Gummi Fasern Kunststoffe, No. 10, 2004, pp.
653-662
Migration of additives in rubber
Anthoine, F. Ignatz-Hoover, B. H. To*
*
Gilbert Anthoine, Flexsys N.V,
St. Stevens Woluwe Zaventem, Belgium Byron H. To, Frederick lgnatz-Hoover, Flexsys America L.P., Akron, Ohio USA
Selected from International Polymer Science and Technology, 32, No. 9, 2005, reference GK 04/10/653; transl. serial no. 15422
The migration of compounding ingredients in rubber
compounds before, during and after vulcanisation
is recognised as an important factor in the overall
properties and performance of rubber articles containing
a number of layers, such as, for example, tyres or
hoses. In certain cases, the migration of compounding
ingredients can be beneficial since the effect of waxes
and paraphenylenediamines as anti-ozonants are
largely determined by the migration mechanism if they
are to provide optimum protection against degradation
by ozone for rubber products in service. In addition,
the dispersion of compounding ingredients such as
oil, curing agents and antioxidants in rubber can be
enhanced by diffusion. In other cases, however, diffusion
at the interface between two rubber materials can be
detrimental to performance by causing a change in the
distribution of the individual materials which may result
in a change in mechanical properties, a loss of adhesion
or the action of antioxidants; the discolouration of light-
coloured products is another familiar example.
This paper describes the fate of various chemical
additives in uncured and cured rubber. It also provides
an overview of earlier works and more recent information
on the migration of compounding ingredients.
Better understanding of this important compounding
phenomenon could enable us to identify the optimum
distribution of ingredients.
1. INTRODUCTION
The migration of compounding ingredients in rubber
compounds before, during and after vulcanisation is
recognised as an important factor in the basic properties
and the overall behaviour of rubber products such as tyres,
International Polymer Science and Technology, Vol. 32, No. 11, 2005
Translation submitted by C. Hinchliffe
for example. In certain cases, the diffusion or migration of
compounding ingredients can be beneficial since waxes
[1, 2] and paraphenylendiamines as anti-ozonants [2, 3]
have to migrate to provide optimum protection against
ozone degradation and fatigue. In addition, the dispersion
of compounding ingredients such as plasticisers, curing
agents and antioxidants can be enhanced by diffusion
in a special rubber compound [4]. However, in other
cases, diffusion through an interface may be detrimental
to the performance of a rubber product because it can
cause changes to the physical properties, such as a loss
of adhesion or antioxidant action and the discolouration
of light-coloured products [3, 4, 5].
In uncured tyres, the migration of curing agents is
of particular significance since they have numerous
interfaces between parts made of different rubber
compounds with different curing systems. Literature
contains references to the fact that several commonly used
curing agents such as sulfur, sulfenamide accelerators
and sulfur donors diffuse relatively easily through an
interface between two rubber compounds [4, 5, 6, 7].
Published data on rubber chemicals are, however, rare
– probably due to the relatively complicated measuring
procedures associated with the problem.
The use of radioactive isotopes as indicators is a very
precise method which is very suitable for tracking the
movements of curing agents in a wide range of ambient
conditions. Due to the relatively high costs and special
procedures required, however, very few studies into the
diffusion of special curing agents in rubber have been
performed using this method. Microinterferometry, an
Second publication with the kind permission of RC&T
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optical procedure, has been used as a slightly simpler
alternative to the use of radioactive isotopes. Unhappily,
the complexity and low precision of this method means it
is of restricted usefulness. In addition, carbon black has
a disruptive influence on microinterferometry and so this
test method is restricted to unfilled rubber compounds.
For this reason, the conclusions discussed in literature
are still of a very general nature. Gardiner demonstrated
that the diffusion coefficients of curing agents tend to
change with their concentration and that sulfur’s rate
of diffusion does not change to any greater degree
with the polymer [4]. He also demonstrated that a
(diffusion-linked) concentration gradient of the curing
agents develops even before any clear crosslinking
reaction occurs during curing. This results in drastic
changes in the rate of vulcanisation and the mechanical
properties. He concluded that additives in elastomer
blends achieve diffusion equilibrium more rapidly than
a system consisting of two layers in which each layer
is constructed from the individual polymer [5]. Lewis et
aI demonstrated that the highest migration speeds of
compounding ingredients occur in cis-polybutadienes,
followed by natural rubber and SBR [6]. These results
