J. Adhesion Sci. Technol., Vol. 17, No. 6, pp.

797– 814 (2003)

Ó VSP 2003.
Also available online - www.vsppub.com

Boric acid ester as an adhesion promoter for rubber

compounds to brass-plated steel cord

GYUNG SOO JEON ¤

Department of Environmental Information, Provincial College of Damyang, Damyang,
Chonnam 517-802, South Korea

Received in Ž nal form 21 January 2003

Abstract—The adhesion between a boric acid ester (BAE) containing rubber compound and a brass-
plated steel cord was investigated to understand the role of BAE as an adhesion promoter. An
improvement in adhesion was shown with the low loading of BAE in the range 0.5– 1 phr, while
signiŽ cant decline of adhesion was not observed with high loading at 2 phr and a long aging time of
15 days. The interphase between the brass plated steel cord and the rubber compound studied using
Auger electron spectroscopy (AES) showed a stabilized adhesion interphase by BAE incorporation,
resulting in the enhancement of the adhesion retention.

Keywords: Boric acid ester; adhesion promoter; cobalt salt; rubber-to-brass bonding; adhesion
interphase; AES; depth proŽ le.

1. INTRODUCTION

Adhesion of rubber to brass-plated steel cord is of paramount importance in steel

belted tires. Brass-plated steel cords inserted in the belt and carcass of tires has long
been used as a reinforcing material to provide a sufŽ cient mechanical strength and
stability to endure cars themselves and their loads. Brass plating on the surface of
steel cords reacts with sulfur in the rubber compound during the curing process of
tire manufacturing, forming an adhesion interphase 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 copper and zinc. Therefore, the adhesion
interphase is very complex in terms of components and content, so good adhesion
can be achieved when the adhesion interphase is formed with a sufŽ cient thickness
and a stable structure.

¤
Phone: +82-61-380-8671. Fax: +82-61-381-9100. E-mail: gjeon@damyang.ac.kr
798 G. S. Jeon

The major components of the adhesion interphase are sulŽ des, oxides and
hydroxides of copper and zinc [1 –3]. Adhesion becomes weak when copper sulŽ de
is not sufŽ ciently grown in the interphase, but the excessive growth of copper sulŽ de
or zinc oxide brings about their own cohesive failures [4]. Thus the optimum growth
of copper sulŽ de is essential to form a large contact interface between the rubber
and the brass, resulting in good adhesion [5 – 7]. Several reagents such as cobalt
salt, resorcinol formaldehyde resin and methylene donor are commercially used
as adhesion promoters to enhance the migration of copper, forming the necessary
amount of copper sulŽ de in the adhesion interphase [8, 9]. A large content of zinc
oxide at the outer surface of the brass induces a cohesive failure, since its mechanical
strength is very weak. On the other hand, the coexistence of zinc oxide with zinc
at the interface is helpful to control the mass transfer rate of reacting species in the
formation of the adhesion interphase [10]. This contributes to the stability of the
adhesion interphase by preventing the excessive growth of its components.
Cobalt salt has been used as an adhesion promoter to accelerate the activation of
sulfur in the interphase by inducing the formation of an adequate copper sulŽ de
layer, thus making better adhesion possible [11, 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 sulŽ de layer which induces
cohesive failure [7]. Boron is well known as a corrosion inhibitor in the adhesion
interphase [13].
Some tire chemicals manufacturers have incorporated boric acid ester (BAE)
into rubber compounds as an organic adhesion promoter together with cobalt
salt [14, 15]. The BAE has been incorporated in the rubber compound together with
Co naphthenate [16]. The enhanced effect of loading of BAE on the adhesion was
reported, but there is no systematic report on the role and optimal loading amount
of BAE.
The interaction between boric acid ester and copper is known. The formation of
the copper complex between the boric acid ester and copper has been studied by
means of Nuclear Magnetic Resonance Spectroscopy [17]. The adsorption of boric
acid ester on silica has attracted considerable attention from surface chemists using
FT-IR spectroscopy [18]. Li et al. reported a strong surface interaction of boric acid
ester with metal oxides [19].
A moderate diffusion of copper into rubber, due to the interaction of boric acid
ester with copper, may be beneŽ cial in the formation of copper sulŽ de with a high
surface area in the adhesion interphase and the control of zinc oxide formation in
the adhesion interphase due to the increased freedom of zinc arising from a lack of
the copper on the cord surface. The af uence of copper sulŽ de with a high surface
area in the adhesion interphase is necessary for the mechanical interlocking of the
rubber compound to the brass-plated steel cord.
Since adhesion between two phases implies that some kind of chemical or
physical interaction has taken place, much attention has been paid to characterize
the adhesion interphase formed between two phases (rubber and brass-plated steel
 Improving the adhesion by boric acid ester 799

