Journal of Elastomers and

Plastics
http://jep.sagepub.com/

Characteristics of Acrylic Rubber Composites with Mica and Carbon Black

Renata M.B. Fernandes, Leila L.Y. Visconte and Regina C.R. Nunes
Journal of Elastomers and Plastics 2010 42: 65 originally published online 13 November
2009
DOI: 10.1177/0095244309349476
The online version of this article can be found at:
http://jep.sagepub.com/content/42/1/65

Published by:
http://www.sagepublications.com

Additional services and information for Journal of Elastomers and Plastics can be found at:
Email Alerts: http://jep.sagepub.com/cgi/alerts
Subscriptions: http://jep.sagepub.com/subscriptions
Reprints: http://www.sagepub.com/journalsReprints.nav
Permissions: http://www.sagepub.com/journalsPermissions.nav
Citations: http://jep.sagepub.com/content/42/1/65.refs.html

>> Version of Record - Feb 2, 2010

OnlineFirst Version of Record - Nov 13, 2009
What is This?

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

Characteristics of Acrylic
Rubber Composites with Mica
and Carbon Black
RENATA M. B. FERNANDES,
AND REGINA C. R. NUNES*

LEILA L. Y. VISCONTE

Instituto de Macromoleculas Professora Eloisa Mano

Universidade Federal do Rio de Janeiro, Centro de Tecnologia
Bloco J, CEP 21945-970, Rio de Janeiro, RJ, Brazil

ABSTRACT: In this work mica or carbon black were used as filler in

composites of acrylic rubber (ACM). The fillers differ not only in nature, mica
being a mineral material and carbon black being organic, but also in form and
particle size. The content of filler varied from 0 to 50 phr and its influence on
ACM was evaluated based on cure parameters, mechanical, and swelling
properties. The cure parameters allow the conclusion that the presence of mica
does not have a negative effect on the cure or processability; the swelling results
indicated a weak interaction between ACM and mica even though the
mechanical properties of ACM composition with 40 phr of mica were found to
be similar to those of 20 phr carbon black. As a result of mica being less
expensive than carbon black, is light colored and easily processible, these
properties are of industrial importance. All properties analyzed were compared
with gum type composition (without filler).
KEY WORDS: acrylic rubber, mechanical properties, mica, swelling properties,
carbon black.

INTRODUCTION

are classified as high-temperature, oilresistant, specialty rubbers [1]. They both have a saturated

CRYLIC RUBBERS (ACM)

*Author to whom correspondence should be addressed. E-mail: rcnunes@ima.ufrj.br

JOURNAL OF ELASTOMERS AND PLASTICS Vol. 42January 2010

0095-2443/10/01 006510 $10.00/0
DOI: 10.1177/0095244309349476
The Author(s), 2010. Reprints and permissions:
http://www.sagepub.co.uk/journalsPermissions.nav

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

65

66

R. M. B. FERNANDES

ET AL.

backbone, which is responsible for the heat and oxidation resistances, and
ester side groups, which contribute to the marked polarity [2]. Due to
their good properties, acrylic elastomers have been widely used in
automobile field and related fields such as sealing, belt, vibration
insulator, gaskets, and hose materials [3,4]. Most of the work and
patents are concerned with mechanical properties of acrylic rubber
blends with other polymers [58]. Fillers are usually used in rubbers to
improve their mechanical properties and to reduce costs; carbon black
and silica are the most common fillers used in rubber compounds [3,9,10].
The term mica stands for a series of silicate minerals and various
micas are structurally similar, although the chemical composition may
vary widely. The most common types are muscovite, phlogopite, and
biotite [11,12]. In this work, the mica studied was muscovite.
The structure and size of the filler influences its dispersion in the
elastomeric matrix and the fillerrubber interaction in the compositions
can be investigated by physico-mechanical behavior. The swelling index,
for instance, is reduced by crosslinks in the filled vulcanizates, as a
result of several mechanisms such as adhesion of the matrix on the filler
surface, chemical bonding of polymer to the filler surface, and formation
of crosslinks near the filler [13]. In this work, the mechanical properties,
cure characteristics, and swelling behavior of acrylic rubber compounded with mica or carbon black were studied.