were intended to enable compound developers to come
up with a general impression of the relative changes
in the concentrations of curing agents in the interior of
a rubber product constructed from layers. However, it
would still be difficult to predict absolute changes or their
impacts on behaviour under production conditions.
2. MIGRATION OF ADDITIVES IN RUBBER
There are at least two mechanisms able to affect the
migration of chemical additives through a rubber
product.
A. Blooming
Blooming may occur in a rubber product when a partially
soluble additive is used in an amount exceeding its
solubility at a specified temperature [8].
For example, a substance dissolved in a rubber
compound at a high compounding temperature becomes
supersaturated when the compound cools down. This
results in the crystallisation of the compounding ingredient:
the crystallisation can be energetically more favourable
on the surface of the compounds than in its interior.
If crystallisation occurs on the surface, a concentration
gradient forms between the layer directly below the
surface (a saturated “solution”) and the interior of the
rubber (supersaturated). This concentration gradient
results in further blooming on the surface until the
concentration of the compounding ingredient reaches the
limit of solubility (saturated) throughout the entire rubber
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product. A compounding ingredient which is present
below its solubility limit tends not to bloom.
The blooming of a anti-ozonant on the surface of a
rubber product is considered to be undesirable since the
anti-ozonant appears on the surface regardless whether
it is required (i.e. there is an impoverishment of active
anti-ozonant through the surface). The occurrence of
superfluous anti-ozonant on the surface could result in
a physical loss of anti-ozonant.
B. Diffusion
In this paper, “diffusion” is defined as the movement of
a compound which is extremely soluble in rubber with
this movement being triggered by a disruption to the
equilibrium. It is known that solutions of compounds in
rubber behave similarly to solutions of substances with a
low molecular weight and are subject to the same laws
as conventional solutions [9, 10]. If the concentration
of a fully soluble component is reduced at a liquid
interface, this component diffuses in order to restore the
equilibrium concentration. In this way, diffusion creates a
protective action on the surface “to the required degree”
(i.e. the blooming of the component is not independent
of the requirement, but diffusion only takes place when
the surface concentration has been impoverished by a
chemical reaction or a physical loss, for example).
Consequently, an anti-ozonant used in an amount
exceeding its solubility has two motive forces which
cause it to emerge on the surface of a tyre: blooming
and diffusion. An ideal anti-ozonant would be one
which is completely soluble and migrates rapidly to
the surface when the effective anti-ozonant effect on
the surface is exhausted.
3. MIGRATION OF CURING AGENTS
Lederer et al [11] describe a relatively simple method that
may be used to measure the diffusion properties of curing
agents through an interface between two uncured rubber
compounds using conventional analytical methods. This
method was used in a study of the migration of several
conventional curing agents in a carbon-black filled
natural rubber compound. The results were subjected to
a mathematical method described by Crank in order to
test the validity of the method, produce diffusion curves
and calculate diffusion coefficients. The following is a
summary of the results of this study.
Figures 1 and 2 show the concentration in dependence
upon distance profiles for a number of curing agents,
namely TBBS, DTDM, sulfur, MBTS and the vulcanisation
retarder CTP after storage for different times and at
different temperatures. Due to their low diffusion rate,
the values for MBTS and CTP are only given for lengthy
 Figure 1. Diffusion of curing agents (3 d at 23 °C)
Figure 2. Diffusion of curing agents (17 d at 45°C)
storage times at the higher temperature. It should be
noted that insoluble sulfur containing about 16% soluble
sulfur was used for this study and that only the diffusion
of the soluble sulfur was measured with a low initial
amount of 0.4 %.
The diffusion profiles clearly show that a significant
quantity of the curing agent automatically migrates
through a compound interface even at room temperature.
As expected, the degree of the change in the quantity of
the curing agents increases as the storage time and/or
temperature increase and the distance from the interface
decreases. The diffusion rate is inversely proportional to
the molecular weight of the diffused substance:
DTDM (MW = 236) > TBBS (238)
> CTP (261) MBTS (332)
Decreasing diffusion rate
The conclusions drawn from this study were as follows:
1. Curing agents tend to migrate automatically between
two rubber compounds and in doing so follow the
conventional diffusion laws:
• the diffusion rate increases as the temperature rises
International Polymer Science and Technology, Vol. 32, No. 11, 2005