cord). The samples of adhesion interphases were prepared by inserting Ž lter paper
between rubber compound and brass plated steel cord and they were analyzed by
AES in order to interpret the adhesion properties [20]. The effect of BAE on the
adhesion property between the rubber compound and brass-plated steel cord was
examined based on the formation and degradation of the adhesion interphase from
the depth proŽ les of the rubber compound/ brass-plated steel cord samples.
The pull-out force and coverage of the rubber compound containing BAE were
compared to those of a BAE-free rubber compound. The in uences of humidity
aging as well as BAE concentration on the adhesion property of BAE-containing
rubber compounds were also investigated.

2. EXPERIMENTAL

2.1. Preparation of rubber compounds

Five rubber compounds with different BAE loadings were prepared. Compositions
of the masterbatch and Ž nal mixed compounds are given in Table 1. Bonding
systems composed of resorcinol formaldehyde resin and a methylene donor such
as hexamethoxymethylmelamine or nitromethylpropanol was excluded in order
to observe the effect of BAE on the structure and composition of the adhesion
interphase more clearly.
The loading amounts of BAE were varied as 0, 0.5, 1.0, 2.0, and 4.0 phr. All
the rubber compounds were mixed as described in ASTM D-3184 using an internal
Table 1.
Composition of rubber compounds used

Component Chemical or Manufacturer Content

Trade name (phr)
Masterbatch
NR SMR-CV60 Lee Rubber Co., Malaysia 100
carbon black N351 Lucky Co., Korea 50
processing oil A#2 Michang Co., Korea 5
activator ZnO Hanil Co., Korea 10
antioxidant Kumanox-RDa Monsanto Co., USA 1
adhesion promoter BAEb Bayer Co., Germany Varied
adhesion promoter Co stearate Manchem Co., UK 0.8

Final Mixing
activator Stearic acid Pyungwha Co., Korea 1.5
accelerator Santocure MOR c Monsanto Co., USA 0.7
sulfur Crystex HS OT 20 Akzo Co., The Netherlands 5
a
2,2,4-trimethyl-1,2-dihydroquinone.
b boric acid ester.
c 2-(morpholinothio)-benzothiazole sulfenamide.
800 G. S. Jeon

mixer (Banbury Mixer model 82, Farrel Co., USA). Ingredients for the masterbatch
were mixed for 10 min at a rotor speed of 40 rpm and discharged at 150 ± C. After
the masterbatch had cooled to room temperature, the Ž nal mixing components were
mixed for 5 min at 30 rpm and discharged at 90 ± C. After mixing, the compounds
were carefully remilled into  at sheets on a two-roll mill (model MKIII, Farrel Co.
USA).
Rheocurves were recorded using a Monsanto Rheometer 100 at 160 ± C. The
t90 time, i.e. the time required to achieve 90% cure, and maximum torque were
determined from the rheograms. Mooney viscosity was also obtained using a
Monsanto MV-200 instrument 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.

