Nippon Gomu Kyokaishi, No. 4, 2000, p.

180

Adhesion of rubber to metal

Y. Ikeda

Translation submitted by K. Halpin

Selected from International Polymer Science and Technology, 27, No. 4, 2000, reference NG 00/04/180; transl. serial no. 14514

1. INTRODUCTION unfortunately, however, productivity is poor. Moreover,

With the discovery of vulcanisation by sulphur in the
nineteenth century, rubber began to find application in
many new fields. The twentieth century saw the development
of numerous synthetic rubbers, with the result that rubber
materials are now essential to daily life in many industrial
and household products, especially automotive tyres.
However, rubber itself is a relatively weak material and is
therefore reinforced before use, the effective reinforcements
including metals, inorganic materials, plastics and fibre.
A significant part of this reinforcing technology relates to
adhesion. Automotive tyres, belts, seismic bearings,
vibration isolators and industrial functional components
have all been developed by improving bonding to rubber
in order to secure enhanced performance and greater
functionality. Adhesion is thus one of the key production
and processing technologies in the rubber industry.
Bonding to rubber during vulcanisation can be effected
by direct bonding, achieved at the same time as mould
processing of the rubber, or by indirect bonding, in which
an adhesive is applied to the adherend and the rubber is
vulcanised in contact with the adhesive coat. Direct
vulcanisation bonding is currently used in the manufacture
of tyres and belts, while indirect vulcanisation bonding is
mostly used for seismic bearings, vibration isolators and
industrial functional components. The low production
costs make direct bonding suitable for mass production
but there are limits to the rubber compounds and metals
that can be used and no universally applicable technology
has emerged. Indirect bonding, on the other hand, is
virtually unlimited as to the species of rubber and adherend
material and can be applied to almost any combination –
because of the global environmental problems posed by
organic solvent based adhesives, moves to water-based
adhesives are now being investigated and some of the
associated problems have still to be solved.
Joining with adhesives involves two interfaces, offering
potential for cohesive failure of the adhesive itself or
interfacial delamination. Expectations have therefore
focused on the development of integral moulding
technology with adhesive-free systems.
Brass plating has long been familiar as a means of
achieving direct vulcanisation bonding to metals, and
with the advent of steel radial tyres, adhesion between
brass plating and rubber has been an important area of
research as a fundamental means of assuring tyre
endurance. Furthermore, recent progress in instrumental
surface analysis has brought advances in the analysis of
interface structure, and numerous reviews of the
mechanism of adhesion have been published (refs. 1–7).
This article outlines the individual technological
developments and flow of research with reference primarily
to the direct bonding of rubber to various metals or alloys
during vulcanisation.
2. ADHESION BETWEEN RUBBER AND BRASS
PLATING
Adhesion between rubber and brass plating has been
extensively studied because of its importance to steel cord-
rubber bonding in the manufacture of steel radial tyres, and
the bonding interface has been analysed by a host of
researchers with the aim of elucidating the mechanism of
adhesion.