• the change in the concentration of the curing agents
falls as the distance to the interface increases and
increases over time
2. A test method using conventional analytical methods
can be used to determine the diffusion coefficients
of curing agents at different storage temperatures
in standard rubber formulations with a high degree
of precision.
3. The diffusion profiles and coefficients depend
upon the type of curing agent. Diffusion is related
to the molecular weight of the diffused material.
The diffusion rate falls as the molecular weight
increases.
4. The concentration influences the diffusion coefficient,
which is understandable since chemical potential is
a function of concentration.
5. The diffusion of curing agents can cause a significant
change to the vulcanisation system at or close to the
interface of a rubber product consisting of layers.
6. The diffusion profiles for a special rubber formulation
may be predicting by using relatively simple analytical
and mathematical procedures from experimentally
obtained data.
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4. MIGRATION OF SULFUR analysis (SEM-EDX scanning electron microscopy with
energy-dispersive X-ray spectroscopy).
In order to obtain a better understanding of the migration
of curing agents, more recent works have been devoted to
the migration of sulfur. The objective of these works was
Results After Preliminary Heat Treatment at
to investigate the migration of sulfur from a belt coating
Different Temperatures
compound with insoluble sulfur into a tread compound
with soluble sulfur at different temperatures. We observed a general trend in the conversion and
A belt coating compound with insoluble sulfur was migration properties of insoluble sulfur when the
brought into contact with a tread compound with soluble temperature was raised from 90 °C to 130 °C. This
sulfur. Both compounds were brought to a thickness of may be summarised as follows:
4.5 mm. The formulations of the compounds investigated
1. At 90 °C: for 30 minutes, there is no conversion
are summarised in Table 1.
of the insoluble sulfur or migration. The soluble
sulfur undergoes pronounced migration
(Figures 3 and 4).
Table 1. ??? 2. At 110 °C: after 20 min, a noticeable, but slow S-
Ingredient Belt I Belt II Tread conversion and migration occurs. The soluble sulfur
NR 100 100 undergoes pronounced migration at this temperature
SBR 96.25 (Figures 5 and 6).
BR 41.25 3. At 130 °C: at this temperature, a significant degree
N 326 45 45 of reversion took place. The migration speed is
N 220 43 comparable with that of soluble sulfur (Figures 7
Stearic acid 1.2 1.2 2.0
and 8).
Zinc oxide 8.0 8.0 2.0 The migration profiles show that a significant quantity
Tackifier 2.0 2.0 of the soluble sulfur migrates automatically through an
Binder 0.5 0.5 interface between two rubber materials. As expected, the
degree of the change in the sulfur concentration increases
CTP 0.2 0.2
as the values for time and temperature increase, but falls
TMQ 1.0 1.0
as the distance from the interface between compounds
6PPD 1.0 1.0 2.0 in contact with each other increases.
CBS 1.0
However, the insoluble sulfur starts to migrate when
DCBS 1.0 1.0 the insoluble sulfur are been reconverted, which usually
Insoluble sulfur 5.0 happens at a temperature of 110 °C. The rate of S-
Soluble sulfur 5.0 1.75 conversion and migration is determined by the time and
temperature. At 130 °C and above, due to the fact that
all the insoluble sulfur has been converted back into the
soluble form, there is no difference between the migration
The sample was subjected to temperature treatment for properties of insoluble and insoluble sulfur.
a specified period. During this treatment, the insoluble
Finally, it is established that the use of insoluble sulfur
sulfur could be partially converted back into soluble
can prevent the migration of sulfur between adjacent
sulfur which would migrate. The relative speed of the two
rubber compounds at processing temperatures below
processes is determined by varying the temperature.
110 °C, which prevents changes in the behaviour of
The sheet of belt compound (dimensions 10 x 10 the compound.
x 0.45 cm) was placed on a sheet made of the tread
compound with similar dimensions. The combined sheets
of compound were placed in a mould. The heat treatment 5. MIGRATION OF ANTIOXIDANTS
for triggering S-conversion and migration took the form
of heating the mould for 10, 20 and 30 minutes in a The selection of the chemical class and the amount of
curing press at temperatures in the range from 90 °C antioxidant added is frequently based on empirical
to 130 °C. Directly after the heat treatment, the mould approaches. More scientific developments have resulted
was placed in another curing press with a temperature in a better understanding of the mode of operation of
of 170 °C to cure the sample. This was necessary to the substituted paraphenylendiamines as anti-ozonants
avoid the presence of any free sulfur. Free sulfur would and permit the postulation of a model of the protective
interfere with the instrument used for the SEM-EDX action of antioxidants.