2.2. Adhesion test

Based on the procedure described in ASTM D-2229, T-test specimens were cured at
160 ± C on a cure press. Curing was continued for 5 min more than the t90 time. The
brass-plated steel cords with 4 £ 0:28 construction in which 4 steel wires having the
same diameter of 0.28 mm were twisted together, manufactured by Hyosung T&C
Co., Korea, were used. The plating weight of the brass was 3.6 g / kg and the copper
content 63.6%. For humidity aging, specimens were placed in a humidity chamber
at 85 ± C under 85% relative humidity 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 was also noted. Each value reported is an average of
six specimens tested. The morphology of the pulled-out steel cord surface after
measuring pull-out force was studied using a scanning electron microscope (JEOL
JSM 7400, Japan).

2.3. Analysis of the adhesion interphase

A brass plated steel cord was covered with a Ž lter paper (pore size: 5 ¹m; catalog
no 142 50, Millipore Co., USA), sandwiched between two uncured pads of rubber
compound, and then placed in a pad mold [20]. Curing and aging conditions for the
rubber compound/ brass plate samples were the same as in the preparation of the
T-test specimens. After the various treatments, samples for the surface analysis of
the adhesion interphase were obtained by peeling away the Ž lter paper. Sulfur from
the rubber compound migrated through the pores of the Ž lter paper and reacted with
the copper and zinc of the brass-plated steel cord, forming an adhesion interphase.
After removing the rubber and Ž lter paper from the brass-plated steel cord, the
adhesion interphase, including copper sulŽ de and zinc oxide, remained on the brass-
plated steel cord.
 Improving the adhesion by boric acid ester 801

The depth proŽ les from the interphase in contact with the rubber compound to
the bulk of the brass were recorded on a Perkin-Elmer Auger spectrometer (model
Phi 670, Perkin-Elmer Co., USA). An area of 10 £ 10 ¹m2 was examined using an
ion beam with a potential of 5.0 kV, a current of 0.03 ¹A, and an incident angle to
the specimen of 60± , i.e. the same conditions as described in previously published
papers [6, 9]. Surface concentrations were determined every 0.5 min from the Auger
peaks of detected elements with compensation for their sensitivities. A sputter
gun with an argon ion beam rastered a 2 £ 2 mm2 area for depth proŽ ling. The
sputtering rate for the brass Ž lm was determined to be 13 nm min¡1 . It was difŽ cult,
however, to determine the sputter rate precisely for the adhesion interphase because
it included various chemical components with variable 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 BAE-containing rubber compound

The cure rates of the rubber compounds varied with the loading amount of BAE as
listed in Table 2. The t90 time did not change signiŽ cantly with an increase in the
loading amount of BAE. Therefore, the cure rate index (CRI) calculated using the
equation 100=.t90 ¡ t2 / was nearly constant.
The mechanical crosslink density, which was calculated by the difference in the
maximum torque and the minimum torque, decreased with increasing BAE loading
in rubber compounds. The mechanical crosslink density changed by incorporating
BAE into rubber compounds. The lower cure rate and the higher crosslink density
of rubber compound are essential to good adhesion. The slow cure rate improved
the mobility of the crosslink agent resulting in its af uence in the region of adhesion
interphases.
Table 2.
Cure propertiesa of green rubber compounds with respect to BAE loading

BAE loading Time (min) CRI e Torque (J)

(phr) t2 b t40 c t90 d (min¡1 ) min max
0 2.2 3.9 6.6 22.7 1.85 6.72
0.5 2.3 3.9 6.7 22.7 1.84 6.64
1.0 2.2 3.8 6.5 23.3 1.76 6.53
2.0 2.2 3.8 6.5 23.3 1.79 6.43
a
The rubber compounds were sheared to §1± and 1.67 Hz at 160 ± C.
b
Time required to attain 2% cure.
c Time required to attain 40% cure.
d
Time required to attain 90% cure.
e
CRI D 100=.t90 ¡ t2 ).
802 G. S. Jeon

Table 3.
Mooney viscoelastic propertiesa of green rubber compounds with respect to BAE loading

BAE loading Time (min) Torque (J)

(phr) t5 b t35 c initial minimum at 4 mind
0 11.8 17.8 8.37 7.07 7.10
0.5 11.9 17.8 7.93 6.77 6.77
1.0 12.4 18.5 7.34 6.08 6.11
2.0 11.7 17.5 7.57 6.18 6.21
a The rubber compounds were sheared to 2 rpm at 125 ± C.
b
Time required to attain minimum torque plus 5 point torque.
c
Time required to attain minimum torque plus 35 point torque.
d Viscosity, ML
1C4;125 ± C .

