Physica B 407 (2012) 3271–3273

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Physica B
journal homepage: www.elsevier.com/locate/physb

About the cure kinetics in natural rubber/styrene Butadiene

rubber blends at 433 K
M.A. Mansilla n, A.J. Marzocca
Laboratorio de Polı́meros y Materiales Compuestos, Departamento de Fı́sica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 1,
C1428EGA Buenos Aires, Argentina

a r t i c l e i n f o abstract

Available online 20 December 2011 Vulcanized blends of elastomers are employed in several goods mainly to improve physical properties
Keywords: and reduce costs. One of the most used blends of this kind is that composed by natural rubber (NR) and
Natural rubber styrene butadiene rubber (SBR). The cure kinetic of these blends depends mainly on the compound
Styrene butadiene rubber formulation and the cure temperature and time. The preparation method of the blends can influence
Blend the mechanical properties of the vulcanized compounds.
Cure kinetics In this work the cure kinetic at 433 K of NR/SBR blends vulcanized with the system sulfur/TBBS
Crosslinks (N-t-butyl-2-benzothiazole sulfenamide) is analyzed in samples prepared by mechanical mixing and
solution blending.
The two methods produce elastomer domains of NR and SBR, which present different micro-
structure due to the cure level attained during vulcanization.
The cure kinetics is studied by means of rheometer tests and the model proposed by Kamal and
Sourour. The analysis of the cure rate is presented and is related to the structure obtained during the
vulcanization process.
& 2011 Elsevier B.V. All rights reserved.

1. Introduction
The advantage of preparing elastomeric compounds is to
produce a new material, sometimes with lower cost, and combine
the properties of the main polymer without the development of a
new synthesis process. In the last years we focused our research
in vulcanized rubber blends. The study of the crosslinks structure
generated by vulcanization in rubber compounds is directly
related with the final mechanical properties of the material. In a
recent article we analyzed the different behavior observed
depending on the preparation method used to obtain the
blend [1]. The objective in this work is to study this influence
on the cure kinetic of the NR/SBR blends.
rubber): 2phr of stearic acid, 5phr of zinc oxide, 2.25phr of sulfur
and 0.7phr of accelerator (TBBS).
Two methods were used for the blend preparation:
a) Mechanical Mixing: The components were mixed in a labora-
tory mill with the proportions of elastomers given in Table 1.
b) Solution Blending: A previous dilution of NR in toluene was
made to remove precipitated impurities. The pure solution
was allowed to evaporate the solvent. Next, NR and SBR were
diluted separately in toluene with a concentration of 20 gr/l
and 18gr/l, respectively. The blends were prepared in solution
with the composition of Table 1, after the chemicals were
added and mechanically homogenized. Finally the solvent was
evaporated at room temperature.

2. Material and methods
Rubber compounds were prepared with natural rubber
(NR-SMR20) and styrene-butadiene rubber (SBR–1502). The
molecular weights of the polymers, Mn, measured by GPC, were
128.260 and 178.830 g/mol for SBR and NR, respectively. The
system of cure had the following quantities (in per hundred of
n
Corresponding author. Tel.: þ54 11 4576 3353; fax: þ 54 11 4576 3357.
E-mail address: mmansilla@df.uba.ar (M.A. Mansilla).
Each compound was characterized at 433 K by torque rheo-
metric curves with an Alpha 2000 MDR and the time t100 to
achieve the maximum torque th was obtained. Also, Dt ¼ th  tl
was estimated, this quantity is related to the elasticity of the
material; tl is the minimum torque. The values of t100 and Dt are
shown in Table 1.
Disk samples of 1.7 mm thickness and 17 mm diameter were
cured in a mold at 433 K up to time t100 to ensure complete
vulcanization. At the end of the curing cycle, the samples were
cooled in an ice-water bath to stop the vulcanization reaction.

0921-4526/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2011.12.084
3272 M.A. Mansilla, A.J. Marzocca / Physica B 407 (2012) 3271–3273

Table 1
Compound formulations, values of t100 and Dt obtained by rheometric measurements at 433 K.

Solution Blending
NR/SBR (phr) 0/100 10/90 20/80 30/70 40/60 50/50 60/40 70/30 80/20 90/10 100/0
t100 (min) 87.6 57.2 53.8 47.2 36.8 41.6 28.1 25.1 16.7 15.8 10.6
Dt (N.m) 0.75 0.73 0.70 0.71 0.70 0.72 0.67 0.67 0.57 0.61 0.55
Mcs(gr/mol)x103 11.5 11.6 14.5 14.2 16.3 12.8 10.9 11.8 42.1 56.6 22.2

Mechanical Mixing
NR/SBR (phr) 0/100 10/90 25/75 50/50 75/25 90/10 100/0
t100 (min) 42.3 38.5 34.4 24.8 17.0 12.8 10.7
Dt (N.m) 0.84 0.82 0.80 0.74 0.65 0.70 0.67
Mcs(gr/mol)x103 12.0 10.9 9.7 8.1 7.6 6.3 5.5

The molecular weight between crosslinks Mcs was estimated

in each sample by means of a swelling technique in toluene [2].
This state is described by the Flory-Rehner relationship [3]:

r ð12=f Þ V 1 v1=3
2m
M cs ¼  ð1Þ
lnð1v2m Þ þ w v22m þv2m

where r is the rubber density and f is the functionality of the

crosslinks, considered as 4 in elastomers cured with sulphur [4].
V1(toluene)¼106.29 ml/mol is the molar volume of the solvent.
v2m is the polymer volume fraction at the maximum degree of
swelling. w is the interaction parameter between the polymer and
the solvent, and was evaluated using a mixture law, starting from
the system NR/toluene and SBR/toluene: w(SBR)¼ 0.524-0.285
v2m [5] and w(NR) ¼0.43þ0.05 v2m [6].