EXPERIMENTAL

Materials
Acrylic rubber (Hycril 1540), containing 5% by weight of available
cure sites, Mooney viscosity ML(14) at 1008C 32.10, was supplied by
stria e Comercio S.A., Rio de Janeiro, Brazil. Mica
Petroflex Indu
muscovita with density of 2.64 g/cm3 and average particle size of
stria e Comercio Ltda,
54.77 mm was supplied by Brasilminas Indu
o Paulo, Brazil, and carbon black furnex type N762 with average
Sa
particle size of 61100 nm and density of 143 g/cm3 was supplied by
o Paulo, Brazil. The other additives,
Columbian Chemicals do Brasil, Sa
used as received, were Struktol WB222 (processing agent; Schill &
Scilacher), Naugard 445 (antioxidant; Uniroyal Chemicals), stearic acid
(retardation agent), sodium stearate (accelerator), and Chemac PAR K
50 (cure agent). The amount of mica and carbon black used were varied
from 10 to 50 phr (parts per hundred resin). In order to compare
the influence of mica or carbon black added, one pure gum type

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

Characteristics of Acrylic Rubber Composites

67

composite was studied. The fillers were dried at 1008C, during 2 h in an

air-circulating oven.
Preparation of Composites
The compositions were prepared on a two-roll mill at a controlled
temperature of about 658C. Acrylic rubber (100 phr) was masticated for
1 min, followed by blending with filler (from 0 to 50 phr); Struktol
WB222 (1.5 phr); Naugard 445 (1.5 phr); stearic acid (1.0 phr); sodium
stearate (4.0 phr); and Chemac PAR K 50 (1.5 phr).
Cure Characteristics
The cure characteristics of the composites were determined on an oscillating disk rheometer, ODR (Tecnologia Industrial, TI100) at 1808C for
60 min, with an oscillating angle of 18, in accordance with ASTM D 2084.
Mechanical Properties
The compositions were cured at 1808C and of 5 MPa pressure in a
compression press. Tensile and tear properties were determined on
the vulcanized sheet using a universal testing machine (Instron 1101).
The tests were carried out at a crosshead speed of 500 mm/min at 258C,
in accordance with ASTM D 412 for tensile strength and ASTM D 624
for tear strength. The Shore A hardness was determined following
ASTM D 2240.
Swelling Index
The test specimens (2 cm2 cm0.2 cm), in triplicates, were kept in
the dark, in acetone at room temperature for 72 h. After that, the
swollen samples were blotted with filter paper and immediately weighed
in a glass-stoppered bottle. The volume fraction of rubber in the swollen
gel (Vr) was then calculated [14].

RESULTS AND DISCUSSION

The cure parameters are shown in Table 1. The increase in minimum

(ML) and maximum torques (MH) was observed for all composites,
except for the lower content of mica for which ML is the smallest, in
comparison with pure gum (without filler).

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

68

R. M. B. FERNANDES

ET AL.

Table 1. Rheometric parameters for ACM/filler composites.

Composites
ACM/Filler (phr)

ML (dN.m)

MH (dN.m)

M (MH  ML)

ts1 (min)

t90 (min)

