. The abundance of carbon on the outermost surface was due to surface
contamination. With increasing sputter time, carbon concentration decreased expo-
nentially. Significant amount of iron was detected starting from 2 min of sputtering
and increased linearly up to 10 min of sputtering. After approximately 4 min of
sputtering, copper and zinc contents were constant with depth, indicating that brass
had not reacted. This depth profile shows that copper sulfide was formed on the out-
ermost surface of the brass-plated steel cord and zinc oxide was formed on the inner
side, although the oxidation states of these elements were not clearly identified.
The intensities and widths of both copper shoulder peak and sulfur peak in the
interphase changed with respect to the type of adhesion promoter and the amount
of accelerator after cure (Figs 7–9).
 1272 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284
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Figure 7. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of unaged
adhesion samples between the rubber compounds loaded with both 2 phr of methylene donor and 4 phr
of methylene acceptor and brass-plated steel cord with respect to loading amounts of accelerator:
(a) 0.4 phr; (b) 1.6 phr.

A copper shoulder peak was observed in the adhesion interphase in case of

the rubber compound containing resinous adhesion promoter regardless of loading
amount of accelerator, but the ratio of sulfur peak to copper shoulder peak in the
adhesion interphase decreased with increasing the loading amount of accelerator
(Fig. 7). For the rubber compounds containing resinous adhesion promoter, sulfi-
dation of copper in the adhesion interphase reduced with increasing the loading
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1273
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Figure 8. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of unaged
adhesion samples between the rubber compounds loaded with 1 phr of cobalt salt and brass-plated
steel cord with respect to loading amounts of accelerator: (a) 0.4 phr; (b) 1.6 phr.

amount of accelerator in the rubber compounds. In the adhesion system of resinous

adhesion promoter containing low accelerator loading, it has been known that the
resin in the rubber compounds attracts strongly the copper in the adhesion inter-
phase [12]. As a result, zinc mobility in the adhesion interphase increased and the
zinc peak became large. The ratio of oxygen peak to zinc peak in the adhesion
interphase decreased with increasing the loading amount of accelerator.
 1274 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284
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Figure 9. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of unaged
adhesion samples between the rubber compounds loaded with 1 phr of zinc borate and brass-plated
steel cord with respect to loading amounts of accelerator: (a) 0.4 phr; (b) 1.6 phr.

For the rubber compound containing cobalt salt, adhesion interphase is differ-
ent from that containing resinous adhesion promoter (Fig. 8). The copper shoulder
peak increased significantly with incorporating cobalt salt in the rubber compounds
supporting the increase in copper mobility during cure. In the adhesion system of
cobalt salt containing low loading of accelerator, the widths of copper sulfide and
zinc oxide in the adhesion interphase became large. With increasing loading amount
of accelerator in the rubber compounds, both copper shoulder peak and sulfur peak
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1275

decreased significantly. Both zinc peak and oxygen peak in the adhesion interphase
became narrow and their intensities also reduced with increasing loading amount
of accelerator. In the adhesion system of cobalt salt containing low loading of ac-
celerator, cobalt salt in the rubber compound increased with copper mobility in
the adhesion interphase. Subsequently, zinc diffusion to the adhesion interphase in-
creased due to the presence of copper vacancies and the zinc peak became large.
A severe dezincification in the adhesion interphase was observed in the adhesion
system of cobalt salt containing low loading of accelerator.
For the rubber compounds containing zinc borate, copper shoulder peak in the
adhesion interphase did not appear clearly, irrespective of the loading amount of
accelerator (Fig. 9). Copper shoulder and sulfur peaks of adhesion interphase for
sample containing zinc borate are very small compared to those for other adhesion
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promoters. This may be explained by the weak interaction between copper on the
steel cord and zinc borate in the rubber compound during vulcanization. It can be
supposed that zinc borate does not accelerate strongly the reaction between cop-
per and sulfur in the adhesion interphase. The asymmetry of both sulfur peak and
zinc peak in the adhesion interphase is observed in the low loading of accelerator
(Fig. 9(a)). For the adhesion system of zinc borate containing low loading of ac-
celerator, it was supposed to form zinc sulfide in the adhesion interphase between
copper sulfide and zinc oxide. The ratio of oxygen peak to zinc peak in the adhe-
sion interphase decreased with increasing the loading amount of accelerator. The
dezincification occurred in the low loading of accelerator.
The zinc profile was similar to the oxygen profile on the outermost surface, re-
gardless of the composition of rubber compound, suggesting the formation of zinc
oxide. But the zinc and oxygen peaks changed with the loading amount of acceler-
ator and the type of adhesion promoter in the rubber compounds.
Suppression of dezincification occurred in the adhesion interphase of the rub-
ber compound containing high loading of accelerator. This may be explained as
follows: some of fully excited copper in the adhesion interphase diffused into the
cobalt salt loaded rubber compound during cure. This phenomenon was accelerated
in the low loading of accelerator and cobalt salt loaded rubber compound. As a re-
sult, the copper mobility increased and also simultaneously zinc activity increased,
resulting in enrichment of the adhesion interphase by zinc (Fig. 8).
Regardless of the type of adhesion promoter incorporated into rubber com-
pounds, the ratio of oxygen to zinc decreased with increasing accelerator loading
(Figs 7–9).
In the case of zinc borate and low loading of accelerator in the rubber compound,
the asymmetry of zinc peak was observed in the adhesion interphase as shown in
Fig. 9(a). This may suggest partial formation of zinc sulfide in the adhesion in-
terphase. For the incorporation of zinc borate and low amount of accelerator into
the rubber compound, it was found that not only zinc oxide but also zinc sulfide
formed in the adhesion interphase. In the cobalt salt and low amount of accelera-
 1276 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284

