ROHSTOFFE UND ANWENDUNGEN

RAW MATERIALS AND APPLICATIONS

Technologien für Kord /

Gummi - Adhäsion in
Technologies for Polymeric Cord/
Reifenanwendungen Rubber Adhesion in Applications
Adhäsion · Resorcinol-Formaldehyd­
latex · RFL · Plasma-Behandlung ·
Reifen
Introduction for reinforcing applications feature com-
Die Adhäsion zwischen Gummi-Matrix Composites made from rubber and rein- patibility with rubber which is sufficient
und verstärkendem Kord ist ein funda- forcing cords are very common and versa- without prior treatment. Therefore, a
mentaler Faktor für die Leistungsfähig- tile goods. Well-known examples of these treatment of the polymeric cord is perfor-
keit und Sicherheit eines Reifens. Üblich are car- and bicycle-tires, as well as several med in order to enhance the compatibility
ist eine Resorcin-Formaldehyd-Latex types of belts and hoses. Clearly, car tires and form a physical or chemical bond. The
(RFL) Behandlung der Korde, um die be- are by far the most important product most common technology is the RFL tech-
nötigte Adhäsion zu erreichen. Oft wird group within all areas of application. nique which will be discussed later on.
dabei zusätzlich eine Epoxid-Behand- Key element is the reinforcement of The best contribution to adhesion co-
lung angewandt, um beide Komponen- the product with cords to prevent large mes from chemical bonding. It provides
ten kompatibel zu machen. Ein Über- deformations of the rubber and, therefo- the strongest and most reliable adhesion
blick über diese chemischen Verfahren re, loss of the actual product function between the adherent layers. Covalent
wird gegeben und neue Entwicklungen when high loads are applied in deman- chemical bonds are the strongest bonds
in diesem Themengebiet werden aufge- ding situations. In order to do so, suffici- and highly durable as well. These bonds
zeigt. Umweltbedenken und neue Ge- ently high adhesive forces between the can be established across the interface of
fahreneinstufungen erfordern sinnvolle composite materials are necessary. A re- two composite layers and, therefore,
Alternativen, weshalb in diesem Artikel inforcing effect is only achievable if the form a stable connection. A requirement
aufgezeigt wird, ob und welche Alter- load forces can efficiently be transferred for chemical bonding is that appropriate
nativen anwendbar sind. Die Plasmabe- from the rubber to the cord. The better functional groups are available on both
handlung der Kord-Oberfläche ist dabei the interfacial bond within the composi- surfaces and that reaction takes place.
eine vielversprechende Möglichkeit. te, the better the product properties will Besides covalent chemical bonds, also
be. In case of lack of adhesion, the cord ionic bonds can be very strong. They can
will not contribute to the composite per- occur in multiple forms like ion-ion, ion-
Adhesion · resorcinol formaldehyde formance, as it will simply slip within the dipole or dipole-dipole bondage. By far
latex · RFL · plasma treatment · tire rubber matrix with only minor work re- the highest contribution to adhesion can
quired. However, the adhesion pheno- be reached by ion-ion interactions. This
A good adhesion between the rubber of menon is affected by several different type can have bonding energies of up to
a tire and the reinforcing polymeric types of interfacial adhesion, which all 450 kJ/mol [1]. The other interaction va-
cord is crucial for the overall tire perfor- have a certain contribution to the overall riants have much lower bonding ener-
mance and safety. Polymeric cords are resultant adhesion. gies as can be seen in Table I [2]. Another
commonly treated by a resorcinol form- In this review, it will be discussed bond type is hydrogen bonding that oc-
aldehyde latex (RFL) coating to obtain which adhesion types contribute in case curs between e.g. hydroxyl functional
the desired adhesion, often in combina- of polymeric reinforcing cords for rubber groups or water molecules. The strength
tion with an epoxy coating in order to matrices with focus on application in car of hydrogen bonds is relatively low with
make the cord surface and the RFL coa- tires. Furthermore, the state of the art a bonding energy of 24 kJ/mol [1].
ting compatible. An overview of these technology will be reviewed and possible
chemical treatments is given, and re- alternatives will be introduced. A compa-
cent developments in this field are rison of these techniques is made and
shown. Environmental and toxicity dis- based on the outcome, and a final con-
advantages are the driving forces to clusion is drawn.
Authors
find suitable replacements; therefore, it
is discussed if the RFL treatment can be Requirements for adhesion André Louis, Jacques W.M.
replaced and which alternative techno- Polymeric cords and rubber are not well Noordermeer, Wilma K. Dierkes,
logies might be suitable. The plasma adhering as there is a lack of compatibility Anke Blume, Enschede,
treatment of the cord surface is one of between them. In general, polymeric The Netherlands
the most promising candidates in this cords have a smooth and inert surface as
field. well as a polar character. Therefore, the Corresponding author:
physical interactions with non-polar rub- Wilma K. Dierkes
ber are weak. The compatibility of both University of Twente
materials is important in order to enable a Dept. of Elastomer Technology
proper wetting of the cords with rubber, and Engineering
which is a necessary prerequisite for ad- P.O. Box 217
hesion phenomena like physical surface 7500 AE Enschede,
Figures and Tables:
By a kind approval of the authors
interactions, mechanical interlocking and The Netherlands
chemical bonding. None of the cords used E-Mail: w.k.dierkes@utwente.nl