Table 4.
Mechanical properties of unaged vulcanizates with respect to BAE loading

BAE loading Hardness Modulus (MPa) T.S.a E.B. b

(phr) (Shore A) 50% 100% 200% 300% (MPa) (%)

0 77 2.62 5.08 11.4 17.2 23.5 431

0.5 76 2.47 4.80 11.1 17.0 24.5 454
1.0 76 2.49 4.87 11.2 17.2 23.8 433
2.0 77 2.51 4.90 11.1 17.0 23.9 441
a Tensile strength.
b Elongation at break.

The viscosity of green rubber compound also varied with BAE loading as shown
in Table 3. The t5 time, indicating the onset of scorch time, was nearly constant
regardless of BAE loading except for 1 phr BAE loading. Viscosity, represented as
torque at 4 min, decreased steadily with BAE loading.
The changes in mechanical properties of vulcanizates with BAE loading were not
remarkable (Table 4). Consistent trends in modulus, tensile strength and elongation
at break with BAE loading were not observed. Although cure characteristics,
viscosity and mechanical properties of the rubber compound slightly varied with
BAE loading, the degrees of variances in these properties were not signiŽ cant. Since
the change in the rubber property with BAE loading is small, the contribution of the
rubber property on the adhesion between the BAE-containing rubber compound and
brass-plated steel cord can be neglected in the discussion of BAE as an adhesion
promoter.

3.2. Adhesion properties of the BAE-containing rubber compound

The change in the adhesion properties of the rubber compound with brass-plated
steel cord was comparable with the incorporation of BAE into the rubber compared
to that of the mechanical properties. Figure 1 shows the pull-out force and rubber
 Improving the adhesion by boric acid ester 803

Figure 1. Adhesion properties of BAE-containing rubber compounds after cure; (A) pull-out force
and (B) rubber coverage.

Table 5.
Adhesion properties of humidity ageda adhesion samples for various rubber compounds with respect
to BAE loading

BAE loading Pull-out force (N) Rubber coverage (%)

(phr) 0b 5 10 15 0 5 10 15
0 610 319 285 258 75 35 30 15
0.5 628 467 353 353 80 65 45 45
1.0 621 434 386 344 80 50 45 40
2.0 610 400 324 300 75 50 45 40
a
The adhesion samples were humidly aged at 85 ± C and 85% relative humidity.
b Aging period (days).

coverage of the BAE-containing rubber compounds after curing without any aging.
There were no signiŽ cant increases with BAE loading in the pull-out force and
rubber coverage in the unaged state. No improvement in adhesion property was
shown with the addition of BAE. Rubber coverage showed the same trend as the
pull-out force. Figure 2 shows that the rubber attached to pulled-out cord surface of
unaged adhesion samples is signiŽ cant regardless of BAE loading amount.
Humidity aging deteriorates adhesion properties, so long aging causes poor
adhesion (Fig. 3). The data after humidity aging for 5 days and 10 days are shown
in Table 5. After humidity aging for 15 days, the pull-out force decreased, but the
decrease was small for the 0.5– 1.0 phr BAE-containing rubber compounds. Further
increase of BAE loading decreased pull-out forces of the rubber compounds. Also
rubber coverage showed similar behavior to that of the pull-out force. The rubber
coverage of the BAE-containing rubber compounds up to 2 phr was higher than that
804 G. S. Jeon

(A) (B)

(C) (D)
Figure 2. SEM micrographs of pulled-out steel cord from unaged adhesion samples with respect to
BAE loading: (A) 0 phr; (B) 0.5 phr; (C) 1 phr; (D) 2 phr.