T/4 International Polymer Science and Technology, Vol. 32, No. 11, 2005
 Figure 3. Determination of sulfur distribution tread/belt I: 30 mins at 90°C; 10 mins at 170°C

Figure 4. Determination of sulfur distribution tread/belt II: 30 mins at 90°C; 10 mins at 170°C

Figure 5. Determination of sulfur distribution tread/belt I: 20 mins at 110°C; 10 mins at 170°C

Figure 6. Determination of sulfur distribution tread/belt II: 20 mins at 110°C; 10 mins at 170°C

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 Figure 7. Determination of sulfur distribution tread/belt I: 20 mins at 130°C; 10 mins at 170°C
Figure 8. Determination of sulfur distribution tread/belt II: 20 mins at 130°C; 10 mins at 170°C
In 1970, Lake [12] developed the theory that chemical
anti-ozonants (such as, for example, disubstituted
paraphenylendiamine) form a protective layer on the
rubber as a result of the reaction of ozone with the
antioxidant; it was demonstrated that the diffusion of
the anti-ozonant is an important factor influencing the
development of this layer.
More recent works by Lattimer et al [13] (using gas
and/or liquid chromatography) and Andries et al (using
ATR, attenuated total reflection) revealed that a superficial
analysis of rubber material exposed to the action of ozone
and containing a substituted paraphenylendiamine as
an anti-ozonant produced an analytical result essentially
identical to the pure anti-ozonant exposed to the action
of ozone; there was no evidence of ozonised elastomers
[15]. Scanning electron microscopy found evidence of a
continuous film of the ozonised protective agent. Andrews
and Braden [16] assumed that when rubber containing
PPD is exposed to the action of ozone, a less flexible layer
of ozonised PPD which is inert to any further ozone attack
forms. The experimental results given above all indicate that
the protective action of anti-ozonants is exerted by a trapping
[17] or protective layer [8]. This means that a sequence of
events such as the following can be postulated:
1. The anti-ozonant appears on the surface of the
rubber product.
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2. The anti-ozonant reacts with ozone and forms a
continuous film.
3. The ozonised film is completely degraded by ozone
or, if it is not extensible, releases a new surface on
extension.
This means that long-term protective action with an anti-
ozonant requires the continuous replenishment of active
anti-ozonant on the surface of the rubber product. The
solubility and migration speed of the anti-ozonant are
significant in that these parameters determine the route
and the appearance of the anti-ozonant on the surface
of the rubber.
The total solubility of antioxidants in the rubber matrix
is desirable to prevent blooming of the compound on the
rubber surface. Luecken et al [3] analysed the surface of
materials containing the four most important commercial
substituted paraphenylendiamines (PPDs). Up to 20
phr, the PPD dialkyl (77 PD) was fully soluble. The C6
alkyl-aryl-PPD (6 PPD) was still soluble at 10 phr, but
began to bloom at 20 phr. IPPD, the C3 analog, had
significant blooming at 3 phr. As expected, the diaryl-
PPD (DTBD) was the least soluble of the anti-ozonants
tested and bloomed in the lowest concentration. Changes
to the ingredients of the formulation, in particular to
the type of elastomer tend to affect the solubility of the
antioxidants used.
 If an antioxidant is completely soluble, its surface
concentration will be proportionate to the amount used
(just like the concentration of the antioxidant at any point
in the rubber). And vice versa, antioxidants added in
amounts above their solubility level will bloom and have
surface concentrations that increase over time.
The actual solubility of the PPDs in the natural rubber
compound can be assessed with reference to the fact
that this corresponds to the concentration at which
blooming first occurs. If blooming is observed in a
material and recorded quantitatively as a function of
time with two or more PPD concentrations, it is possible
to calculate a blooming rate from the gradient of the
curve. If the blooming rate is plotted as a function of the
PPD concentration, the PPD concentration at which the
blooming rate is equal to zero should correspond to the
maximum solubility at this test temperature.
In addition, to complete solubility, a second desired
property of an antioxidant is its rapid migration to the
surface of the rubber product as soon as the effective
activity of the antioxidant on the surface is exhausted.
There is only a limited amount of published literature
on the diffusion behaviour of antioxidants in rubber
materials. In 1968, Lewis et al [18] studied the migration
of accelerators and antioxidants in natural and synthetic
rubber. In their study, compounds with labelled C14
atoms were placed in pre-cured rubber discs swollen
with solvents. Radioactive and non-radioactive discs were
physically pressed together in a C-clamp and the migration
was tracked from the increase/decrease in radioactivity
between the discs. The only antioxidant investigated
was diphenylparaphenylendiamine (DPPD). The authors
identified a substantially complete equalisation of the DPPD
concentration after 250 h contact at 100 °C. The quickest
migration took place in cis-polybutadiene, followed by
natural rubber and SBR. An attempt was made to modify
this work by measuring the increasing/decreasing ozone
resistance of adjacent materials as a measure for the
migration of antioxidants.
Figure 9. Migration of 6PPD in natural rubber at 50°C
International Polymer Science and Technology, Vol. 32, No. 11, 2005
As described in detail in the study performed by