T/24 International Polymer Science and Technology, Vol. 28, No. 8, 2001
 Since rubber and brass plating can be bonded directly
in sulphur vulcanisation systems, it is clear that adhesion
arises at least as a result of chemical reactions between the
brass and rubber. The reaction zone is considered to be
very thin, less than 100 nm. The following factors are
known to affect the formation of the reaction zone in
adhesion (ref. 3):
(1) plating factors:
(1) the Cu/Zn ratio in the plating,
(2) the plating thickness,
(3) the amounts of Zn and ZnO at the surface;
(2) rubber factors:
(1) the nature of the compounding agents,
(2) the amounts and ratios of the compounding
agents;
(3) environmental factors:
(1) the curing conditions,
(2) ageing conditions.
The complex way these factors affect formation of the
reaction zone has made it difficult to establish a theory of
adhesion.
Two views of adhesion are currently advocated: chemical
bonding, dependent mainly on primary bonds; and physical
bonding via the reaction zone. However, no definitive
conclusion has yet been reached.
Ooij (ref. 8) analysed the bonding interface between
brass and rubber by XPS and found the concentration
distribution of elements in the direction of depth as shown
in Fig. 1. An interfacial layer of thickness approximately
100 nm is evidently formed at the bonding interface, and
consists of two layers: zinc oxide containing a small
brass concentration rubber
Depth, nm
Fig. 1 XPS analysis of rubber-brass bonding interface
International Polymer Science and Technology, Vol. 28, No. 8, 2001
Thickness of sulphide layer (nm)
Fractional pull strength (%)
Thickness of
sulphide layer
fractional pull
strength
Alloy ratio (Cu %)
Fig. 2 Adhesion and sulphide thickness/composition in relation
to brass Cu content
amount of zinc sulphide on the metal side of the interface,
and copper(I) sulphide on the rubber side of the interface.
Since the copper sulphide in the bonding interface is a non-
stoichiometric compound Cu S, and primary bonds
1.97
such as Cu–S-rubber could not be detected, physical
bonding was postulated.
Haemers (ref. 9) likewise analysed the brass-rubber
interface by XPS and obtained the results shown in Fig. 2.
Cu2-xS is absent when there is less than 50% of Cu, while
only Cu2-xS occurs when there is 80% or more of Cu, and
in both cases adhesion is poor. Good adhesion requires
the present of suitable quantities of both Cu2-xS and ZnS,
and the author postulates chemical bonding which requires
primary bonds like Cu-rubber-S formed directly via reaction
of Cu with rubber-S linkages. This does not mean primary
bonds have been detected, however.
Using brass foil, Kretzschmar (refs. 10,11) fabricated
bonds with a rubber compound limited to cure accelerator
and sulphur only, and examined ultrathin sections
containing the bonding interface by TEM/EDX. As shown
in Fig. 3, two zones were identified: a ZnO layer extending
approximately 100 nm from the brass and a CuxS layer
extending another 250 nm like a resinous projection.
100 nm
rubber
Fig. 3 TEM micrograph of rubber-brass bonding interface
T/25
The thickness of the reaction zone was found to increase
greatly with increasing sulphur content.
The mechanism of adhesion is being widely studied by
interfacial analysis in the expectation that elucidation of
the mechanism will serve to establish a more durable
method of bonding.
2.1 Steel cord and brass plating (ref. 12)
Zinc is believed to have the role of inhibiting reaction
between copper and sulphur in adhesion to brass plating.
Experiments showing that there is an optimum level of
copper in the brass have been carried out by Maessele (ref.
13) and Haemers (ref. 9), who report that adhesive
strength reaches a maximum at a copper content of
approximately 60–80%. The brass plating used for bonding
to rubber has a copper content of around 63% but as a ZnO
layer is formed on the surface, the surface Cu content is
lower than in the interior and the existence of a concentration
gradient in the depthwise direction has been documented
by Ooij (ref. 14), Haemers (ref. 9), Kato (ref. 4) and others.
Drawn brass-plated steel cord in particular has recently