Figure 3. Adhesion properties of BAE-containing rubber compounds with humidity aging; (A) pull-
out force and (B) rubber coverage. Humidity aging: 15 day, 85 ± C and 85% relative humidity.
 Improving the adhesion by boric acid ester 805

of the BAE-free rubber compound after humidity aging of 15 days. As shown in

Fig. 3, a small incorporation of BAE into rubber compound signiŽ cantly improves
adhesion stability against humidity aging. Figure 4 shows that BAE addition into
the rubber compound is very beneŽ cial to increase the rubber coverage for pulled-
out cord surface of humidity aged adhesion samples. The BAE-free and humidity
aged adhesion samples mainly showed interfacial failure but BAE-containing
and humidity aged adhesion samples dominantly showed cohesive failure in the
adhesive.
Figure 5 and Table 6 show the pull-out force and rubber coverage of the BAE-
containing rubber compounds after thermal aging. The trend of adhesion property
with BAE loading after thermal aging is similar to that after humidity aging.
Figure 6 shows SEM micrographs of pulled-out steel cord from adhesion samples
thermally aged for 15 days with respect to BAE loading.
The effect of BAE loading into the rubber compound on its adhesion properties
can be summarized as: (1) The enhancement in the unaged adhesion properties was
not signiŽ cant, (2) a low loading, below 1.0 phr, was sufŽ cient for the enhancement

(A) (B)

(C) (D)
Figure 4. SEM micrographs of pulled-out steel cord from adhesion samples humidity aged for 15
days with respect to BAE loading: (A) 0 phr; (B) 0.5 phr; (C) 1 phr; (D) 2 phr.
806 G. S. Jeon

Figure 5. Adhesion properties of BAE-containing rubber compounds with thermal aging; (A) pull-out
force and (B) rubber coverage. Thermal aging: 15 day, 95 ± C.

Table 6.
Adhesion properties of thermally-ageda adhesion samples for various rubber compounds with respect
to BAE loading

BAE loading Pull-out force (N) Rubber coverage (%)

(phr) 0b 5 10 15 0 5 10 15
0 610 453 396 287 75 80 80 70
0.5 628 550 432 368 80 90 80 80
1.0 621 520 442 399 80 80 65 85
2.0 610 492 424 359 75 95 80 75
a
The adhesion samples were thermally aged at 95 ± C.
b
Aging period (days).

of the adhesion retention even after humidity aging treatment, and (3) severe
degradation of adhesion properties was observed with humidity aging for the BAE-
free rubber compound. This summary suggests that BAE loading is considerably
effective in maintaining adhesion stability against hostile environment.

3.3. Examination of the adhesion interphase

The formation, growth and deformation of an adhesion interphase between the
BAE-containing rubber and the brass-plated steel cord can be monitored from the
adhesion sample with Ž lter paper placed at the interphase. Since the Ž lter paper
adheres neither to rubber nor to brass, the brass-plate steel cord is easily detached
from the rubber compound after cure. The analysis of the surface layer on the brass-
plated steel cord provides information on the formation and disappearance of chem-
ical components in the adhesion interphase during curing process. Figure 7 shows
 Improving the adhesion by boric acid ester 807

(A) (B)

(C) (D)
Figure 6. SEM micrographs of pulled-out steel cord from adhesion samples thermally aged for 15
days with respect to BAE loading: (A) 0 phr; (B) 0.5 phr; (C) 1 phr; (D) 2 phr.

