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J. Adhesion Sci. Technol., Vol. 16, No. 6, pp.

653 667 (2002)


VSP 2002.

Adhesion of brass /cobalt / copper-plated steel cord


to a typical rubber compound
CHANGWOON NAH 1; , BONG YOUNG SOHN 2 and SOO-JIN PARK 3
1 Department of

Polymer Science and Technology, The Research Institute of Industrial Technology,


Chonbuk National University, Chonju 561-756, Korea
2 Kumho Tire R&D Center, Kwangju 506-040, Korea
3 Advanced Materials Division, Korea Research Institute of Chemical Technology,
Taejon 305-600, Korea
Received in nal form 5 January 2002
AbstractA new bonding system is described in an attempt to improve the adhesion stability
of brass-plated steel cord to rubber without deterioration of initial adhesion performance. Two
brass/ cobalt/ copper-platedsteel cords with different cobalt layer thicknesses were prepared, and their
adhesion performance including adhesion stability to rubber compound were measured and compared
with those of conventional brass-plated steel cords. It was found that the new cords showed not only
an excellent adhesion stability against aging conditions, notably humidity aging, but also a superior
initial adhesion performance. The excellent adhesion stability was explained by the suppressed
dezinci cation reaction of brass by cobalt layer.
Keywords: Adhesion; steel cord; rubber compound; cobalt layer.

1. INTRODUCTION

Brass-plated steel cords have been widely accepted in the tire industry for providing
a good adhesion performance to rubber [1 3]. Extensive research has been carried
out to understand the fundamental aspects of adhesion of brass-plated steel cords
to rubber, and an excellent review paper was published in 1979 by van Ooij [1].
Recently, many efforts have been made by both tire and steel cord manufacturers to
improve the service life of a steel-belted radial tire through a recapping technique,
where the worn-out tread is rebuilt several times using a new rubber compound. For
such a recapping technique, adhesion stability is one of the most important factors,
To

whom correspondence should be addressed. Fax: +82-63-270-2341. E-mail: cnah@moak.


chonbuk.ac.kr

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C. Nah et al.

since the tire will fracture at the interface between the steel cord and rubber, if there
is no adhesion.
It has been known that the major cause for degradation of brass-to-rubber bonding
is dezinci cation, where the zinc is removed from the brass surface under aqueous
conditions during the service period [1, 4, 5]. If brass dezinci cation occurs, the
copper content in the outermost layers will increase and will cause a drastic increase
in the reactivity of the brass toward the sulfur in the rubber layer, resulting in an
excessive growth of copper sul de layer, which gradually becomes nonbonding with
increasing thickness [6 10]. Thus, the service life of the brass-plated steel cord can
be extended considerably if dezinci cation is suppressed. Many attempts have been
made to suppress dezinci cation [1, 11 16]. It can be suppressed by making an
alloy with small amount of metals such as Ni, Co, Sb, Sn, etc. [1, 11]. Ternary
alloy plating containing cobalt or nickel with copper and zinc instead of brass has
been reported to be very insensitive to moisture, salt, steam, or ammonia [12 14].
Another approach by van Ooij [15] to improve the adhesion stability of steel cord
consisted of direct plating of an ultrathin copper lm (<50 nm in thickness) to steel
cord. An excellent adhesion performance was reported. Cho et al. [16] con rmed
the advantage of copper- lm-plated steel cord in terms of adhesion durability. They
reported that although the initial adhesion properties were inferior to those of brassplated cord, they were superior after humidity and salt aging treatments, indicating
an improved bond stability. However, the commercial production of the copper lm-plated steel cords is not yet successful since a breakthrough technology is
required on how to coat such a thin copper lm evenly onto somewhat rough steel
wire surfaces. Thus, there is a clear need to develop a new bonding system to
provide not only a better adhesion performance including its stability, but also the
possibility for commercial production of steel cords.
In this investigation, a new bonding system was studied to improve the adhesion
stability as well as its performance, while the processibility of the steel cord was
comparable to that of commercial manufacturing. The bonding system was a
brass-thin cobalt-thin copper-plated steel cord, where two different thicknesses of
cobalt were applied to determine its effect on adhesion performance. The adhesion
property of the steel cords to rubber was investigated, together with adhesion
stability under conditions of thermal, humidity, and salt solution agings.