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 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

Adhesion caused by interfacial diffusi- 1 Typical bond energies of common bonding types [2]
on is a surface interaction that can build
up sufficient adhesion levels, if both ma- Type Example E (kJ/mol)
terials are actually compatible and well Covalent C-C 350
in contact. The contact interface is then Ion-ion Na+…Cl- 450
crossed by molecules of both sides diffu- Ion-dipole Na+…CF3H 33
sing into each other. Unlike rapid chemi- Dipole-dipole CF3H…CF3h 2
cal reactions or van der Waals interac-
London dispersion CF4…CF4 2
tions, diffusion processes are rather slow
with reaction times ranging from minu- Hydrogen bonding H2O…H2O 24
tes to years [3]. In case of polymeric in-
teractions, it is reported that long-chain 2 Typical recipe of RFL dip system for rayon cord in phr [8]
molecules tend to adhere better because Component Parts (wet) Parts (dry)
of their ability to be present in both ma-
Resorcinol 9.4 9.4
terials by reptation. The interfacial depth
can have a range of up to 100 nm [4]. Formaldehyde (37 %) 13.8 5.1
Electrostatic effects are another sur- Sodium hydroxide (10 %) 7.0 0.7
face interaction that can induce adhesi- Water 157.8 -
on. The adhesive interface can allow Vinyl-Pyridine-SBR-latex (40 %) 212.0 84.8
electron transfer if there is a dissimilar
Water 100.0 -
electronic structure between the materi-
als. In particular in metal-polymer sys- TOTAL 500.0 100.0
tems, this phenomenon can be an expla-
nation for adhesion and account for the between both components of the com- executed, the preparation of the RFL dip
resistance to separation. However, in pu- posite is thereby the critical parameter system has to be done. It consists of two
re polymer composites, this effect is very for gaining the best overall performance major production steps; in a first step
weak and negligible in comparison with from such products. The main function resorcinol is dissolved in water to obtain
covalent or ionic bonds [5]. of a composite adhesive is to gradually an aqueous solution. Subsequently form-
Mechanical interlocking is an impor- transfer the load stress from the rubber aldehyde and sodium hydroxide as con-
tant factor for adhesion too. A good ex- matrix to the reinforcing cord. A blend of densation catalyst are added with the
ample is gluing of wooden pieces, where casein and natural rubber latex was the aim to form methanol groups (resole) on
the adhesion is mainly realized by me- first adhesive system, which gave accep- the resorcinol.
chanical interlocking of the glue in the table levels of adhesion for rayon [6]. The This mixture is stirred for 6 hours at
rough wooden structure. In such a case introduction of stronger rayon cords and room temperature to form a resin soluti-
the bonding strength depends on the full-synthetic cords like polyester led to on. The second step is the introduction of
surface roughness and the mechanical increased adhesion requirements and the latex: Under gentle stirring the resin
properties of the glue. Polymeric cords therefore to the development of new is added to the latex to ensure good mi-
typicall y have a highly orientated, inert adhesives. The resorcinol formaldehyde xing of the dip system [8]. Finally this
surface. Therefore, the contribution of latex (RFL) dip is a common industrial “dip solution” is allowed to mature for 24
the filaments to the overall adhesion standard for about 75 years [7] already hours before further use. The final dip
between cord and rubber is minor, as based on an aqueous dip system. The re- properties are shown in Table III. An in-
they tend to easily slip out of the interlo- sin which is formed by the resorcinol and crease of formaldehyde concentration
cking if a force is applied. With a high formaldehyde provides bonding to the increases the rate of methanol-group
degree of branching the situation is dif- cord. The latex component bonds to the formation. The optimal formaldehyde to
ferent, but this technique is not applied rubber compound due to co-vulcanizati- resorcinol ratio is about 2 to 1, and yields
in the field of cord-rubber-adhesion. That on. The term “RFL-treatment” covers a a complete methanol reaction. Further-
being said with respect to the exception large variety of treatments. They share more, the formaldehyde concentration
of older use of cotton, where the main the same technique but differ in formu- increases the viscosity of the resin be-
contributing factor to adhesion came lation and application. The system is ad- cause of the formation of higher molecu-
from fibrillation of the cotton-fibers. justed to be suitable for the materials lar weight products [6].
used for a specific composite, as each In the case of polyamide or rayon cords,
Resorcinol Formaldehyde Latex (RFL) cord type and rubber may require diffe- a standard treatment with RFL dip is suf-
Systems – State of the art rent treatment conditions. ficient, as the reactivity of these cords is
A lot of rubber articles for highly deman- Multiple steps are required for the high enough. A condensation reaction
ding applications are commonly rein- application of a RFL dip system. A typical between the resin (resole) and the poly-
forced rubber/cord or rubber/steel com- recipe for such an adhesive dip is shown meric cord takes place, see Figure 1 for an
posite materials. The reinforcement ef- in Table II [8]. These values may vary example with nylon cord. The dipping
fect comes from the combination of two within certain limits, but to simplify pro- process is straight forward, as the cords
very different materials: On one hand cedures it is convenient to use standard are dipped with the RFL solution and the
the highly elastic rubber and on the recipes which maintain adequate adhe- deposited layer is then dried and cured by
other hand a cord with high strength and sion levels in several applications. Before exposure to heat. Commonly, a treatment
low elongation properties. The adhesion the actual treatment of a cord can be time of 1 to 2 minutes at a temperature in