AES depth proŽ les of the unaged adhesion interphase formed between the BAE-
free rubber compound and brass plated steel cord. At the outer surface of the brass
plated steel cord adhered to the BAE-free rubber compound, carbon, copper and
sulfur were detected. Beneath these elements, zinc, oxygen and iron were detected.
The af uence of carbon at outermost interphase is due to surface contamination.
With increasing sputter time, carbon concentration decreased exponentially. Iron
detected signiŽ cantly from 6 min of sputtering and increased linearly up to 20 min
of sputtering. After 12 min of sputtering, copper and zinc contents were constant
with depth, indicating non-reacted brass. This depth proŽ le shows that copper sul-
Ž de is formed on the outer surface of the brass plated steel cord and zinc oxide on the
inner side, although the oxidation states of these elements are not clearly identiŽ ed.
The contents of copper and sulfur on the outer surface decreased on the BAE-
containing rubber compounds (Fig. 8). A copper peak shoulder was observed in
the adhesion interphase adhered to the rubber compound regardless of BAE loading
but the ratio of sulfur content to copper shoulder content increased on the outer
surface with increasing BAE loading. Also copper peak shoulder decreased with
808 G. S. Jeon

Figure 7. AES depth proŽ les of C, O, S, Fe, Cu and Zn for the adhesion interphase of unaged adhesion
samples between the BAE-free rubber compound and brass plated steel cord.

increasing BAE loading. Zinc and oxygen peaks were observed on the inner surface
of the brass plated steel cord rather than copper and sulfur peaks after cure. Both
zinc and oxygen peaks decreased with increasing BAE loading and the zinc peak
shape was not the same as that of oxygen peak. This indicates that the incorporation
of BAE induces formation of a new compound in the adhesion interphase and the
suppression of dezinciŽ cation which is important for good adhesion stability. As
shown in Fig. 8D, the S peak is larger than that of shoulder copper peak in the
adhesion interphase for BAE-containing adhesion samples. This result suggests the
formation of ZnS layer in the adhesion interphase which suppresses the growth of
adhesion interphase, especially copper sulŽ de layer. Since it is known that BAE
interacts strongly with copper [17], the migration of copper to the rubber side will
be accelerated with BAE loading. Though the BAE has a high afŽ nity to copper,
this afŽ nity does not exclusively play a role in the formation of adhesion interphase
(copper sulŽ de). As soon as an adhesion sample cures, parallel reactions of ZnS and
copper sulŽ de layers formation occur. For the BAE-containing adhesion samples,
the formation of ZnS is faster than that of the copper sulŽ de layer compared to
BAE-free adhesion samples. This was conŽ rmed in Fig. 8 where a signiŽ cant
difference in the shapes of copper and sulfur peaks was present for the BAE-
containing adhesion samples.
The zinc proŽ le was similar to the oxygen proŽ le on the outer surface, regardless
of BAE incorporation, suggesting the formation of zinc oxide. However, the
detected depth and the amount of zinc oxide formed varied with BAE incorporation.
 Improving the adhesion by boric acid ester

Figure 8. AES depth proŽ les of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of unaged adhesion samples between the rubber compound and
brass plated steel cord with respect to BAE loading: (A) 0 phr; (B) 0.5 phr; (C) 1 phr; (D) 2 phr.
809
810 G. S. Jeon