tor into the rubber compound, cobalt may play the role of accelerating the copper
sulfide formation in the adhesion interphase as shown in Fig. 8(a).
Humidity aging is a very effective way to investigate the degradation of adhesion
properties due to changes in the adhesion interphase. Depletion and accumulation
of surface components with incorporation of different adhesion promoters was dif-
ferent before and after humidity aging.
For the rubber compound containing resinous adhesion promoter, adhesion in-
terphase changed significantly with increasing accelerator loading amount in the
rubber compound (Fig. 10). Both sulfur peak and copper shoulder peak decreased
with increasing loading amount of accelerator in the resinous adhesion promoter
loaded rubber compound. Also, both the oxygen peak and zinc peak decreased with
increasing loading amount of accelerator in the rubber compound. For the low load-
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ing of accelerator and resinous adhesion promoter, the severe growth of adhesion
interphase after humidity aging is responsible for the poor adhesion retention as
summarized in Fig. 1.
For the cobalt salt loaded rubber compound, adhesion interphase did not grow
significantly compared to those rubber compounds containing either resinous adhe-
sion promoter or zinc borate. Especially the copper and sulfur peaks for low loading
amount of accelerator did not change significantly upon humidity aging treatment.
For the cobalt salt and high accelerator loaded rubber compound, the adhesion in-
terphase, especially zinc and oxygen peaks, grew excessively under humidity. The
presence of cobalt salt in the rubber compound transformed the structure of copper
sulfide from amorphous to crystalline during humidity aging [42]. With increasing
loading amount of accelerator, the intensities of both zinc peak and oxygen peak
decreased whereas widths of zinc peak and oxygen peak increased (Fig. 11(b)). It
was found that the high loading of accelerator in cobalt salt loaded rubber com-
pound made it easy for the dezincification of adhesion interphase to occur during
humidity aging.
With incorporating zinc borate into the rubber compound, the growth of adhe-
sion interphase was accelerated after humidity aging. Unlike in the other adhesion
promoters loaded rubber compounds, the sulfur peak showed significant asymmetry
after humidity aging (Fig. 12). The width of sulfur peak in zinc borate loaded rub-
ber compound after humidity aging decreased with increasing accelerator loading
amount. The increase of zinc activity due to the incorporation of zinc borate into the
rubber compound brings about significant formation of zinc sulfide as well as severe
dezincification in humidity aging treatment. The role of zinc sulfide has been sug-
gested to retard the migration of reacting species across the interphase between the
rubber and brass [7, 19]. This means that the incorporation of zinc borate controls
the migration of copper into the adhesion interphase and enhances significantly the
formation of zinc sulfide. The zinc sulfide layer suppresses further growth of both
copper sulfide and zinc oxide during humidity aging.
The adhesion interphases after thermal aging for the adhesion samples of brass
coated steel cords to rubber compounds loaded with various adhesion promoters
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1277
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Figure 10. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of
humidity aged adhesion samples between the rubber compounds loaded with 2 phr of methylene
donor and 4 phr of methylene acceptor and brass-plated steel cord with respect to loading amounts of
accelerator: (a) 0.4 phr; (b) 1.6 phr. Humidity aging: 15 days, 83◦ C and 95% relative humidity.