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 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

adhesion between cord and subcoating:

3 Final dip properties of a typical formulation [6]
the molar mass determines the number
Properties Value Parts (dry) of end groups which are available for
Dip solids (%) 18-26 9.4 such a reaction. However, there is an ex-
pH 9 to 10 5.1 cess of epoxy groups in the sub coating
compared to the number of reactive
Formaldehyde/resorcinol molar ratio 2/1 0.7
functional groups on the cord surface.
Resin/latex ratio 15-20/100 - The unreacted epoxy groups react later
on with the RFL top coating. The reaction
1 is shown in Figure 3.
The epoxy groups may form hydroxy-
ether structures with the resorcinolic
hydroxyl groups of the RFL. Via this ap-
proach, the epoxy groups form chemical
bonds with both, the cord surface and
the RFL-coating. This is followed by the
reaction of the RF-resin with the rubber
compound (Figure 4). Overall, this sys-
tem creates good adhesion levels with
Fig. 1: Reaction scheme of a resole and nylon molecule forming a covalent bond [6].
chemical bonds through three different
interfaces.
2 A very interesting aspect of the cross-
linking between rubber matrix and the
RFL latex is the high affinity of the RFL
dip towards the sulfuric accelerator mo-
lecules. This was demonstrated by Wen-
nekes [7], who did SEM-EDX linescans of
Fig. 2: Reaction scheme of a resole and nylon molecule forming a covalent bond [6].
the RFL-rubber-interface. A high number
of sulfur counts was found in the latex
the range between 130 ˚C and 150 ˚C is Most polymeric cords feature a high- phase of RFL: The accelerator migrates
sufficient to achieve good adhesion levels. ly inert surface which makes them unre- from the rubber phase during vulcaniza-
In general it can be said, that the RFL active - not only towards rubber, but al- tion (Figure 5) as the RFL initially does
dip systems still deliver a very good per- so towards the RFL coating. In such a not contain any sulfuric components.
formance for adhesion promotion bet- case no adhesion promotion is obser- The adhesion is significantly influenced
ween rubber and reinforcing cords. That ved. An intermediate layer – a sub-coa- by these migrating accelerator compo-
is the main advantage of this treatment, ting – is necessary, that reacts during nents of the rubber compound. The affi-
but it also shows some drawbacks, which the drying process with the cord surface nity towards polymeric or cyclic sulfur
are the driving forces to substitute the and later on in a second step with the molecules is only moderate. Furthermo-
RFL treatment by alternative techniques. RFL top coating. re, an inverse correlation between the
These drawbacks are in first instance en- In case of polyester (PET) and aramid atomic sulfur content in the RFL dip near
vironmental and health aspects caused cords, the use of epoxides as intermedia- the actual interface and adhesion was
by the use of toxic chemicals, as well as te layer is common as it results in suffici- observed.
the multistep processing that is costly ent adhesion. The epoxy-group reacts
and requires time and effort. In particu- with the functional groups on the poly- Alternative Techniques
lar formaldehyde is a problematic key mer backbone of e.g. aramid, or with the A detailed understanding of the RFL-
ingredient, as it is now reclassified by the end groups of a polymer chain in polyes- technique raises the question, which
European Committee of Risk Assessment ter. A schematic drawing of such a reac- kind of alternatives may be of interest for
(RAC) to be carcinogenic (1B) and muta- tion is shown in Figure 2. a potential replacement. Clearly, modifi-
genic (2) [9]. A restriction on the use of If these reactions occur with the end cation of the cord surface properties is
formaldehyde might be possible within groups of the polymer chains of the cord, the key element here with the aim to
Europe in the future. the molar mass of the chains affects the establish a method which enables cova-
lent bonds between cord and rubber
3 matrix. This can be done during the pro-
duction of the cord in such a way, that