With an increase in the loading amount of BAE, the detected depth of zinc shifted to
the outer surface and the content of zinc oxide in the adhesion interphase decreased.
The fast migration of copper to the rubber side results in voids at the brass side,
inducing the shift of zinc to the outer surface and activating the zinc due to the loss
of bonded copper. Therefore, the formation of ZnS instead of ZnO in the adhesion
interphase is accelerated by virtue of BAE as corrosion inhibitor and prevents
excessive growth of copper sulŽ de, resulting in the lowering of dezinciŽ cation in
the adhesion interphase.
Humidity aging is a very effective way to investigate the degradation of adhesion
properties due to the change in the adhesion interphase, compared to thermal aging
which induces mainly the decline of mechanical properties of the rubber compound.
Figure 9 shows the depth proŽ les of the humidity-aged adhesion interphases formed
on the brass side adhered to the rubber compound. The width and shape of copper
and sulfur peaks at the outer surface were unchanged with an increase in the loading
amount of BAE. For the BAE-free adhesion samples, adhesion interphase grows
excessively and deforms as shown in Fig. 9A. Intense sulfur peaks were observed
on the outer surface of the brass plated steel cord adhered to the rubber compound
with low BAE loading.
As in unaged adhesion samples, the ratio of sulfur content to copper shoulder
content increased signiŽ cantly with BAE loading after humidity aging. The high
concentration of S compared to Cu suggests the af uent formation of ZnS. For the
low BAE loading, the high concentration of ZnS plays a major role in high adhesion
stability. The contents of zinc and oxygen in the adhesion interphase decreased with
an increase in the BAE loading, indicating that BAE suppressed the dezinciŽ cation
during humidity aging.
The enhancement of zinc activity due to the loss of bonded copper brings
about large formation of ZnS instead of severe dezinciŽ cation in humidity aging
treatments because of BAE as corrosion inhibitor. The role of zinc sulŽ de is
suggested to retard migration of reacting species across the interface between rubber
and brass [7, 21]. The suppression of the migration improves the stability of the
adhesion interphase. The depth proŽ les of the humidity-aged adhesion interphase
for the BAE-containing rubber compounds with the brass plated steel cord were
considerably different from the unaged ones in contents of copper sulŽ de and zinc
oxide on the outer surface of the brass plated steel cord.
In the unaged sample, copper was depleted from the outer surface by BAE loading
into the rubber, and loss of copper was signiŽ cant after humidity aging. Depletion
and accumulation of surface components with BAE loading was different before
and after humidity aging, especially the sulfur concentration.
This can be explained by a strong interaction between BAE and copper. The
acceleration of copper migration to the rubber will be helpful in the formation of
copper sulŽ de, which is the major component of the adhesion interphase between
the rubber compound and brass. In the unaged sample, copper was depleted by
BAE, but high reactivity of zinc with water induced a severe dezinciŽ cation in
 Improving the adhesion by boric acid ester

Figure 9. AES depth proŽ les of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of humidity aged adhesion samples between the rubber
compound and brass plated steel cord with respect to BAE loading: (A) 0 phr; (B) 0.5 phr; (C) 1 phr; (D) 2 phr. Humidity aging: 15 days, 85 ± C and 85%
811

relative humidity.
 812
G. S. Jeon

Figure 10. AES depth proŽ les of Cu, S (top) and Zn, O (bottom) for the adhesion interphases of thermally aged adhesion samples between the rubber
compound and brass plated steel cord with respect to BAE loading: (A) 0 phr; (B) 0.5 phr; (C) 1 phr; (D) 2 phr. Thermal aging: 15 days and 95 ± C.
 Improving the adhesion by boric acid ester 813

humidity aging, causing a high accumulation of copper sulŽ de in the adhesion

interphase.
This means that the BAE enhances the migration of copper and the formation of
a large amount of zinc sulŽ de, and not of copper sulŽ de. The thick layer of zinc
sulŽ de suppresses the rapid further growth of copper sulŽ de and zinc oxide during
humidity aging. Slow growth of copper sulŽ de during humidity aging proceeded at
the BAE-containing rubber compound. Moderate amounts of copper sulŽ de and
zinc sulŽ de formation in the adhesion interphase of the BAE-containing rubber
compound are also conŽ rmed from the observation of the high depletion of copper
in the AES depth proŽ le of the unaged brass plated steel cord adhered to the rubber
compound containing high loading of BAE.
Also, the effect of adhesion interphase on thermal aging is shown in Fig. 10. For
the BAE-free adhesion sample, the adhesion interphase is severely oxidized. The
shape difference between copper shoulder peak and sulfur peak is prominent with
increasing BAE loading, supporting the formation of zinc sulŽ de. With increasing
BAE loading, dezinciŽ cation in the adhesion interphase was signiŽ cantly less.