2. EXPERIMENTAL

2.1. Preparation and evaluation of a rubber compound


A typical rubber compound used in tire industry was prepared to distinguish the
difference in adhesion performance of the various steel cords investigated. The
compound composition was as follows: natural rubber (Standard Malaysian Rubber
SMR 10, Lee Rubber Co., Malaysia), 100 phr; carbon black N326 (Lucky Co.,
Korea), 65 phr; aromatic processing oil (A#2, Michang Co., Korea), 5 phr; cobalt

Adhesion of steel cord to rubber

655

salt (Manobond, Rhone Poulenc Co., France), 2 phr; resorcinol formaldehyde


resin (B18S, Indspec Co., USA), 2 phr; zinc oxide (Hanil Co., Korea), 8 phr;
stearic acid (Pyungwha Co., Korea), 0.8 phr; antidegradent (2,2,4-trimethyl-1,2dihydroquinone), 2 phr; cure accelerator (N -dicyclohexyl benzothiazole-1-sulfenamide), 0.8 phr; and sulfur, 5 phr.
All compound ingredients except the curatives and stearic acid were mixed using
an internal mixer (82BR, Farrel Co., USA) for 10 min and dumped at about 150 C.
The curatives were then mixed in a two-roll mill (8422, Farrel Co., USA) according
to the procedure described in ASTM D3182 and D3184. The Mooney viscosity
and scorch time, typical indices for occurrence of pre-vulcanization during rubber
processing in the rubber industry, were measured using a Mooney viscometer
(Monsanto, USA) according to ASTM D1646. The cure characteristics were
determined using a moving die rheometer (MDR, Monsanto, USA) at 160 C. The
hardness of vulcanizates was measured using a Shore A durometer according to
ASTM D2240, and the tensile properties were determined with a tensile tester
(Instron 6021) at a crosshead speed of 500 mm /min and at room temperature, as
described in ASTM D412.
2.2. Preparation and compositional analysis of steel cords
Three types of steel cords: brass-, brass / low Co/Cu-, and brass / high Co/Cuplated steel cords were prepared and are denoted as Brass, Low-Co, and High-Co,
respectively. In making the steel cords, a steel rod of 5.5 mm in diameter was
drawn until a diameter of 1.65 mm, was reached and a brass of 63.5 : 36.5 Cu : Zn
was electroplated on the surface of the wire using 5.0, 4.0, and 4.5 g/kg wire for
the preparation of Brass, Low-Co, and High-Co cords, respectively. In the cases
of Low- and High-Co preparations, small amounts of cobalt (0.48 g/ kg for LowCo and 1 g/ kg for High-Co) were plated further onto the brass plating, and nally
copper was plated onto the brass / cobalt-plated lament for the sake of improving
drawing processibility. The plated wires were then nally drawn to make laments
of 0.3 mm in diameter, which were twisted together to make cords of 3 0:3 high
tensile (HT) construction and used in adhesion tests with the rubber compound.
The composition and average plating thickness were analyzed by the inductively
coupled plasma (ICP) (Flame M-120E, Spectra Co., Germany) method, where the
plating materials were dissolved in concentrated nitric acid and were quantitatively
determined using a known calibration curve.
2.3. Evaluation of adhesion properties between steel cords and rubber
T-test specimens were cured at 160 C on a hot press according to the procedure
described in ASTM D2229. Curing was maintained for 10 min longer than the
t90 , i.e. time required for 90% crosslinking, to compensate for initial induction
time for complete heat transfer. To investigate the adhesion stability, three types
of aging experiments were performed in this study. Thermal aging was done in