Luecken et al, a cured sheet, such as is normally used
for tensile tests, made of 100 phr NR and with an added
amount of 4 phr PPD, was placed between two sheets
made of an identical reference material containing no
PPD. The migration of the antioxidant from the middle
rubber samples to the outer rubber samples was tracked
by determining the changes to the ozone resistance of
the internal and external materials. The ozone tests on
the materials were performed by observing the decrease
in the modulus at 100 % extension. The samples were
tested for three months under exposure to ozone under
static, dynamic and intermittent conditions. The results of
the ozone tests were presented as hours to the retention
of 70 % of the modulus at 100 % extension as the sum
of the results of tests on a single compound under static,
dynamic and intermittent conditions. The experimental
results obtained by the authors for 77PD and DTPD
revealed that 77PD migrates the most quickly and
achieves a state of equilibrium after less than a month.
The migration speed of the 6PPD is between the values
determined for 77PD and DTPD and a state of equilibrium
is achieved after approximately three months.
These results clearly show in all cases that a
substantially complete migration of the antioxidant takes
place within one to two months. This demonstrates the
futility of attempting to optimise the ozone protection for
tread or sidewall materials in the laboratory as individual
structures since antioxidants have no problem migrating
through a rubber product consisting of layers.
In view of the fact that a certain amount of antioxidant
is usually lost on the surface due to leaching (for example
IPPD and 77PD), adequate ozone protection can only
be attained if the lost antioxidant is replenished. This
would occur if the antioxidant migrated or diffused out
of the interior of the rubber products at an appropriate
speed. As Figure 9 shows, the 6PPD migrates through
rubber from a zone of with a higher concentration to a
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zone with a lower concentration. The diffusion tracked by
UV analyse of cut pieces taken from a 12 mm sandwich
comprising one 4 mm thick rubber sample containing 3
phr of 6PPD and two 4 mm thick unprotected samples.
These results show that antioxidant lost on the surface
is replaced at a reasonable rate by material from the
interior of the rubber.
Luecken et al presented values for the relative
solubility and the diffusion capability of anti-ozonants
on the surface and through the matrix of natural rubber.
Their work discusses different diffusion mechanisms and
their interdependence with regard to whether, at the test
temperatures, the anti-ozonant is present in the rubber at
its solubility limit or below this. In addition, if PPDs are
added to both the carcass compound and the sidewall
compound, higher PPD concentrations may be retained
in the sidewall over an extended period of time. In the
latter case, the carcass acts as a “reservoir”, which
should result in an extended tyre life and improved
retreadability.
Radial car tyres were produced with the antioxidants
listed in Table 2 in the sidewall and carcass.
Table 2. Distribution of antioxidants
Anti-ozonant
Tyre constituents
Tyres A Tyres B
Carcass - 2.5
Sidewall 3.0 3.0
Immediately after curing, the tyres were stored in a
nitrogen atmosphere in order to prevent the oxidative
loss of PPDs. During eight-weeks storage, transverse
pieces were cut from the tyres. The amount of 6PPD in
the sidewalls and carcasses was determined.
Figure 10. Diffusion of anti-ozonant in car tyre carcasses and sidewalls, no anti-ozonant in the carcass
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Figure 10 shows the analytical results for the tyres A
(without 6PPD in the carcass). There was an extremely
strong diffusion of 6PPD from the sidewall to the carcass.
If 2,5 phr of 6PPD was added to the carcass compound
(tyres B), there was only a very small degree of diffusion
as shown in Figure 11.
After eight weeks, the tyres B still had 1.4 % by
weight 6PPD in the sidewall (40 % more than the tyres
without 6PPD in the carcass). The concentration of
6PPD decreased slightly in the sidewall (Figure 11) and
remained constant in the carcass. The diffusion in the
tyres is obviously not restricted to the sidewall and the
carcass. The tread, which comprises a large weight of
rubber, also undergoes a diffusion of ingredients.
Test strips were mounted on cars. The sidewall
evaluations with these test strips are shown in Figure 12.
Increasing the PPD content in the carcass to 4 phr
produced the best performance. Similarly improved
behaviour was identified with regard to crack formation
in the tread.
The perhaps much more important field of application
of the “reservoir concept” of the carcass is the field of
high-quality truck tyres. Increasing the longevity of the
tyres will result in better retreadability.
To summarise, it is established that the use of high
amounts of antioxidants, in particular anti-ozonants/
antioxidants such as, for example, 6PPD/TMQ in the
carcass covering compound can achieve improved long-
term resistance of tyres in that the carcass functions as
a reservoir for the replenishment of antioxidants to the
sidewall and tread [19]. It should be made clear that
the antioxidants seek to achieve an equilibrium within
the whole tyre, regardless of which tyre components
they were added to. Different amounts of 6PPD in the
carcass covering compound clearly demonstrate the
“reservoir effect”.
International Polymer Science and Technology, Vol. 32, No. 11, 2005
 Figure 11. Diffusion of anti-ozonant in car tyre carcasses and sidewalls, 2.5 phr anti-ozonant in the carcass