3. Results and discussion

Fig. 1(a) shows some of the rheometric curves. They were

analyzed using a model for isothermal cured rubber [7,8], which
expresses the state of cure (y) as:
kr ðtt o Þn
y¼ ð2Þ
1 þ kr ðtt o Þn
kr is the rate constant, n is the order of the kinetic reaction, t0 is
an induction time and t is the reaction time. The state of cure
is obtained by normalizing the torque rheometric curve, using
y ¼(th  tt)/(th  tl) where tt is the torque at time t.
Fig. 1(b) shows cure evolution during the vulcanization process
for some compounds prepared by different methods and the
fitting to Eq. (2). It was found that the fitting is very good not
only for the pure compounds, but also for the blends.
The kinetic parameters obtained for each compound are given
in Fig. 2 as function of the NR content in the compound. The cure
rate increases in both preparation methods with the NR content.
This is caused by the higher reactivity of NR because it has more
hydrogens of allyl and benzyl groups. These ones are more
reactive with the free radicals during the vulcanization process
than other hydrogens [9].
As an empirical proposition, we suggest a mixing law for the Fig. 1. (a) Rheometer torque curves vs. cure time. (b) Comparison between y and
analysis of the parameters obtained. A mixing law series Eq. (2) for samples vulcanized at 433 K prepared by different methods.
kr ¼ fNRkNR
r þf
SBR SBR
kr can be used to fit these data successfully
(Fig. 2(a)), where fNR, fSBR are the weight fraction while kNR and
kSBR are the cure rates for each rubber. In the case of samples
prepared by solution blending the cure rate values are lower than preparation. The solution blending technique consists in dissol-
those obtained by mechanical mixing. ving once the SBR and twice the NR. This process diminishes the
The molecular weight between crosslinks. Mcs, is higher in the chains entanglements, which implies a decrease in the rubber
blends prepared by solution blending (see Table 1). In the SBR viscosity [10]. This fact was confirmed by measurements of the
sample the values are similar. The difference is stronger when the Mooney viscosity (ML 1þ 3 1001C) in an Alpha MV2000 viscosi-
compound is richer in NR. The higher is Mcs, the lower is the meter, following ASTM D1646-04. The values obtained were: 87.8
crosslinks density, because they are related inversely. The con- MU for raw NR and 33.5 MU for NR dissolved once in toluene and
sequence of this fact is also reflected in the values of Dt. This later on evaporated. For the SBR, the viscosities were: 56.5 MU
behavior is a consequence of the differences in the sample and 43.7 MU for the raw material and the elastomer after the
 M.A. Mansilla, A.J. Marzocca / Physica B 407 (2012) 3271–3273
Fig. 2. Kinetic parameters for the samples. The lines represent a mixing law
applied to fit the data (See text).
dissolving treatment. It implies that the dissolution process has a
strong effect on the NR disentanglement.
Fig. 2(b) shows the variation of the order of the kinetic
reaction, n, with the NR content in the blend. In the case of SBR,
the values of n are similar to those obtained in a previous paper
of our group [11]. n can be fitted by an expression of the type
1/n¼ fNR/nNR þ fSBR/nSBR where nNR and nSBR are the order of
the kinetic reaction for the NR and SBR pure compounds.
Fig. 2(b) shows a reasonable fit to the data. In a previous study
[12], an empirical correlation was presented between n and the
network chain density (nc 1/ Mcs):

(2010) T3–12.
log 1=M cs ¼ A þBlogn ð3Þ
Fig. 3 shows Mcs versus n according to the form of Eq. (3).
In the case of the mechanical mixing preparation, Eq. (3) can be
used for fitting the data reasonably. For samples prepared by
solution blending a remarkable change is observed when the
compounds are richer in NR. Eq. (3) can be applied from pure SBR
to NR70/SBR30.
An observation of the samples by means of SEM [1] shows that
the two phases are clearly detected in the blends mixed
3273
Fig. 3. Correlation between the order of the kinetic equation n and Mcs.
mechanically. However, for the solution preparation the phases
were not distinguished, which indicates an improvement in the
miscibility.
4. Conclusions
The rheometer curves of NR/SBR prepared by mechanical
mixing and solution blending cured at 433 K, were successfully
described by the Kamal-Sourour model. The cure rate depends on
the blend composition and can be fitted by a mixture law
considering the cure rates of the pure compounds. The order of
the cure reaction also depends on the composition and can be
fitted by a parallel law.
A considerable change in Mcs is observed when the samples
prepared by solution are richer in NR. This fact would be related
not only to the crosslinks formed during the vulcanization, but
also to the minor quantity of entanglements present in the
material prepared by solution blending. An empirical relationship
that links the reaction order with Mcs was settled down in the
whole range of samples prepared by mechanical mixing and in a
limited region of composition in the case of solution blending.
Acknowledgments
This work was supported by the University of Buenos Aires
and CONICET, both from Argentina.
References
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