656

C. Nah et al.

an air oven at 100 C. For humidity aging, the prepared adhesion specimens were
placed in a humidity chamber (Weiss Technik, model 305B) at 75 C and 85%
relative humidity. For salt solution aging, the adhesion specimens were completely
immersed in 20 wt% NaCl solution at room temperature. The same aging periods
of 5, 10, and 15 days were used for all the cases described above.
The pull-out force was determined as the maximum force exerted by the adhesion
samples using a tensile tester (Instron 6021) at a crosshead speed of 100 mm /min
at room temperature. The rubber coverage, de ned as the relative amount of
rubber left on the surface of pulled-out cord, was also determined for six identical
specimens and averaged. Thus, a bare steel cord is ranked as 0%, and a fullycovered cord is ranked as 100% rubber coverage.
2.4. Surface analysis of steel cords
The pulled-out surfaces of steel cords were observed to investigate the locus of failure with a scanning electron microscope (SEM, JEOL, 840A). For a compositional
analysis of the adhesion layer, steel cords pulled-out from the rubber compound
were immersed in 1,3-diisopropylbenzene solution for 24 h to dissolve the rubber
component present on the surface, and the remaining small rubber particles were
removed with a soft tissue. The depth pro les from the outer cord surface to the
inner cord were recorded on an Auger spectrometer (Physical Electronics Phi610).
A surface area of 20 20 m2 was examined at a potential of 5.0 keV, a current of
60 nA, and an incident angle of 60 to the specimen. Surface concentrations were
determined every 30 s from the Auger peaks of detected elements with compensation for their sensitivity factors. A sputter gun with an argon ion beam of 2 2 mm2
raster area was used for depth pro ling at a sputter rate of 9 nm/ min. Ta2 O5 was
used as a standard material for determining the sputter rate.

3. RESULTS AND DISCUSSION

3.1. Physical properties of the rubber compound


A typical rubber compound, widely used in the skim-coat compound of steel cords
in the tire industry, was selected for a practical comparison of adhesion performance
of three different steel cords prepared in our study. Table 1 shows the Mooney
viscosity and cure properties of the compound. The Mooney viscosity and scorch
time, t5 , representing a safety index for pre-vulcanization during processing at
125 C were found, respectively, to be 70 dN m and 9.7 min, which are typical values
for a commercial tire compound for adhesion. A typical value can also be seen for
cure time, t90 , representing an optimum cure time required for 90% vulcanization.
Thus, the rubber compound can be processed and vulcanized in a conventional way.
Table 2 shows the physical properties, before and after thermal aging, of the
rubber vulcanizate. Both hardness and 50%-modulus, de ned as the tensile stress at

Adhesion of steel cord to rubber

657

Table 1.
Mooney viscosity and cure behavior of the rubber compound
Mooney viscometer
Mooney viscosity
ML1C4 @125 C (Mooney unit)
Scorch time, t5 (min)

70
9.7

Cure rheometer at 160 C


Maximum torque, MH (dN m)
t40 (min)
t90 (min)

51.6
4.5
9.8

Table 2.
Physical properties of rubber compound before and after thermal aging
Aging period
at 105 C (day)

Hardness
(Shore A)

50%-Modulus
(MPa)

Tensile strength (MPa)

Elongation-atbreak (%)

0
3
5

75
86
88

2.28
5.59

24.1
7.3
6.0

419
71
38

50% elongation, increased, while tensile strength and elongation-at-break decreased


to one sixth and one tenth of unaged values, respectively, as the aging time was
increased to 5 days. Thus it can be inferred that if the locus of failure is mainly
through the rubber compound, the adhesion force will be strongly affected by
thermal aging. Nevertheless, the selected rubber compound showed the right
physical properties for the proper evaluation of adhesion performance for different
steel cords.
3.2. Plating composition and thickness of newly-prepared steel cords
To con rm the plating composition and thickness, the plating materials dissolved
from plated cords were analyzed by the inductively coupled plasma (ICP) method.
The peak intensity was converted into relative weight per 1 kg of steel lament used
in cord manufacturing and into corresponding plating thickness by considering the
lament geometry, as shown in Table 3, together with data for zinc and copper
for Brass, Low-Co, and High-Co cords. The plating weight and thickness of
High-Co were found to be more than ve times larger that those of Low-Co,
namely, the thicknesses for Low- and High-Co cords were found to be 1 and 5 nm,
respectively. The total plating weight was not constant, but found to be of the
order of High-Co > Brass > Low-Co, even though the amount of initial plating
before drawing was adjusted to have similar thicknesses. This seems to be due
to the difference in loss of plating materials during the drawing process, since the
extensibility is different for each material. Nevertheless, the prepared three cords

C. Nah et al.

658

Table 3.
Plating compositions and thickness for three steel cords investigated
Composition
Zn
Cu
Co
Total

Weight (g/ kg)


Thickness (nm)
Weight (g/ kg)
Thickness (nm)
Weight (g/ kg)
Thickness (nm)
Weight (g/ kg)
Thickness (nm)