Figure 12. Tyre tests for the concept of the “carcass reservoir”

New Development – Quinone Diimine (QDI)
N-phenyl-N’-1, 3 dimethylbutyl-p-quinonediimine [20,
21] is a chemical which has recently come onto the
market and which has a multifunctional activity in
diene rubber cured with sulfur. Following the curing,
some of the QDI can no longer be extracted from the
vulcanisate. It was also found that the residual QDI is
converted to 6PPD. The bound antioxidant is not active
like a migrating anti-ozonant, since it is no longer able
to diffuse through the vulcanisate to reach the surface
of the rubber material. However, the bound antioxidant
provides a better protective action against the oxidative
ageing of rubber exposed to aggressive environments
where conventional antioxidant would migrate out of
the material. Studies into the accelerated ageing of
materials subjected to azeotropic extraction, followed
by hot-air ageing produced evidence of this “bound
antioxidant” effect. The results obtained with NR-based
rubber materials protected with QDI and 6PPD and
tested in this way are shown in Figures 13 and 14.
After extraction (cyclohexane/acetone mixture 1:2) and
five days ageing at 80 °C, the material containing the
QDI displays less hardening compared to the material
with PPD and better retention of the tensile strength.
This advantage is also observed with ageing tests in
the open air.
Standard test pieces for the ASTM tensile test were
produced an exposed to ageing in the open air for