functional groups become available on
the cord surface, or via chemical post-
production treatments. Such a treatment
should not affect the bulk properties of
the cord and, to be a valid alternative,
should preferably add a significant ad-
vantage over the existing state of the art
Fig. 3: Reaction scheme of a resole and nylon molecule forming a covalent bond [6].
technology.

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 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

Alternative dipping systems 4

A first approach to find alternative solu-
tions within the field of chemical treat-
ments is in fact the use of similar treat-
ments like RFL, but using alternative che-
micals. The difficulty of this approach is
to replace the problematic chemicals by
health- and environmentally-friendly
ones. Doing so has the advantage, that
the existing processing equipment could
be used without major investment costs.
However, besides tailored variants of the
RFL technique for each cord or applica-
tion, no major innovations were introdu-
ced in this field. Attempts were taken to
reduce the amount of resorcinol and
formaldehyde in the resin [6]. The prob-
lem thereby is that these measures ne-
gatively affect the adhesion strength,
which of course is not desired.
Recently, a RF-free dip solution for ny-
lon cords was introduced onto the market
Fig. 4: Sulfur crosslinking between the rubber matrix and the latex molecules of the RFL
[10]. The intention is to completely avoid
system [7].
the classical resorcinol formaldehyde che-
mistry, but still use the established dip-
ping bath concept. Therefore, the proces- (polyester), in which unsaturated bonds dipped resin, and the transition of forces
sing steps are similar and an aqueous are added in each case through linear or from the stiff cord material to the elastic
system, which has the advantage of good cyclic dicarboxylic acids. According to the rubber compound is much steeper. The
wetting ability of the cord, is used too. patent, the amount of unsaturation can chemical reaction between rubber matrix
According to the corresponding patent be scaled freely and, therefore, be adjus- and the cord is shown Figure 6.
[11], an acrylic resin is dissolved in water ted to the amount necessary for the ap-
and a certain pH-value is set. The fol- plication. However, unlike chemical sur- Plasma treatment
lowing components are added stepwise: face treatments, this method definitely Another interesting alternative is plasma
epoxy, polyisocyanate and latex. The re- changes the material properties of the treatment. It is the subject of many artic-
sult is a dipping solution, which can be polymeric cord. This significant disadvan- les nowadays, covering a large variety of
applied in the usual way. This dip-type is tage is counteracted by the fact, that this possible applications. There have been
claimed to be not as hazardous as RFL for method makes dipping processes com- numerous attempts to improve the ad-
human health and to be more environ- pletely unnecessary. Besides, as it can re- hesion between cord and rubber matrix;
mentally friendly. Clearly, the epoxy and duce production time and effort and many of them more or less successful.
isocyanate groups are responsible for the doesn’t require expensive chemicals for However, first trials based on vacuum
interaction with the cord, while the latex the dipping process, an introduction into systems require batch-wise treatment
responds to the vulcanization process of the market is probable. In contrast to the cycles, which are not desirable for indus-
the rubber matrix. In fact, the acrylic-resin traditional RFL technique, this adhesion trial purposes. That is the reason why the
takes over the role of the RF resin. Instead system misses the intermediate layer of a focus shifted to atmospheric plasma sys-
of the typical brownish finish of RFL, the
RF-free dipping has a whitish appearance. 5 Fig. 5: SEM-EDX
In general, the mechanical properties of linescan for sulfur
the RF-free dipped materials are compara- in the RFL-rubber
ble or higher than RFL-treated ones, but in interface [7]
particular the fatigue adhesion perfor-
mance is reported to be improved [10].