been found to have a layer of reacted phosphate, a
component of the wire drawing lubricant, at the extreme
surface, as shown in Fig. 4 (ref. 6).
Although steel cord is the tyre cord material used in the
largest quantities, it is problematic in that, as well as giving
heavier tyres than organic fibre and thus running against
the trend to reduced tyre weight, it gives unsatisfactory wet
heat adhesion.
Special heat treatment of low carbon steel of reduced
impurity content affords a composite microstructure with
martensite as reinforcing disperse phase in a ferrite matrix,
and extremely fine, ultrahigh strength extreme gauge steel
cord (Saifer‚) has been developed by cold drawing and
toughening this material (ref. 15). The use of a resin
coating material improves adhesion to rubber while also
enhancing fretting fatigue performance and an outstanding
reinforcing effect is therefore obtained, attracting interest
outermost surface
Zn3(PO4 )2
interior
Fig. 4 Model of steel cord surface
T/26
as a potential tyre cord. High tensile wire variously
containing Cr, Ni and Mo has also been developed, and
as extreme gauge steel wire can be produced from these
materials, this should make it possible to reduce tyre weight
(refs. 16–18).
The incorporation of cobalt and nickel in the brass as
alloying components is known to be useful in preventing
the reduction of adhesive strength by moisture during
vulcanisation. The components are introduced by plating
over the brass followed by thermal diffusion, or are
deposited from the vapour state by ion beam sputtering.
Anti-ageing adhesion is thereby improved. Since cobalt
plating allows the content of organic cobalt salts in the
rubber to be eliminated or much reduced, the rubber can
be compounded so that deterioration in adhesion with time
or thermal degradation of strength and elongation can be
inhibited. Moreover, the amount of sulphur components,
which have hitherto been present at a relatively large
content, can be reduced, with the result that thermal ageing
of the rubber can be prevented and the corrosion fatigue
resistance of the steel cord can be improved.
2.2 Rubber compound
Rubber compounds have also been modified in various
ways to enhance adhesion. An examples is the use of silica.
Silica is used to improve the rubber tear strength, fatigue
endurance characteristics, wear resistance, self heating,
hardness, modulus, rolling resistance and adhesion. Silanol
groups on the silica surface are said to enhance compatibility
with metal oxides.
Evans et al. (ref. 19) used precipitated silica in natural
rubber filled with carbon black containing organic cobalt
salts as an adhesion promoter and analysed the physical
properties and adhesion of the rubber. Increase in silica
content improved tear strength and bonding in composites,
and compounds high in silica and low in sulphur were
found to have greater tear strength and adhesive energy.
residual lubricant
Cu2O
ZnO containing Cu
β-CuZn
α-CuZn
International Polymer Science and Technology, Vol. 28, No. 8, 2001
Since adhesive energy increases linearly with increase in
silica, it is clear that the use of silica has an effect on the
interfacial layer formed on the metal wire.
Hewitt (ref. 20) has investigated the mechanism whereby
silica improves adhesion between natural rubber and
brass from the standpoint of the rubber compound. In
sulphur-containing peroxide-crosslinked natural rubber
compounds, both the pull strength and rubber coverage
improved at silica 10–40 phr. In silica-zinc oxide-resin
(resorcinol-formalin, hexamethoxymethylmelamine)
systems, maximum adhesive strength was developed at
silica 5–12 phr and zinc oxide 1–2 phr. Replacement of
part of the carbon black with silica gives a state of total
adhesion. In compounds of silica reinforced elastomer,
reaction of zinc oxide with the silanol surface readily
affects crosslinking, viscosity and reinforcing effects.
Adhesion to brass is likely to be affected in the same way,
and Hewitt attributes his results to the zinc inhibitory effect
of silica at the interface.
Two different adhesion promoters (RFS: resorcinol-
formaldehyde-silica, and cobalt compounds) are normally