Brass

Low-Co

High-Co

1.23
87
2.26
159

3.49
246

0.95
67
2.06
145
0.01
1
3.02
213

1.22
86
2.58
182
0.08
5
3.88
274

were thought to be appropriate for comparing adhesion performance, especially in


terms of its stability, since a key parameter to adhesion stability is expected to be
the amount of cobalt plating, rather than the total amount of plating materials.
3.3. Adhesion properties and their stability
Table 4 shows the effect of thermal aging on the adhesion properties for the three
types of steel cords investigated. The pull-out forces for unaged Low- and HighCo cords were slightly higher than that of Brass cord, while the rubber coverage
was about the same for all the cases. The thermal aging effect was found to be
very signi cant on the pull-out force, i.e. the initial pull-out force dropped to about
40% of its initial value, regardless of the cord type. However, in terms of rubber
coverage, Low-Co cord showed the highest resistance to thermal aging and Brass
cord the lowest. However, it should be noted that the rubber coverage of Brass
still remained at about 80% even after 15 days thermal aging, indicating that the
major adhesion failure occurred in the rubber compound matrix, and not at the
rubber cord interface. Thus, the observed strong effect of thermal aging on pullout force could be explained by the poor resistance of the rubber compound itself to
thermal aging, as can be seen in Table 2.
Table 5 shows the effect of humidity aging on adhesion performance. The Low-Co
cord showed the highest adhesion durability among the cords in terms of both pullout force and rubber coverage. A fairly good adhesion stability was also observed in
the case of High-Co cord, when compared with that of Brass cord. One of the major
reasons for the degradation of adhesion under high moisture conditions, as with the
present humidity aging, is the dezinci cation reaction, where zinc is dislodged from
the brass surface forming ZnO or Zn(OH)2 through reaction with water [1, 4, 5].
The resultant copper-rich brass becomes highly activated and reacts with sulfur or
sulfur-containing polymer molecules resulting in accelerated formation of cuprous
sul de which causes a gradual weakening of the bond with increasing thickness. It
was suggested that cobalt suppressed such a dezinci cation reaction of brass-plated
steel cord [1, 1114]. Thus, the observed enhancement in adhesion stability for

Adhesion of steel cord to rubber

659

Table 4.
Adhesion properties of Brass-, Low-, and High-Co cords to rubber compounds after thermal aging at
100 C in air an oven
Cord

Brass
Low-Co
High-Co

Pull-out force (N)

Rubber coverage (%)

Aging period (day)

Aging period (day)

10

15

10

15

427
450
455

346
368
404

248
261
257

175
201
178

92
95
95

91
92
91

86
95
95

80
94
87

Table 5.
Adhesion properties of Brass-, Low-, and High-Co cords to rubber compounds after humidity aging
at 75 C in 85% relative humidity
Cord

Brass
Low-Co
High-Co

Pull-out force (N)


Aging period (day)

Rubber coverage (%)


Aging period (day)

10

15

10

15

427
450
455

408
444
448

327
398
361

362
432
418

92
95
95

88
95
95

79
89
91

76
95
94

Low- and High-Co cords may be explained by the reduced dezinci cation reaction
due to a thin cobalt plating.
In order to support the explanation of the cobalt effect, the chemically-cleaned
surfaces of pulled-out cords were analyzed using Auger specroscopy to investigate
the composition of adhesion interfaces. Figures 1 3 show the AES depth pro les
before and after humidity aging at 75 C and 85% relative humidity for Brass, Low-,
and High-Co cords, respectively. In the case of Brass cord (Fig. 1), a considerable
compositional change was observed during humidity aging, i.e. considerably higher
concentrations of oxygen and zinc were observed after a sputtering time of 5 min,
suggesting an increase in the formation of ZnO or Zn(OH)2 . The copper and sulfur
contents at short sputtering times became higher, and the peaks became broader,
indicating an increased thickness of copper sul de. The observed changes in
compositional pro les are thought to be responsible for the poor adhesion stability
for Brass cord.
However, the compositional pro le did not change as much for Low-Co cord after
humidity aging, as shown in Fig. 2. In this case, we could not detect cobalt due
probably to extremely low concentrations (0.5% for Low-Co and 1.8% for HighCo of total plating thickness). An intermediate change was found in the case of
High-Co cord, as shown in Fig. 3. The relatively stable composition pro les at the
adhesion interfaces for cobalt-plated cords can again be explained by the suppressed
dezinci cation reaction by cobalt.

