ROHSTOFFE UND ANWENDUNGEN

RAW MATERIALS AND APPLICATIONS

Natural rubber
Cel II
Nanocomposites
Ageing

The influence of ageing caused by
heating on nanocomposites prepared
by co-coagulation of natural rubber
latex and Cel xanthate mixtures was
studied in this work. For comparison
purposes, carbon black natural rubber
vulcanizates were also prepared. The
amount of Cel II (Cel II) varied from 0 to
30 phr, while carbon black from 0 to
35 phr. The different composites were
analyzed as for crosslink density, dynamic and mechanical properties, before and after ageing.

Einfluss der Alterung auf dynamische und mechanische Eigenschaften von NR/Cel II Nanocomposite
Naturkautschuk
Cel II
Nanocomposite
Alterung
Der Einfluss der Hitzealterung auf
Nanocomposite, die durch Co-Koagulation von Naturkautschuk-Latex und Cellulosexantat hergestellt
wurden, ist untersucht worden. Zum
Vergleich der Eigenschaften wurden
rugefullte Vulkanisate herangezogen. Die Verbundwerkstoffe wurden hinsichtlich ihrer Vernetzungsdichte und der mechanischen Eigenschaften vor und nach der Alterung untersucht.

446

Ageing Effect on Dynamic and

Mechanical Properties
of NR/Cel II Nanocomposites

Nanocomposites are a new class of composite, constituted of particle-filled polymers for which the dispersed particles
have at least one dimension in the nanometer range. One can distinguish three types of nanocomposites, depending on
how many dimensions of the dispersed
particles are in the nanometer range [1].
When the three dimensions are in the order of nanometers, we are dealing with
isodimensional nanoparticles, such as
spherical silica nanoparticles obtained by
in situ sol-gel methods, but also can include semiconductor nanoclusters and
others. When two dimensions are in the
nanometer scale and the third one is larger,
forming an elongated structure, we consider nanotubes or whiskers as, for example,
carbon nanotubes or Cel whiskers which
have been extensively studied as reinforcing nanofillers yielding materials with exceptional properties. The third type of nanocomposites is characterized by only one
dimension in the nanometer range. In this
case the filler is present in the form of
sheets of one to a few nanometer thick
to hundreds to thousands nanometers
long.
Because of the small size of the structural
unit (particle, grain or phase) and the high
surface-to-volume ratio, nanostructured
materials exhibit unique behavior compared to conventional materials with micron-scale structures [2].
In the area of polymers (especially elastomers) one is always searching for improved
mechanical properties to fit certain specific
applications. Reinforcement of elastomers
is normally achieved by adding nano-scaled fillers, such as carbon black and silica
[3]. However, it is difficult to control the
morphological structure of the resulting
material, particularly the degree of filler dispersion. In situ generation of inorganic filler, typically silica, through the sol-gel process provides an interesting method to
overcome these problems [4].
In the special case of the use of Cel as reinforcing agent, the efficiency is related to
the nature of Cel itself and in particular to

its crystallinity, which in turn is dictated by

its molecular structure [5].
As elastomeric systems are important in
the field of industrial materials, they are often used in many critical service and applications. As a result, the estimation of the
ageing behavior of an elastomer is a matter of great concern from the technological
point of view [6].
A fruitful approach to lifetime prediction of
any organic material is a molecular understanding of the chemical processes involved in the course of ageing. In polymer-based materials, chain scissions, crosslinking
reactions and oxidation. The two main
ageing processes in rubbers are oxidation
and ozonolysis. Oxidation ageing generally
occurs quite slowly at ambient temperatures, but may have serious consequences as
the temperature is increased. Oxidation of
rubbers can involve the reaction of free radicals present in the rubber with molecular
oxygen. The free radicals can be formed by
the decomposition of hydroperoxides,
which are present in the rubber in minute
amounts after processing. These reactions
then lead to chain scission and/or additional crosslinking, depending on the type of
rubber. For instance, oxidation of natural
rubber is initially dominated by chain scission, which causes the rubber to soften.
This softening is followed by an increase
in crosslinking, which then leads to hardening. Both processes result in a weaker,
brittle polymer. At ambient temperatures
the main ageing mechanism involves the
presence of ozone from the atmosphere.
The reaction with ozone leads to chain
A. F. Martins, L. L.Y. Visconte,
R. H. Schuster, F. Boller, Hannover and
Regina C.R. Nunes,
Rio de Janeiro (Brazil)
Corresponding author:
Regina Ceila Reis Nunes
Federal University
Macromolecular Institut
bl. J. Ilha do Fundao
21945-970 Rio de Janeiro Brazil