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Figure 13. Modulus after extraction and subsequent ageing Figure 14. Relative tensile strength after extraction and
(5 d at 80 °C) subsequent ageing (5 d at 80 °C)

Figure 15. 6 months ageing of NR in the open air in SEV formulation

Figure 16. 6 months ageing of SBR in the open air in SEV formulation

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 Figure 17. 3 months ageing in the open air

six month; the materials were with SEV systems (sulfur
1.5 phr, TBBS 1.5 phr) based on NR and SBR. The
results are these experiments are shown in Figures 15
and 16.
QDI can also be used to replace combinations of TMQ
and PPD. Ageing tests in the open air have shown that
materials containing QDI underwent a lower increase in
the modulus at 100% extension that materials with PPD
and had a better retention of the elongation at break.
This is shown in Figure 17.
Protective Wax
The most frequently used antioxidants for the protection
of rubber is a combination for a wax blend and PPDs.
Waxes act by migrating to the surface of the rubber where
they provide a physical barrier to prevent attacks from
ozone under static conditions. Solubility and mobility
determine the formation of wax layers on the surface
of the rubbers, as shown in Figure 18.
Waxes do not offer any identifiable protective
action under dynamic conditions. This is probably a
consequence of the non-extensibility or the poor adhesion
of the protective film on rubber. PDs provide chemical
protection against ozone attacks under both static and
dynamic conditions.
However, they are not as effective with exposure to
ozone under static conditions as protective waxes. Lederer
et al [22] demonstrated the versatility of protective wax/
PPD systems in the development of a balance protection
under both static and dynamic stresses in a wide range
of temperatures (Figure 19).
6. CONCLUSIONS
Chemical additives, such as, for example, vulcanisation
agents and antioxidants tend to migrate through the
rubber material in both uncured and cured state.
The degree of migration depends upon the type of
additive, its solubility and its ability to react with other

Figure 18. Impact of solubility and mobility on the blooming of protective wax

International Polymer Science and Technology, Vol. 32, No. 11, 2005 T/11
 Figure 19. Impact of quantity of protective wax/PPD on the anti-ozonant action in an NR/BR sidewall

ingredients in the rubber and the ambient conditions. 7. SUGGESTIONS FOR FURTHER RESEARCH
A better understanding and quantification of the
migration of chemical additives would enable compound In order to be able to predict exact diffusion profiles
manufacturers to identify the design criteria for the for special rubber compounds, it will be necessary to
additives and/or the conceptions for the development determine the following factors and their impacts on the
of compounds in a suitable way which could enable migration of chemical additives:
optimum distribution of these additives in rubber to • the solubility of the additives in different polymers
achieve optimum material behaviour. • changes to the types of polymer at the interface
• changes to the types and quantities of the fillers at
the interface
• changes to the types and quantities of oils and other
significant ingredients at the interface
Nomenclature
• variations in a wide range of storage and curing
CBS N-cyclohexyl-2-benzothiazole
temperatures
sulfenamide
When these questions have been resolved, it will be
CTP N-(cyclohexyl)thiophthalimide
possible to produce a detailed evaluation of the impact of
DCBS N,N’-dicylcohexyl-2-benzothiazole
physical, dynamic properties and properties associated
sulfenamide
with the adhesion between different layers and how they
DTDM Dithiomorpholine are linked with behaviour under the conditions of use.
DTPD Mixture of ditolyl PPD
IPPD N-isopropyl-N-phenyl-p-phenylene
diamine 8. REFERENCES
MBTS Benzothiazyl disulfide 1. P. J. DiMauro, H. L. Paris, and M. A. Fath,
6PPD N-(1,3-dimethylbutyl)-N’-phenyl-p- Rubber Chemistry Et Technology, 52, 973
phenylenediamine [1979)
77PD N-N’-bis-(1,4-dimethylpentyl)-p- 2. D. A. Lederer and M. A. Fath, Rubber
phenylenediamine Chemistry & Technology, 54, 415 (1981)
TBBS N-Tert-butyl-2-benzothiazyl sulfenamide 3. J. J. Luecken, B. H. To, and G. H. Kuhls, “New
TMQ Polymerised 1,2 dihydro-2,2,4- Consideration in Selection of Anti-ozonants for
trimethyl quinoline Tires” presented at a meeting of the Plastics and