used for bonding to steel tyre cord, but because of
environmental and handling problems, a promoter
comprising a cobalt compound and methylene donor
replacement for formaldehyde has been developed
(ref. 21).
3. ADHESION BETWEEN RUBBER AND NON-BRASS
PLATING
3.1 Adhesion between rubber and zinc plating
Another metal well known for its ability for direct bonding
to rubber during vulcanisation is zinc. Since the rate of
sulphidation of zinc is very much slower than for copper,
zinc appears to buffer the reaction between copper and
sulphur in bonding between rubber and brass. Moreover,
the strength of bonding between zinc and rubber is much
weaker than between brass and rubber, and a rubber
additive such as a cobalt salt or HRH (Hisil-resorcinol-
hexamethylenetetramine) is normally required for adhesion
to zinc (ref. 22). The work of Ashida et al. (refs. 23, 24) has
established the following in this respect: of the various
cobalt salts available, cobalt naphthenate is effective;
sulphenamides are best as cure accelerators, followed by
thiazole accelerators; and thiurams lose the accelerative
effect by complexing with cobalt. During vulcanisation, the
cobalt and sulphur precipitate on the zinc sheet in direct
proportion to the amount of cobalt naphthenate added.
However, cobalt is not detected from zinc surfaces giving
imperfect bonding in high temperature cure; at the same
time, the amount of sulphur present decreases. This suggests
that adhesion occurs through migration of cobalt and
sulphur to the zinc surface.
International Polymer Science and Technology, Vol. 28, No. 8, 2001
Mori et al. (ref. 25) bonded zinc plated steel cord
directly to SBR-NR during vulcanisation and investigated
the effect of sulphur and cure accelerator on adhesion and
the adhesive promoting effect of the naphthenate salts of
different metals. Nickel naphthenate was found effective in
enhancing adhesive strength, while a cure accelerator
comprising the thiazole MBTS and the sulphenamide BBS
gave high peel strength and rubber coverage. The thiuram
accelerator TMTD reacted with cobalt naphthenate during
vulcanisation, reducing its cure accelerating efficacy, and
inhibited migration of cobalt to the zinc surface, resulting
in imperfect adhesion.
3.2 Adhesion between rubber and zinc alloy plating
Nishimura et al. (ref. 26) have investigated the cure
adhesion to rubber of a ternary alloy made by adding a
third component (Ni, Co, Fe, Sn) to copper-zinc alloy. The
third component was found to have a marked effect. For
example, Cu–Zn–Ni alloy plating remains almost unoxidised
in initial bonding, and resists corrosion in wet heat tests.
Cu–Zn–Ni ternary alloy plating affords excellent bond
endurance, an effect attributed to corrosion resistance.
In view of the problematic corrosion resistance of brass
plating films, Ooij (refs. 27–29) et al. explored cure
adhesion between rubber and plating films of various non-
copper alloy systems such as Zn–Ni, Ni–Zn/Zn–Ni, Co–Zn
and Ni-Zn/Zn–Co. The addition of organic cobalt salt, an
adhesion promoter, was found to improve adhesion
between rubber and Zn-Ni alloy plating film and Ni-Zn/
Zn-Ni alloy plating film. A two-layer film of Zn-80 wt% Ni
alloy plating deposited over a Zn-1 wt% Co primer plating
gave good adhesion. Cohesive failure of the rubber
occurred with a Ni–Zn/Zn–Co alloy plating film, while
room temperature rolling of the plating film resulted in
mixed delamination. However, cohesive failure of the
rubber occurs after ageing tests. This was said to be
because the metal plate gets thinner in rolling and so
develops flexibility, and because the ageing test promotes
cohesive failure of the rubber, inhibiting interfacial
delamination between rubber and plating.
3.3 Adhesion between cobalt thin films and rubber
(ref. 30)
Good adhesion is obtained in vulcanisation bonding to
cobalt thin film made by the dry plating process when the
rubber compound is vulcanised with a reduced addition of
sulphur and organic cobalt salts are omitted. The bond
obtained retains its excellent endurance in the wet heat test.
Fig. 5 shows the results from TEM examination of ultrathin
sections containing the union cross-section of the bond.
T/27