are shown in Figs 13–15. The adhesion interphases after thermal aging are very
different from those after humidity aging.
For the resinous adhesion promoter loaded rubber compound, the sulfur peak
in the adhesion interphase did not vary with increasing loading amount of accel-
erator. For the low loading amount of accelerator and resinous adhesion promoter
loaded rubber compound, the shoulder in the copper peak did not appear clearly
 1278 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284
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Figure 11. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of
humidity aged adhesion samples between the rubber compounds loaded with cobalt salt of 1 phr
and brass-plated steel cord with respect to loading amounts of accelerator: (a) 0.4 phr; (b) 1.6 phr.
Humidity aging: 15 days, 83◦ C and 95% relative humidity.

indicating a very weak interaction between copper in the brass-plated steel cord
and the resinous adhesion promoter in the rubber compound during thermal aging
treatment. The adhesion interphase did not grow significantly during thermal ag-
ing treatment. The oxygen and zinc peaks in the adhesion interphase became sharp
with increasing loading amount of accelerator in the rubber compound, indicating
suppression of dezincification.
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1279
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Figure 12. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of
humidity aged adhesion samples between the rubber compounds loaded with zinc borate of 1 phr
and brass-plated steel cord with respect to loading amounts of accelerator: (a) 0.4 phr; (b) 1.6 phr.
Humidity aging: 15 days, 83◦ C and 95% relative humidity.

For the cobalt salt loaded rubber compound, the width of sulfur peak in the
adhesion interphase increased only slightly with increasing loading amount of ac-
celerator. As a consequence of interaction between copper and cobalt salt, the zinc
mobility in the adhesion interphase depended on the loading amounts of accelerator
and cobalt salt.
 1280 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284
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Figure 13. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of
thermally aged adhesion samples between the rubber compounds loaded with 2 phr of methylene
donor and 4 phr of methylene acceptor and brass-plated steel cord with respect to loading amounts of
accelerator: (a) 0.4 phr; (b) 1.6 phr. Thermal aging: 15 days at 100◦ C.

For the zinc borate loaded rubber compound, the sulfur peak in the adhesion in-
terphase decreased significantly with the loading amount of accelerator (Fig. 15).
The widths of zinc peak and oxygen peak in the adhesion interphase changed with
the loading amount of accelerator. For the low loading of accelerator and zinc bo-
rate loaded rubber compound, the zinc peak and oxygen peak are broad compared
to those for high loading of accelerator and zinc borate loaded rubber compound.
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1281
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Figure 14. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of
thermally aged adhesion samples between the rubber compounds loaded with 1 phr of cobalt salt and
brass-plated steel cord with respect to loading amounts of accelerator: (a) 0.4 phr; (b) 1.6 phr. Thermal
aging: 15 days at 100◦ C.

From the above results, it can be assumed that the zinc borate in the rubber com-
pound controls the formation of zinc oxide, and it depends on the loading amount
of accelerator in the rubber compound during thermal aging.
Recently Fulton and coworkers [43, 44] reported that the zinc in the adhesion
interphase originated, to some extent, from the ZnO in the rubber whereas the ma-
 1282 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284
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Figure 15. AES depth profiles of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of
thermally aged adhesion samples between the rubber compounds loaded with 1 phr of zinc borate and
brass-plated steel cord with respect to loading amounts of accelerator: (a) 0.4 phr; (b) 1.6 phr. Thermal
aging: 15 days at 100◦ C.

jority of the zinc oxide layer originated from the zinc in the brass coating of the
steel tire cords.

4. Conclusions
The adhesion property of the rubber compounds to brass-plated steel cord was
found to be largely dependent on the type of adhesion promoter and the loading
 G. S. Jeon / Journal of Adhesion Science and Technology 22 (2008) 1255–1284 1283

amount of accelerator in the rubber compound. The adhesion of rubber compounds

containing zinc borate to brass-plated steel cords was very sensitive to loading
amount of accelerator in the rubber compound. The enhancement in the unaged
adhesion properties was significant with high loading of accelerator in the rubber
compound containing zinc borate. For cobalt salt incorporation, interfacial failure
between adhesion interphase and rubber compound occurs dominantly after humid-
ity aging, whereas a cohesive failure occurs predominantly in the weak boundary
layer closely adjacent to the adhesion interphase for both resinous adhesion pro-
moter and zinc borate. Under thermal aging, for the incorporation of both resinous
adhesion promoter and cobalt salt into the rubber compound, the extent of adhesion
retention after thermal aging increased with increasing loading amount of acceler-
ator in the rubber compounds. But with the incorporation of zinc borate, the extent
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of adhesion retention decreased significantly. From the analysis of adhesion inter-

phases by AES depth profiling, it was found that suppression of dezincification
occurred in the adhesion interphase of the rubber compound containing high load-
ing of accelerator.

Acknowledgement
This work was supported by the Korea Research Foundation Grant funded by the
Korean Government (MOEHRD, KRF-2007-521-D00150).

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