T/12 International Polymer Science and Technology, Vol. 32, No. 11, 2005
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1-4, 1980
4. J. Brooke Gardiner, Rubber Chemistry Et
Technology, 42, 1058 (1969)
5. J. Brooke Gardiner, Rubber Chemistry Et
Technology, 41, 1312 (1968)
6. J. E. Lewis, Marvin L Deviney, Jr., L E.
Whittington, Rubber Chemistry & Technology,
42, 892 (1962)
7. G. J. Van Amerongen, Rubber Chemistry & Tech-
nology, 37, 1965 (1964)
8. F. H. Andrews and M. Braden, Journal of
Applied Polymer Science, 6, 449 (1962)
9. S. D. Razumovski and L. S. Batashova, Rubber
Chemistry & Technology, 43, 1340 (1970)
10. E. R. Erickson, R. A. Berntsen, E. L Hill and
P. Kusy, Rubber Chemistry & Technology, 32,
1062, (1959)
11. D. A. Lederer and G. H. Kuhls, “diffusion of Cu-
ratives” presented at the 121” Rubber Division
of the American Chemical Society, Philadelphia,
PA, May 4-7, 1982.
12. G. J. Lake, Rubber Chem. Technology, 43,
1230 (1970)
13. R. P. Lattimer, E. R., Hooser, H. E. Diem, R. W.
Layer, and C. K. Rhee, American Chemical
Society, Rubber Division, National Meeting,
May 1980
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Rubber Chem. Technology, 48, 41 (1975)
15. J. C., Andries, C. K. Rhee, R. W. Smith,
D. B. Ross, and H. F. Diem, Rubber Chem.
Technology, 52 (4), 823-37 (1979)
International Polymer Science and Technology, Vol. 32, No. 11, 2005
16. E. H. Andrews and M. Braden, Journal of
Applied Polymer Science, 7, 1003 (1963)
17. S. D. Razumovskii and L. S. Batashova, Rubber
Chem. Technology, 43, 1340 (1970)
18. J. E. Lewis, M. L. Deviney Jr., L E. Whittington,
Rubber Chemistry & Technology, 42, 892
(1969)
19. Flexsys Technical Bulletin (ORC-14): Carcass
Stocks - Antidegradant Reservoir Concept
20. Fred lgnatz-Hoover, Otto Maender, Ray Lohr,
“N-(1,3-Dimethybutyl)-N’-phenyl Quinone
Diimine - A Review of a Multifunctional
Chemical for the Rubber Industry”. Presented
at the fall meeting of the Rubber Division,
American Chemical Society, Cleveland, OH,
October 21-24, 1997
21. Fred lgnatz-Hoover, Rabin Datta, “The Use of
Rubber Chemicals to Enhance the Performance
of Black Filled Elastomer Blends” Presented at
Carbon Black World 97, March 1997, San
Antonio, 7X
22. D. S. Lederer and M. A. Fath, “Effect of Wax
and Substituted p-Phenylenediaminc Anti-
ozonants in Rubber” presented at a meeting of
the Rubber Division American Chemical Society,
Detroit, Ml, October 7-10, 1980
(No date given)
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