0.5 µm
0.1 µm
Fig. 5 TEM micrograph of rubber-Co bonding interface
A comparatively uniform reaction zone is observed between
the rubber and cobalt, and clear differences are evident in
the zone of reaction with cobalt and brass, these presumably
accounting for the difference in adhesion.
AES analysis in the direction of depth below the surface
of the cobalt revealed the presence of sulphur in the
extreme surface layer, cobalt immediately below the sulphur
layer, and copper below the cobalt. It would hence appear
that only cobalt and not copper reacts with the sulphur.
3.4 Adhesion between rubber and electroless nickel alloy
plating
Mori et al. (refs. 31, 32) treated an electroless Ni plating
alloy rubber alloy
S Ni
Ni
6 µm
(Cu 0 mol.%) (Cu 31.0 mol.%)
Fig. 6 Linear EDS analysis of rubber-Ni alloy plating film bonding interface
T/28
film with triazine and found that good adhesion was
exhibited when 1,3,5-triazine-2,4,6-trithiol was used as
the rubber cure system for CR or EPDM and 1,3,5-triazine-
2,4,6-trithiol monosodium salt was used for NR. An optimum
addition exists for each system, and the endurance is
claimed to be similar to that obtained with existing cure
adhesives.
The effects of cure temperature and cure time in the
indirect vulcanisation bonding of nickel plating to NR
compounded with triazine thiol (RTD) were also investigated
(ref. 32). RTD was reported to act as a binder between the
rubber and nickel plating as the cure temperature was
raised or the cure time was lengthened; reaction at the
interface increased, an ample reinforcing layer was formed
and peel strength increased. Furthermore, in the
vulcanisation bonding of Ni plating thin films to fluoro-
rubber of the triazine thiol tetrabutylammonium salt curing
type (ref. 32), bonds of outstanding heat resistance and oil
and water resistance were obtained. In this case the
triazine thiol was considered to play an important role as
an interfacial binder in primary bonding of the interfacial
reinforcement layer and the interface. Ikeda et al. (refs. 34,
35) produced Ni–Cu–P alloy films of different alloy
composition by electroless plating and bonded the films to
rubber during vulcanisation. Adhesion strong enough for
cohesive failure of the rubber to occur was obtained up to
a Cu content of around 20 mol.%. At Cu contents above 20
mol.%, however, the rubber coverage of the rubber-
delaminated plating showed a tended to decrease and
mixed delamination or interfacial delamination appeared
once the Cu content exceeded 50 mol.%. Although peel
strength showed a tendency to decline after the water-
resistant ageing test, this was attributed to ageing or
hardening of the rubber, and to a decline in interlaminar
strength as water penetrated the sulphide layer at the
specimen edge.
Fig. 6 shows the results of linear analysis by EDS of the
adhesion interface in unions of rubber with alloys of different
rubber alloy rubber
Cu
S
S
Ni
6 µm 6 µm
(Cu 54.0 mol.%)
International Polymer Science and Technology, Vol. 28, No. 8, 2001
 Table 1 Effect of alloy composition in bonding to electroless Pd alloy plating film during rubber