Modified fibre-polymers
Using unsaturated bonds within the
chain backbones of the cord-polymer,
which can form covalent bonding bet-
ween the cord and the rubber matrix,
was recently patented [12]. The unsatura-
ted moieties are added during the syn-
thesis of the polymer. The condensation
comprises the reaction of diamines and
dicarboxylic (nylon) or dihydroxylic acids

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 ROHSTOFFE UND ANWENDUNGEN
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6 Fig. 6: Crosslink The first possibility is the use of plasma in

reaction between a cleaning and activation step to enhance
rubber matrix the reactivity of the cord surface towards a
and unsaturated dipping step. Surface cleaning is a process
nylon during that is commonly performed with inert
vulcanization gases, as chemical modification of the
[11].
surface is not desired. The aim is to remo-
ve contaminants from the substrate sur-
face. Possible contaminants are for ex-
ample oil, dust, oxides, biological and che-
mical agents. Metastable energetic partic-
les are suspected to be responsible for the
destruction process of contaminants. Sur-
face cleaning is an important factor and in
7 most cases necessary before proceeding
with additional steps.
In the case of surface activation, the
aim is to modify the surface energy of a
substrate in order to reach a specific sur-
face property and thus make it receptive
for a certain reaction. Usually this is done
with oxygen groups as they introduce
polar and hydrophilic moieties which in-
crease the material’s surface energy. This
effect is used for painting, printing, coa-
ting or bonding processes. Another pos-
sibility is a surface modification in which
fluorination of the substrate surface
creates anti-adherence properties by lo-
wering the surface energy [15].
Another possibility is a plasma sur-
Fig. 7: An atmospheric pressure plasma jet treating a polymeric cord.
face coating. This is a deposition process,
which adds a new surface layer to the
tems, which can be installed in a conti- cally conductive as well as chemically acti- substrate and thereby changes the func-
nuous line similar like a dipping bath in ve media. The number of free electrons tionality of the substrate surface while
case of dipping systems. per unit volume is defined as the electron the bulk properties remain unchanged.
The application of plasma treatment density and refers also to the term “plas- Of particular interest is plasma enhan-
within the field of adhesion und coating ma density”. The degree of ionization of a ced chemical vapor deposition (PECVD),
technology is well known and subject of plasma is the proportion of atoms that as it allows plasma polymerization. A
many research projects. Plasma is an ext- have been converted to ions by excitation. precursor is vaporized and then fed into a
remely high energy state of a gas, in While in the past the focus was on va- plasma chamber, where the substrate’s
which a variety of oppositely-charged par- cuum plasma that was actively used by surface is treated with the precursor in
ticles caused by ionization is present, scientists, the focus shifted in the last de- the plasma stream. The plasma acts here
while it has an overall electrically quasi- cade to atmospheric plasma that made in as a chemically active media and activa-
neutral charge. It is considered as a state particular industrial applications possible. tes coating reactions. The activated pre-
of matter, which is much higher activated It is a versatile tool which can be used for cursor molecules get in contact with the
than a solid, liquid or gas state. Sir William cleaning, etching, activating and coating substrate surface and react with it to
suggested in 1879, that this state is the applications. Plasma devices are available form a coating layer. Two modes of intro-
‘fourth state of matter’ [13]. The term in several configurations, best known are ducing the precursor are possible. In the
‘plasma’ was first used by Irving Langmuir atmospheric pressure plasma jets (APPJ) direct mode, the precursor is mixed with
in 1929 to denote this state in an article or dielectric barrier dischargers (DBD). An a carrier gas before being fed into the
about gases in electrical discharge tubes example for an APPJ treating polymeric plasma chamber. This can cause a com-
[14]. An ionization process can be estab- cord is shown Figure 7. Common for these plete atomization of the precursor mole-
lished, when gas particles are subjected technologies is the use of air as ionization cules, as the high energy particles of the
to high energy radiation, electrical fields gas, because it is inexpensive, safe, easy plasma separate the molecules into ions.
or high caloric energy. The energy level in to supply and suitable for most industrial In the remote mode, the precursor is fed
a gas increases significantly by external applications. However, other ionization inside a reaction chamber into the after-
excitation, and ionization can take place. gases can be hydrogen, oxygen and nitro- glow of the plasma, which contains less
As a result, electrons of the gas atoms are gen, as well as noble gases. reactive particles. The partially (but ran-
released and positively charged heavy For the improvement of adhesion bet- domly) broken precursor is then able to
particles are produced. Thus plasma con- ween polymeric cords and a rubber mat- introduce new functional groups onto
tains free charge carriers and is an electri- rix, two plasma approaches are of interest. the substrate surface [16].