KGK Kautschuk Gummi Kunststoffe 57. Jahrgang, Nr. 9/2004

scission and the formation of polymeric

peroxides, which can also increase the
rate of oxidative ageing [7].
As those processes are related to substantial modifications of the macromolecular
backbone, substantial damage in mechanical properties are expected, even at
low rate of conversion (less than 0.1 %)
[8]. The extent of degradation is very difficult to be predict because reactions and
the rate at which a rubber degrades will
depend on many factors such as the operating temperature, chemical environment,
loading conditions and type of rubber [8].
In this work crosslink density, dynamic and
mechanical properties of natural rubber
(NR) and Cel II (Cel II) nanocomposites, before and after ageing, were studied. The
systems were prepared by co-coagulation
of natural latex and Cel xanthate mixtures,
so that filler content varied from 0 to
30 phr. Through transmission electron microscopy (TEM) these composites were
found to contain Cel II dispersed at the nanoscale range. Carbon black filled natural
rubber samples were also prepared by the
conventional mixing. The properties of the
vulcanisates were investigated before and
after ageing.

Experimental
Natural rubber and Cel II nanocomposites
were prepared by co-coagulation, as described elsewhere [9]. Mixing was carried

out on a Berstorff two-roll mill at 55 8C.

The formulation used followed ASTM D
3184. For comparison carbon black filled
natural rubber mixes were prepared following the same conditions as for Cel II. The
loading of carbon black N 762 was varied
from 0 to 35 phr.
The cure parameters were determined according to ASTM D 2084 on an Oscillating
Disk Rheometer, Monsanto model 100S
(ODR), operating at 140 8C and 38 arc. Vulcanization was carried out in an electrically
heated hydraulic press at 140 8C, The cure
times were previously determined in the
rheometer. From the resulting vulcanized
sheets, samples for the mechanical tests
were cut.
Stress-strength measurements were carried out on an Instron Universal Machine,
model 1101, according to ASTM D 412, at
room temperature and crosshead speed of
500 mm/min. Hardness was determined
according to ASTM D 2240.
The crosslink density was determined from
equilibrium swelling in heptane at room
temperature by using the Flory-Rehner
equation
[10].
Small
specimens
(2.0  2.0  0.2 cm) dried to constant
weight were allowed to swell in the
dark, in sealed bottles until no further
swelling occurred. The volume of imbibed
heptane was calculated from the difference between the weights of swollen and
deswollen samples.

Fig. 1. Tensile strength of NR/Cel II before and after ageing

KGK Kautschuk Gummi Kunststoffe 57. Jahrgang, Nr. 9/2004

Dynamic mechanical thermal analysis were

carried out according to ASTM D 4065 in a
Rheometric Scientific, model MK III, DMTA
analyzer. As mode of deformation, single
cantilever bending was used at a heating
rate of 2 8C/min; a frequency of 1 Hz in
the temperature range  80 to 40 8C.
The phase morphology was examined by
Transmission Electron Microscop (TEM)
using a Zeiss EM 902-machine. Thin sections (max. 100 nm) were prepared with the
ultramicrotome Ultracut FC 4 E, (Cambridge Instruments) at 153 173 K and deposited on non-treated 400 mesh copper
grids.
Composites were submitted to accelerated
ageing in an air-circulating oven at 70 8C
for 72 hours. After ageing, crosslink density, dynamic and mechanical properties
were determined.