Composition Peel strength Solder wettabilityb) Rubber coverage

Alloy
(mol. %) (kN/m) spread area (mm2) (%)

Pd 100 29.2 5.1 100

Pd-P 99.3:0.7 28.8 4.7 100

Pd-P 97.5:2.5 26.4 4. 3 98

Pd-P 93.0:7.0 20.7 – 80

Pd-Ni-P 51.6:30.1:16.3 27.5 1.1 98

Pd-Ni-Pa) 51.6:30.1:16.3 28.7 – 100

Pd-Ni-P 36.0:54.2:9.8 – 1.4 interfacial peel

Pd-Ni-Pa) 36.0:54.2:9.8 27.9 – 100

Pd-Ni-P 29.0:63.0:8.0 – 1.4 interfacial peel

Pd-Ni-Pa) 29.0:63.0:8.0 27.9 – 98

a)
Immerse 10 min in 10% hydrochloric acid, then wash with water and dry at room temperature
Solder ball: Sn:Pb = 6:4, 1 mm diameter; solder fusion temperature: 215°C, 20 sec
b)

copper content. In all cases sulphur is localised at the

interface between the rubber and alloy film, implying that a

x 600000
sulphide layer has formed at the interface. The thickness of

30 nm
this layer would have some bearing on the peel strength.

3.5 Adhesion between rubber and electroless Pd

alloy plating (refs. 36–40)
When vulcanisation bonding to electroless Pd-P alloy
plating using NR was carried out at different sulphur
additions and hot water resistant ageing tests were run with
immersion for 3 days in water at 95°C, the peel strength
invariably peaked at a sulphur addition of 2.5 parts.
Although a decrease in peel strength was noted when more p q r s t
sulphur than this was added, the result was cohesive failure
of the rubber in every case. The decrease in peel strength
would hence appear to be due to a decline in tear strength
due to hardening or deterioration of the rubber, indicating
that the Pd-P alloy plating film adheres strongly to the
rubber and has excellent durability.
The peel strength in adhesion between a Pd-P
plating film and rubber tended to decline as shown
in Table 1 as the P content of the plating film increased.
Moreover, the rubber coverage of the plating surface after
the peel test decreased with increase in P content. The
solder wettability of the plating surface clearly decreases
as the P content increases, implying that an oxide film forms
more easily on the plating surface as the P content is
increased. Fig. 7 TEM micrograph of rubber-Pd plating film bonding interface