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 ROHSTOFFE UND ANWENDUNGEN
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In literature, the aim of using the plas- 8 Fig. 8: Effect of

ma technique is twofold: either the am- plasma treat-
bition is to replace RFL completely or to ment on rayon
reduce the number of dipping steps by cord in compari-
replacing the epoxy sub-coating by a son to untreated
rayon cord and
plasma surface activation. Van Ooij et al.
RFL dipped rayon
[17] applied plasma treatment to untrea- cord.
ted aramid and polyester cords. The ioni-
zation gas was argon and the precursors
were pyrrole and acetylene. Enhance-
ments of the H-pullout forces as well as
improved adhesion to rubber compounds
and epoxy adhesives were found, in par-
ticular if acetylene as precursor was
used. Only activating these cords was not
successful and did not improve the adhe-
sion, but it was not harmful either. Hu-
dec et al. [18 - 23] worked with untreated
polyester cords and a plasma reactor
using nitrogen as ionization gas. Cleaning
of the cord with acetone before the plas- butane and nitrogen [28] or the plasma caution measures are necessary. Howe-
ma treatment was found to be beneficial treatment with an atomized mixture ver, besides reducing this specific health
for the adhesion. Overall, the plasma comprised of a polymerizable monomer, risk, the RF-free dip technology is compa-
surface activation with nitrogen was re- a halogenated saturated hydrocarbon rable to the RFL-technique and is still
ported to be very successful and the ad- and a carrier gas [29]. All these approa- using problematic chemicals which
hesion level was comparable to the level ches show that plasma treatment has cause an environmental burden. Besides,
of RFL-coating. The plasma modified sur- the potential to be a suitable solution for a significant reduction in the product
face did not undergo aging when it was the replacement of the RFL treatment. price is not expected, and it is likely that
exposed to air before further processing. RF-free cords need to match the proper-
The use of a maleic acid bath after the Comparison and Outlook ties of the RFL-treated cords closely.
treatment to establish grafting onto the Each type of adhesion promotion tech- Otherwise, a direct replacement would
polyester surface had no significant ef- nique has its advantages and disadvan- not be possible, as e.g. the construction
fect, neither had the addition of butadie- tages, in particular the RFL industrial of the tire needs to be adjusted as well.
ne to the nitrogen ionization gas a signi- standards. The RFL-coating is well estab- A no-dip solution is a radically different
ficant effect on the adhesion. lished and delivers a good adhesion per- approach compared to the two previous
De Lange et al. [24] compared oxygen formance resulting in high quality pro- ones. In fact it is an innovative solution, as
and nitrogen plasma versus chemical ducts. Therefore, it fulfills the main re- it solves the problem at its origin. While
treatment with the aim to replace the quirements and justifies its position in using a multiple dip system is rather a
epoxy coating by plasma in the case of the market, even though the disadvanta- work-around solution to gain adhesion,
aramid cord. It was concluded, that the ges are significant. The dipping process the idea of adding unsaturated mono-
introduction of hydroxyl-groups was the itself is here the main issue: The produc- mers in the cord-polymers is a direct way
key element for the adhesion with the re- tion requires a relatively high effort, as of getting adhesion. Therefore, it will be a
sin of RFL. The number of hydroxyl-groups two dipping steps are necessary, which major simplification as it reduces the