Results and discussion

The mechanical properties before ageing
are presented in Figures 1 3. From the results of tensile strength it can be observed
that, compared to unfilled NR, the highest
value of the stress at break (Fig. 1) is achieved by the composite containing 15 phr of
Cel II, while the elongation at break (Fig. 2)
decreases more accentuately as the filler
content increases above 15 phr. Both
groups of results indicate an optimum filler
content for good tensile properties at

Fig. 2. Elongation at break of NR/Cel II before and after ageing

447

Fig. 3. Hardness of NR/Cel II before and after ageing

15 phr. It is interesting to note that the presence of Cel II in amounts up to 15 phr reinforces NR, without changing the elongation at break (Fig. 2).
Concerning hardness (Fig. 3), the increasing incorporation of Cel II into NR causes
a continuous increase in this property.
As a practical criterion for the stiffness of
rubber vulcanizates the modulus at
300 % (r300 ) was investigated. The results
of r300 obtained for NR/Cel II composites
before ageing (Fig. 4) correlate well with
hardness data.
In comparison to the mechanical properties demonstrated before ageing, the tensile strength (Fig. 1) and strain at rupture
(Fig. 2) of the unfilled NR decrease, while
the NR/Cel II composites exhibit an increase in tensile strength and a decrease
in elongation at failure. It is interesting
to emphasize that the composite containing 15 phr of Cel II was the one to present
the best ageing resistance. The drop in
elongation at break after ageing is caused
mainly by the weakening of the matrix as a
result of the main chain scission. The crosslink maturation reactions, which result in
the conversion of polysulphidic linkages
into di- and monosulphidic ones, also
might be contributing towards the decrease in strain at break [11].
Hardness data after ageing are in accord
with the tensile strength results after
ageing, up to a filler content of 15 phr.

448

Fig. 4. Modulus at 300 % of NR/Cel II before and after ageing

Above this critical filler concentration,

the effects of degradation become more
evident.
The modulus at 300 % of the aged samples are shown in Figure 4. The benefit of
incorporating Cel II is clearly seen by a large
increase in this parameter. Again, the unfilled sample reveal the detrimental ageing
effects. The decrease in the modulus value
for NR gum upon ageing is due to the general weakening of the matrix resulting
from the extensive main chain scission.
The results of the investigation of ageing
on network structure are shown in Fig. 5.
Before ageing, the presence of Cel II induces a significant increase in the apparent
crosslink density. Up to 15 phr there is
an increase in crosslinking density observed. However, as more Cel II is added,
the crosslink density increases significantly.
Both groups of values suggest a strong
rubber-filler interaction.
After ageing, a dramatic increase in the
crosslink density is observed for both the
unfilled NR and the NR/Cel II composites.
The most pronounced effect is shown by
unfilled NR. This results from both oxidative crosslinking and the post-curing reactions [11]. For most applications crosslink
density must be sufficient to give the rubber mechanical integrity so that it can bear
loads and present deformation recovery.
However, the crosslink density should
not be so high as to make the polymer

chains immobilized, which then would

lead to a hard, brittle rubber [7].
Figures 6 and 7 show tan delta and the elastic modulus vs temperature for NR/Cel II
vulcanizates before ageing. As a characteristic feature of the unfilled system are the
two preeminent relaxations: the first,
around  50 8C, which corresponds to
the glass transition temperature (Tg ) of
the NR and the other one, between
 25 and  20 8C, related to its crystallization temperature (Tc ).
It is known that vulcanized NR also undergoes crystallization. The degree to which it
occurs depends upon factors such as the
level of strain in the rubber, temperature
and the nature of the crosslinking or curing
system. If a high-sulfur curing system is
used, enough sulfur will react with NR to
reduce the regularity of the molecules.
Molecular irregularity reduces the capability of this rubber vulcanizate to crystallize.
Under appropriate conditions, however,
crosslinked NR will crystallize [12].
From Figure 6, it can also be observed that
in all NR/Cel II vulcanizates NR forms supramolecular crystaline organisations, as indicated by the melting signal (Tc ) which does
not vary significatively with the filler incorporation. Thus, Cel II does not prevent crystallization of natural rubber probably due
to its very fine dispersion. The crescent incorporation of Cel II narrows tan delta
peaks which is an indication of good di-