International Polymer Science and Technology, Vol. 28, No. 8, 2001 T/29
 Fig. 7 shows the results from TEM examination of Oxides of phosphorus are formed at the outermost
ultrathin sections containing the union interface. A very surface of Pd-P alloy platings, the oxide layer forming more
fine, nebulous reaction zone of thickness approximately easily as the P content increases. It may be inferred that
30 nm was identified at the interface. Fig. 8 shows adhesive strength decreases because reaction with sulphur
the results from EDS analysis of the reaction zone. is inhibited by the oxide layer, giving rise to a non-uniform
The relative abundance of Pd and S clearly changes going sulphide layer.
from the rubber layer to the plating layer. A gradient effect
was thus observed in the reaction zone: instead of a
uniform reaction product being formed through the reaction
zone, sulphur-rich PdxS is formed in the vicinity of the
rubber while palladium-rich PdxS is formed in the vicinity
of the plating layer.

s
p

Intensity
Intensity

Energy (keV) Energy (keV)

q t
Intensity

Intensity

Energy (keV) Energy (keV)

r
Intensity

Energy (keV)

Fig. 8 EDS analysis of different regions in Fig. 7

T/30 International Polymer Science and Technology, Vol. 28, No. 8, 2001

Shearing adhesion (MPa)
iron stainless brass zinc aluminium
steel
❑ – peroxide only
■ – zinc acrylate and peroxide
Fig. 9 Crosslink bonding between different kinds of metal sheet
and a zinc acrylate compound of EPDM
4. ADHESION BETWEEN NON-PLATED METALS
AND RUBBER
4.1 Zinc acrylate-organic peroxide rubber compounds
(refs. 41–44)
When the metallic crosslinking promoter zinc acrylate or
zinc methacrylate is used in the crosslinking system in
combination with a peroxide, adhesion to the metal substrate
is much increased even without pre-treatment of the metal
surface; at the same time, the mechanical properties
improve. This adhesive effect was seen with EPDM, NR,
EVA, CSM and silicone rubber alike. Fig. 9 shows the
crosslinking adhesive effect obtained with an EPDM
compound for different metals. The shearing adhesion
rises on compounding with zinc acrylate, reaching 0.5
MPa at 2 phr and 11.4 MPa at 20 phr. The Ca and Mg salts
are also effective for adhesion, though not as effective as
the zinc salts. Zinc methacrylate is less highly reactive than
zinc acrylate, and adhesion is poorer. The mechanism of
adhesion is completely unknown but the zinc acrylate or
zinc methacrylate presumably deposits on the metal surface
where it reacts with the rubber.
4.2 Polyacetylene film adhesive
Ooij (ref. 45) has found that a plasma polymerised
polyacetylene film deposited on steel gives excellent
adhesive strength in respect of high sulphur, cobalt-
containing tyre cord compounds. This is because the film
reacts chemically with the rubber during vulcanisation. It
would hence be possible to achieve direct vulcanisation
bonding to rubber with a continuous process by coating
steel cord with the film. However, compared with brass-
plated cord, the bonds have poor resistance to salt water
deterioration.
International Polymer Science and Technology, Vol. 28, No. 8, 2001
4.3 Polyacrylic acid derivative water-soluble polymer
adhesives (refs. 46–48)
Water-soluble polymer coupling agents have been obtained
by chemically modifying some of the carboxylic acid
groups in polyacrylic acid with hydroxyamine groups to
raise affinity with metals, and then chemically modifying
the derivative with allyl glycidyl ether to achieve
copolymerisation with EPDM. Good bonds were obtained
when the coupling agents were coated on stainless steel
and dried at 120°C and the steel then was bonded with an
EPDM peroxide crosslinking system. The bonds withstood
a 22 hour autoclave test at 135°C with water/glycol (50/
50) under a pressure of 0.25 MPa. The effect is attributed
to complex formation between the hydroxyamine groups
in the polymer and the Fe ions in stainless steel, resulting
in the formation of a chemically and thermally stable
bonding layer. The bonding of EPDM and fluorocarbon
(FKM) elastomer to metals by making chemical modifications
to polyvinylamine is also being investigated and bonds of
excellent heat-resistance and resistance to chemicals are
being obtained.
4.4 Plasma treatment
Costantino et al. (ref. 49) have plasma polymerised
hexamethyldisiloxane to aluminium surfaces with oxygen
as carrier gas, bonded silicone elastomer to the metal using
hydroxyl-terminated poly(dimethylsiloxane) as sealant with
methyltrimethoxysilane and titanic acid catalyst as the
hardener, and obtained excellent bonds characterised by
cohesive failure of the adherend. Moreover, in a study of
the direct bonding of fluoro-rubber to aluminium, Momose
et al. (ref. 50) have found that argon plasma treatment of
the aluminium in the presence of Teflon (PTFE) increases
adhesive strength, which also increases with rise in treatment
temperature; they further observed that an increased
concentration of hydrophilic groups due to removal of
carbon impurity from the treatment surface and the presence