660

C. Nah et al.

Figure 1. AES depth pro les of Brass pulled-out from rubber compound before and after humidity
aging for 15 days: upper (unaged), lower (aged).

Adhesion of steel cord to rubber

661

Figure 2. AES depth pro les of Low-Co pulled-out from rubber compound before and after humidity
aging for 15 days: upper (unaged), lower (aged).

662

C. Nah et al.

Figure 3. AES depth pro les of High-Co pulled-out from rubber compound before and after humidity
aging for 15 days: upper (unaged), lower (aged).

Adhesion of steel cord to rubber

663

Table 6.
Adhesion properties of Brass-, Low-, and High-Co cords to rubber compounds after salt solution (20%
NaCl) aging at room temperature
Cord

Pull-out force (N)

Rubber coverage (%)

Aging period (day)

Brass
Low-Co
High-Co

Aging period (day)

10

15

10

15

427
450
455

407
418
445

361
385
379

339
379
367

92
95
95

91
93
95

73
81
82

73
76
76

Table 6 shows the effect of salt solution aging on adhesion performance. The
pull-out force of Low-Co cord remained around 85% of its initial value, while
Brass and High-Co cords remained at about 80%, after salt solution aging for 15
days, which is the extreme aging condition. Rubber coverage was also found to be
slightly higher for cobalt-plated cords than for brass-plated cords after aging. The
enhancement in adhesion stability was much smaller when compared with that of
humidity aging. This might be due to a different mechanism of salt corrosion from
dezinci cation during humidity aging. A further study is necessary to understand
the exact mechanism of salt corrosion in more detail.
Figures 4 and 5 show SEM photographs of pulled-out surfaces of thermal- and
salt solution-aged cords, respectively. In the case of thermal-aged cords (the whole
surfaces were covered with typical fracture patterns of rubber) suggesting that the
adhesion failure mostly took place through the rubber matrix in the vicinity of
adhesion interfaces. However, in the cases of salt solution aging, much severer
aging conditions in terms of adhesion stability of brass-plated cord, some part of
the surface became smoother, indicating an interfacial failure and lower rubber
coverage. Moreover, the smooth regions were found to be largest for Brass and
smallest for Low-Co cords. A similar trend was also observed in the case of
humidity aging.
Based on the observed adhesion results, it can be concluded that an application
of thin cobalt and copper layers onto brass-plated cord keeping the total amount
of plating constant enhances not only the initial adhesion performance, but also
the adhesion stability. Moreover, the ease of mass production of the new cords is
comparable with that of conventional brass-plated cord, if the processing variables
are carefully optimized. Thus, the suggested cord structure is expected to contribute toward improving the service life of steel-reinforced rubber articles such as
tires.

664

C. Nah et al.

(A)

(B)
Figure 4. SEM photographs of pull-out surfaces of steel cords after thermal aging for 15 days:
(A) Brass; (B) Low-Co; and (C) High-Co.

4. CONCLUSIONS

A new brass-plated steel cord containing a thin cobalt layer (a few nanometers thick)
was prepared for improving the adhesion stability to rubber. The initial adhesion
performance of the cobalt-plated cords was superior to that of conventional brassplated ones. The effect of thermal aging was profound in terms of adhesion force

Adhesion of steel cord to rubber

665

(C)
Figure 4. (Continued).

(A)
Figure 5. SEM photographs of pull-out surfaces of steel cords after salt solution aging for 15 days:
(A) Brass; (B) Low-Co; and (C) High-Co. The circled areas indicate interfacial failure and lower
rubber coverage.

regardless of the cord type due to the reduced mechanical strength of rubber itself
by thermal aging, but a marginal improvement in stability was observed in terms
of rubber coverage. The adhesion stability of the cobalt-plated cords, especially

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C. Nah et al.

(B)

(C)
Figure 5. (Continued).

the low cobalt cord, was considerably improved against aging conditions, notably
humidity aging. Thus, the newly suggested bonding system can be a practical
way to improve the adhesion stability of steel cord-reinforced rubber articles, while
maintaining good initial adhesion performance.

Adhesion of steel cord to rubber

667

Acknowledgements
The authors would like to thank Mr. Young Goo Kim at the R&D center of
KISWIRE Ltd. for Auger and ICP analyses.

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