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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
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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
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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.
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
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)
Elongation-atbreak (%)
0
3
5
75
86
88
2.28
5.59
24.1
7.3
6.0
419
71
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C. Nah et al.
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Table 3.
Plating compositions and thickness for three steel cords investigated
Composition
Zn
Cu
Co
Total
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
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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
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
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).
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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).
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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).
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Table 6.
Adhesion properties of Brass-, Low-, and High-Co cords to rubber compounds after salt solution (20%
NaCl) aging at room temperature
Cord
Brass
Low-Co
High-Co
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.
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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
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.
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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