of strongly adsorbed CF2 components are important to
adhesion, and that adhesive strength increases several fold
compared with untreated aluminium when a film of plasma
polymerised cyclohexane is first formed on the aluminium
and then treated with argon plasma and argon plasma in
the presence of PTFE, the adhesive strength being related
to the thickness of the polymer film.
5. CONCLUSIONS
The bonding of rubber to metals during vulcanisation has
been reviewed above, inclusive of various new methods.
Although the mechanism of reaction is still unclear, a
wealth of experimental results indicate that the important
T/31
adhesion factor in direct vulcanisation bonding is the
formation of a sulphide layer at the interface due to
reaction of the metal with sulphur in the rubber, and that
some interaction occurs between this sulphide layer and
rubber.
A host of problems including the state of the metal
surface, migration of sulphur and adhesion promoter from
the rubber matrix, the reactions at the interface, the rate of
reaction and diffusion at the interface, expression of
physical or chemical interaction, and the formation of
gradient structure, have still to be solved before better
methods of adhesion can be established. Further research
will hopefully reveal the mechanism of adhesion it its
entirety.
REFERENCES
1. W.J. van Ooij, Kautchuk. Gummi Kunstoffe, 44,
1991, p. 348
2. K. Mori, Nippon Gomu Kyokaishi, 65, 1992, p. 61
3. Y. Ishikawa, Nippon Gomu Kyokaishi, 65, 1992,
p. 86
4. H. Kato, Nippon Gomu Kyokai Koenkai, 41, 1995,
p. 50
5. B.G. Grouther, Rapra Rev. Rep. 8, 1996, p. 97
6. T. Hachinosuka, Nippon Gomu Kyokaishi, 70, 1997,
p. 293
7. Y. Ikeda, Nippon Setchaku Gakkaishi, 34, 1998,
p. 488
8. W.J. van Ooij, J. Surface Science, 68, 1977, p. 1
9. G. Haemers, Rubber World, 182, 1980, p. 26
10. T. Kretzschmar, F. Hofer and K. Hummel, Kautchuk.
Gummi Kunststoffe, 45, 1992, p. 1038
11. T. Kretzschmar, K. Hummel and F. Hofer, Rubber
Chem. & Technol., 66, 1993, p. 837
12. S. Fukuhara, Porifairu, 31, 1994, p. 39
13. A. Maeseele and E. Debruyne, Rubber Chem. &
Technol., 42, 1969, p. 613
14. W.J. van Ooij, Rubber Chem. & Technol., 52, 1979,
p. 605
15. Nippon Kinzoku Gakkai Kaiho, 28, 1989, p. 313
16. Japan Patent Kokai No.1992-73280
17. Japan Patent Kokai No.1990-61185
18. Japan Patent Kokai No.1990-19444
19. R.R. Evans, Meet. Rubber Div. ACS, 147, 1995,
p. 30
T/32
20. N.L. Hewitt, Rubber World, 210, 1994, p. 19
21. L. White, Eur. Rubber J., 178, 1995, p. 22
22. W.E. Weening, Kautchuk. Gummi Kunststoffe, 31,
1978, p. 227
23. M. Ashida, T. Fukumoto and T. Watanabe, Nippon
Gomu Kyokaishi, 50, 1977, p. 807
24. M. Ashida, M. Nakatani and Y. Takemoto, Nippon
Gomu Kyokaishi, 57, 1984, p. 544
25. K. Mori, Shi Xiaodong and H. Hirama, Erasutoma
Toronkai Koen Yoshishu, [Elastomer Symposium,
Abstracts of Papers], 11th, 1998, p.178
26. Y. Nishimura, S. Yamamoto and H. Nakata, Proc.
57th Annual Conf. Int. Wire Assoc., 26, 1987
27. J. Giridhar and W.J. van Ooij, Surf. Coat. Technol.,
52, 1992, p. 17
28. J. Giridhar and W.J. van Ooij, Surf. Coat. Technol.,
53, 1992, p. 35
29. J. Giridhar and W.J. van Ooij, Surf. Coat. Technol.,
53, 1992, p. 243
30. M. Yoshikawa, E.K. Sim and Y. Kusano, Intern'l.
Rubber Conf. Kobe, 95, 1995, p. 119
31. K. Mori and K. Ishikawa, Showa Densen Rebyuu, 44,
1994, p. 150
32. H. Hirama and K. Mori, Erasutoma Toronkai Koen
Yoshishu, [Elastomer Symposium, Abstracts of
Papers], 11th, 1998, p. 174
33. K. Mori, Porima Daijesuto, 47, 1995, p. 34
34. Y. Ikeda, H. Nawabune and S. Mizumoto, Nippon
Gomu Kyokaishi, 67, 1994, p. 376
35. Y. Ikeda et al., Internat. Rubber Conf., 95, Kobe,
1997, p.151
36. Y. Ikeda, H. Nawabune and S. Mizumoto, Nippon
Gomu Kyokaishi, 63, 1990, p. 503
37. Y. Ikeda, H. Nawabune and S. Mizumoto, Nippon
Gomu Kyokaishi, 64, 1991, p. 372
38. Y. Ikeda, H. Nawabune, S. Mizumoto and M. Sasaki,
Mem. Konan Univ. Sci. Ser., 44, 1997, p. 155
39. Y. Ikeda et al., Internat. Rubber Conf. 97, Kuala
Lumpur, 1997, p. 651
40. Y. Ikeda, H. Nawabune, S. Mizumto and M. Sasaki,
Erasutoma Toronkai Koen Yoshishu, [Elastomer
Symposium, Abstracts of Papers], 11th, 1998, p.182
41. R. Costin and W. Nagel et al., Meet Rubber Div.,
ACS, 146, 1994, p. 23
International Polymer Science and Technology, Vol. 28, No. 8, 2001
42. R. Costin and W. Nagel et al., Rubber World, 212,
1995, p. 18
43. R. Costin and W. Nagel et al., Meet Rubber Div.
ACS, 153, 1998, p. 16
44. R. Costin and W. Nagel et al., Rubber World, 219,
1998, p. 18
45. W.J. van Ooij, Intern'l. Rubber Conf., 95, Kobe,
1995, p. 107
46. C.P.J. van der Aar and L. van der Does, Intern'l.
Rubber Conf., 97, Nuremberg, 1997, p. 185
International Polymer Science and Technology, Vol. 28, No. 8, 2001
47. C.P.J. van der Aar and L. van der Does, Meet.
Rubber Div. ACS, 153, 1998, p. 16
48. C.P.J. van der Aar and L. van der Does, Rubber
World, 219, 1998, p. 22
49. G. Costantino and D.B. Zeik, J. Inorganic
Organometallic Polym., 4, 1994, p. 425
50. Y. Momose and T. Murohashi, Hyomen Gijutsu, 47,
1996, p. 927
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