3.4. Role of BAE as an adhesion promoter

BAE has a strong interaction with copper and forms a metal complex [17]. Though
the migration of copper to the rubber side is expected to be enhanced by the
incorporation of BAE, the BAE across the interface between the rubber compound
and brass leads to moderate amounts of copper sulŽ de and zinc sulŽ de formation in
the adhesion interphase. The signiŽ cant formation of zinc sulŽ de in the adhesion
interphase of BAE-containing adhesion samples is very beneŽ cial to improve the
adhesion stability against hostile environments. Incorporation of BAE into the
rubber suppresses the growth of copper sulŽ de resulted from af uence of zinc
sulŽ de, which is regarded as a diffusion barrier for copper in brass plated steel,
in the adhesion interphase during hostile aging treatment.
The incorporation of BAE into the rubber compound does not increase unaged
adhesion properties. The acceleration of copper migration by BAE resulted
in activated zinc which was easily sulŽ dized, not oxidized, in the humidity
aging treatment. Therefore, moderate level of zinc sulŽ de plays a major role in
maintaining adhesion stability in various aging treatments.

4. CONCLUSIONS

Adhesion stability between rubber compounds and brass-plated steel cords is

considerably enhanced by incorporation of BAE. Copper migration to the rubber
bulk was accelerated by BAE incorporation, resulting in moderate copper sulŽ de
and zinc sulŽ de formation and the enhancement of adhesion stability. The loading
of BAE suppressed dezinciŽ cation signiŽ cantly after humidity aging. BAE acts as
an adhesion promoter in hostile environments.
814 G. S. Jeon

REFERENCES
1. W. J. van Ooij and A. Kleinhesselink, Appl. Surface Sci. 4, 324 (1980).
2. W. J. van Ooij, Kautsch. Gummi, Kunstst. 30, 739 (1977).
3. G. G. Kurbatov, V. G. Beshenkov and V. I. Zaporozchenko, Surf. Interface Anal. 17, 779 (1991).
4. G. E. Hammer, R. M. Shemenski and J. D. Hunt, J. Vac. Sci. Technol. A 12, 2388 (1994).
5. G. S. Jeon, M. H. Han and G. Seo, J. Adhesion Sci. Technol. 13, 153 (1999).
6. G. S. Jeon, M. H. Han and G. Seo, Korean J. Chem. Eng. 16, 434 (1999).
7. G. S. Jeon, Y. M. Kim and G. Seo, Hwahak Konghak 36, 179 (1998).
8. G. Seo, J. Adhesion Sci. Technol. 11, 1433 (1997).
9. G. S. Jeon, M. H. Han and G. Seo, J. Adhesion 69, 39 (1999).
10. G. S. Jeon, M. H. Han and G. Seo, Korean J. Chem. Eng. 16, 248 (1999).
11. L. R. Barker, NR Technol. 12, 77 (1981).
12. W. J. van Ooij and M. E. F. Biemond, Rubber Chem. Technol. 57, 686 (1984).
13. A. K. Chandra, A. Biswas, R. Mukhopadhyay and A. K. Bhowmick, J. Adhesion 44, 177 (1994).
14. M. Pieroth and R. Schubart, Kautsch. Gummi Kunstst. 43, 385 (1990).
15. M. Pieroth, D. Holtkamp and A. Elschner, Kautsch. Gummi Kunstst. 46, 112 (1993).
16. D. Holtkamp and A. Elschner, G. Muller and M. Pieroth, Surf. Interface Anal. 23, 155 (1995).
17. J. van Haveren, J. A. Peters, J. G. Batelaan, A. P. G. Kieboom and H. van Bekkum, J. Chem.
Soc. Dalton Trans. 2649 (1991).
18. J. Liu, P. Ying, Q. Xin and C. Li, Appl. Surface Sci. 126, 16 (1998).
19. C. Li, S.-F. Fu, H. Zhang and Q. Xin, J. Chem. Soc., Chem. Commun. 17 (1994).
20. P. Persoone, P. De Volder and R. De Gryse, Solid State Commun. 92, 675 (1994).
21. Y. Ishikawa, Rubber Chem. Technol. 57, 855 (1984).