KGK Kautschuk Gummi Kunststoffe 57. Jahrgang, Nr. 9/2004

Fig. 5. Crosslink density of NR/Cel II before and after ageing

spersion, as well as lowers tan delta values,

a consequence of higher elastic moduli. In
addition, lower values of Tg for composites
containing 20 and 30 phr of Cel II, as compared to unfilled NR are found, while filler
contents of 10 and 15 phr do not alter the
Tg of NR. Lower Tg values indicates again a
good dispersion of Cel II in the elastomeric
matrix.
From Figure 7 it can be seen that the crescent incorporation of Cel II causes an increase in the elastic modulus of NR/Cel II
vulcanizates, more pronounced in the transition and rubbery regions. For the latter, it
can be observed that the increase of the
elastic modulus is related to the higher
crosslink density of the filled vulcanizates
before ageing (Figure 5). The difference
between the composites containing 10
and 15 phr of Cel II is the higher stability
of the crosslinkings for that one with
15 phr of filler throughout the temperature range.
A rubber network consists of chemical
crosslinks, physical entanglements, and
loose chain ends. The effective crosslink
density contains a contribution due to chemical crosslinks and another one due to
chain entanglements and loose chain
ends, acting as physical crosslinks in the
rubber. This is usually estimated by swelling measurements, from modulus values
in the rubbery region or from stress-strain
data [13]. It is interesting to note that the
composites containing 20 and 30 phr of

Fig. 6. Tan delta versus temperature of NR/Cel II before ageing

Cel II present Tg values lower than that

for the unfilled natural rubber, as already
mentioned, and higher crosslink densities.
Thus, these composites probably have a
small contribution from chemical crosslinks, which effectively restrict molecular
motion of the polymeric chains.
DMTA data taken after ageing are presented in Figures 8 and 9. The results of tan
delta (Figure 8) show that Tg s were all shifted towards lower temperatures, around
 55 8C, when compared to the results before ageing (Figure 6). This corroborates
the previous statement that the effect caused by degradation is mainly due to chain
scission. Another finding is that, after
ageing, the composites no longer exhibit
a crystallization temperature.
From Figure 9 it can be observed that, after
ageing, the elastic moduli are higher than
those before ageing (Figure 7), mainly in
the rubbery plateau. In addition, the highest effect of degradation is on composites
containing 20 and 30 phr of filler, as they
present E 0 values smaller than the one containing 15 phr in the entire range studied,
thus corroborating the hardness results described before. After ageing, the higher values found agree with the results of crosslink density discussed earlier.
The properties of carbon black vulcanizates before ageing are presented in Table 1.
From the results of stress-strain experiments, it can be observed that, as compared to unfilled NR, the highest value of the

KGK Kautschuk Gummi Kunststoffe 57. Jahrgang, Nr. 9/2004

tensile strength is achieved by the composite containing 30 phr of carbon black,

while the elongation at break decreases
as the filler content increases. No reinforcing effect for NR composites with 10
and 20 phr of carbon black N 726 could
be observed. According to the literature
[13], the occurence of a maximum in the
tensile strength-loading curves for reinforcing blacks in NR depends on the nature of
the rubber compound and the mixing conditions. Sometimes tensile maxima are not
observed where gums have high strength.
This is observed in the in this work also.
Concerning the reinforcing effect on NR,
Cel II was more efficient than carbon black
N 762. In addition, the maximum reinforcement could be achieved with an amount
of Cel II which was half the amount of carbon black without any loss in the elongation at break.
Data of hardness and modulus 300 % for
the carbon black composites are larger
than that for the unfilled one. However,
both properties were found to be inferior
in this case than in NR/Cel II nanocomposites.
The effective crosslink density for NR/CB
composites increases as the filler content
increases, passing through a maximum
at 30 phr of carbon black. Once again,
these results are lower than those for
NR/Cel II nanocomposites.
The properties of NR/CB composites after
ageing are also shown in Table 1. The ten-

449

Tab. 1. Properties of NR/CB vulcanizates before and after ageing

Property

Tensile Strength
(MPa)

Elongation at break
(%)

Hardness
(Shore A)

Modulus at 300 %
(MPa)

Effective Crosslink density

(mol/cm3)  104

Carbon black content (phr)