created by both plasma treatments was means that high costs for equipment number of processing steps and comple-
lower than in case of an epoxy-layer. and production have to be taken into ac- tely avoids additional chemicals. Therefo-
Therefore, plasma treatment could not count. Furthermore, the health issues of re, less energy is used and there is no
generate an improved adhesion level. the resins used nowadays require an ext- health issue or environmental burden.
The industry contributed as well to ra effort in terms of protective measures However, it is a question how complicated
the developments in the field of plasma in the production facilities. Disposal of it is to add unsaturated bonds to the poly-
treatment with focus on reinforcing chemical waste is another major cost mer. This has to be balanced against the
cords for rubber reinforcement. Back in factor due to their environmental bur- advantages of less processing steps. A
the 1990’s, different studies were carried den. However, RFL-coatings are still disadvantage of this technology is, that
out to enhance the adhesion of the RFL- mainly used due to the fact that almost the cord-rubber-interface is completely
coating by a CF4/O2 plasma treatment all current products on the market are different from the RFL-treated one: The
[25, 26]. Another approach was to use a based on the properties defined by RFL- resin-latex coating is missing, which re-
vinyl-compound in combination with a coated reinforcing cords. sults in a steep transition from the stiff
plasma treatment [27] followed by a RFL The application of RF-free dips has cord to the highly elastic rubber. The RFL-
dip. Currently the aim is clearly to use a one significant advantage over RFL: As coating with its intermediate properties
plasma treatment alone as a replace- described above, the acrylic resin recipe forms a good transition zone, and there is
ment for the RFL technique. Examples is less toxic and therefore much less criti- no equivalent when applying a non-dip
are the application of an atmospheric cal to be used in production. This simpli- adhesion technology. The added unsatu-
plasma with a gas mixture of propane, fies production procedures as less pre- rated bonds will also affect the cord pro-

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 ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS

perties, as they are attached to the main a direct bond between cord and rubber. It [8] C. Crowther, Handbook of Rubber Bonding
chains of the polymer. This change in cord is to note, that the plasma treatment only (Revised Edition) (2003), Rapra Technology Li-
properties will most likely make adjust- affects the surface which is accessible by mited, Shropshire, UK.
ments necessary to the material specifica- the plasma. Therefore, an untreated zone [9] RAC adopts seventeen scientific opinions, Eu-
tions by the manufacturers. inside the cord remains where single fila- ropean Chemicals Agency (2012), 14 Decem-
Plasma treatment is an innovative ments of the cord fail to participate in ber 2012, http://echa.europa.eu/view-artic-
way to promote adhesion. The applica- crosslink reactions during vulcanization. le/-/journal_content/c89bdb13-09e9-497c-
tion of this technique is efficient and The response of a plasma coated compo- 8e73-ddae13a842c8, Helsinki, Finland.
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Figure 8 which as obtained after an APPJ- in different properties in the finished Industry, Istanbul, Turkey, inv.: A.F. Mahalle-
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Fig. 9: Comparison of RFL dip coating and plasma polymerization coating. unpublished results.

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