0
10
20
30
35

Before ageing
21.5
20.1
20.4
23.0
18.0

18.9
21.1
20.7
16.4
11.1

0
10
20
30
35

700
550
500
500
450

550
550
500
425
300

0
10
20
30
35

42
43
47
52
52

42
41
46
50
56

0
10
20
30
35

2.58
4.17
6.83
8.63
8.30

2.19
3.89
4.84
7.75
11.1

0
10
20
30
35

2.58
3.51
3.85
4.01
3.72

11.30
3.47
3.64
4.47
4.37

sile strength shows a maximum at 20 phr

of filler, hardness is not affected by ageing
and modulus 300 % decreases for all carbon black composites studied, except for
that containing 35 phr. These two latter
parameters present different behavior after ageing and cannot be correlated.

The effective crosslink density results after

ageing are similar for 10 and 20 phr of carbon black, when compared to those before ageing, and highest at 30 phr. The values of this parameter for the composites
with 30 and 35 phr of carbon black increase upon ageing. These results are in

Fig. 7. Elastic modulus versus temperature of NR/Cel II before ageing

450

After ageing

agreement with the tensile strength of

NR/CB composites after ageing.
According to the literature [11] carbon
black causes an increase in the rate of
main chain scission and crosslink scission,
more pronounced when a conventional
vulcanization system is used. It accelerates
the oxygen uptake of sulphur-cured rubber
and the reaction is accompanied by a rapid
degradation of the polymer. The catalysis
of oxidation of rubber by carbon black
could involve the breakage of polysulphidic linkages and cyclic sulphides in the network, whose concentration is much higher
in the conventional vulcanizates, into
mono- and disulphidic ones. Because of
the higher rate of oxygen uptake of carbon-black filled vulcanizates, penetration
of oxygen to the inner layers of the vulcanizates will be slower in these layers. This
causes the presence of a fairly undegraded
inner layer of rubber in the vulcanizate. During the tensile test most of the applied
stress can be carried by this undegraded
layer. In the case of the unfilled vulcanizate, the rate of oxygen uptake is much
slower but the rate of penetration of oxygen to the inner layer is not hindered as in
the case of the carbon black-filled vulcanizates. Hence chances for the presence of
an undegreaded inner layer are less. The
results obtained are in agreement with
this reasoning.

Fig. 8. Tan delta versus temperature of NR/Cel II nanocomposites after

ageing

KGK Kautschuk Gummi Kunststoffe 57. Jahrgang, Nr. 9/2004

vulcanizates, before and after ageing. Before ageing, this filler participates on crosslinking and reinforces the composites,
indicating a good rubber-filler interaction.
The best performance was achieved by the
composite with filler content of 15 phr.
After ageing, NR/Cel II composites showed
better properties and, again, the composite with 15 phr of Cel II was the best
one. From these observations, it can be
said that either the ageing conditions
used in this work were not severe
enough and/or somehow Cel II protects
natural rubber from an acCelerated degradation.

Acknowledgements

Fig. 9. Elastic modulus versus temperature of NR/Cel II nanocomposites after

ageing

The authors thank the Brazilian funding

agency, Conselho Nacional de Desenvolvimento Cientfico e Tecnologico (CNPq) and
Fundacao Universitaria Jose Bonifacio
(FUJB) for providing the financial support,
and Fibra S.A. for supplying Cel xanthate.

References

Fig. 10. Transmission

electron microscopy
of NR/Cel II nanocomposite containing
15 phr of Cel II

Comparing the after ageing results for NR/

Cel II and NR/CB composites, it can be concluded that Cel II is more efficient in preventing a fast degradation and loss of properties of the natural rubber due to its excellent dispersion in the elastomeric matrix
and the strong rubber-filler interaction.
The nanocomposite character of these NR/
Cel II systems was proven by transmission
electron microscopy and is presented in Fi-

gure 10. Cel II is well dispersed and has a

nanofibrilar structure. In this work, only the
composite contaning 15 phr of Cel II is
shown, since it is the one to give the
best performance.

Conclusions
Cel II has large influence on mechanical
and dynamic properties of natural rubber

KGK Kautschuk Gummi Kunststoffe 57. Jahrgang, Nr. 9/2004

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