ACM/Mica
100/0
100/10
100/20
100/30
100/40
100/50

1.92
1.81
2.26
2.37
2.49
2.49

14.92
15.48
16.27
18.42
18.76
21.13

13.00
13.67
14.01
16.05
16.27
18.64

1.20
1.20
1.80
1.80
1.80
1.20

24.60
23.40
22.20
23.40
22.80
24.60

ACM/Carbon black
100/10
100/20
100/30
100/40
100/50

2.37
2.60
3.16
3.62
4.07

17.29
16.44
22.15
26.78
29.83

14.92
16.84
18.99
23.16
25.76

1.20
1.20
1.20
1.20
0.60

22.20
19.80
21.00
23.40
25.20

ML is associated with the viscosity; in carbon black compositions ML

increases with filler content increasing. This can indicate the presence of
rubberfiller interactions caused by carbon black particle of colloidal
dimensions, spherical in form, and with high surface area [15,16]. In the
case of mica addition to ACM rubber, ML increases a little at first and
then is maintained at an approximately constant value. Two kinds of
behavior can be taking place: the ACMmica interaction is weak and the
platelet form of mica improves the processability and as a consequence
the viscosity is low [17].
MH is associated with molecular stiffness [15,18] and again, the best
results are given by carbon black as the filler. The influence of both
fillers is best analyzed through
M(MH  ML). The influence of carbon
black was more effective suggesting better interaction of this filler with
the elastomeric matrix. Although the mica used in the present work has
a very large particle size compared to carbon black, the
M values show
some similarity considering the compositions with 40 phr and 50 phr of
mica and those with 20 phr and 30 phr of carbon black, respectively.
Neither the scorch time (ts1) nor the cure time (t90) of the compounds
have changed significantly with the addition of the fillers, with values
very close to pure gum. This means that these fillers amounting up to
50 phr do not prejudice the cure behavior.
The mechanical properties related to stress at break, strain at break,
and rupture energy of the investigated composites are shown in Table 2.
From the area under the graphic of strain versus stress, it is possible
to calculate the rupture energy, necessary to break the sample

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

69

Characteristics of Acrylic Rubber Composites

Table 2. Stress at break, strain at break and rupture energy
values for ACM/filler composites.
Composites
ACM/Filler (phr)

Strain at
break (%)

Stress at
break (MPa)

Rupture
energy (J/m)

ACM/Mica
100/0
100/10
100/20
100/30
100/40
100/50

180
150
180
190
200
180

0.65
0.57
0.85
1.18
1.34
1.73

12.67
11.03
17.47
26.83
28.63
34.95

ACM/Carbon black
100/10
100/20
100/30
100/40
100/50

150
150
160
150
125

0.86
1.45
3.06
3.00
5.66

15.15
30.89
54.91
54.42
83.35

under stress. With exception of strain at break that remains nearly

constant, all the other properties increase with the increasing filler
content. The reinforcing influence of carbon black is outstanding,
compared with mica, but the values for mica composites although lower
are higher for the pure gum. As observed in
M cure parameter, there is
a similarity in properties between the composite with 40 phr of mica
with the one with 20 phr of carbon black. Because of these results this
mineral filler can be characterized as semi-reinforcing agent for ACM
compounds. This proposition can still be corroborated by the values of
tear strength showed in Figure 1, which again are very similar in the
case of these two compositions.
Figure 1 shows the influence of mica and carbon black on tear
strength, of acrylic rubber mixtures. Tear strength values increased
with the filler content. Beyond 40 phr of carbon black in the mixture,
tear strength decreased but for acrylic rubber with mica, tear strength is
still increasing. This means that the limit of mica can be higher than
50 phr without causing damage to this property. Again, composites with
20 phr and 30 phr of carbon black have, respectively, the same tear
strength as ACM with 40 phr and 50 phr of mica. All these results have
technological properties since mica composites are light colored and this
filler is less expensive than carbon black (mica costs U$0.45/kg and
carbon black U$2.67/kg according to the suppliers).
Table 3 shows the results for modulus at 100% and hardness of acrylic
rubber mixtures with mica and carbon black. Again, the compounds

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

70

R. M. B. FERNANDES

ET AL.

12.5
Carbon black
Mica

Tear strength (kN/m)

10.0

7.5

5.0

2.5

0.0
100/0

100/10

100/20

100/30

100/40

100/50

Composites ACM/Filler (phr)

FIGURE 1. Tear strength as a function of filler content in acrylic rubber composites.

Table 3. Modulus at 100% and hardness of acrylic rubber blends.

Composites
ACM/Filler (phr)

Modulus at
100% (MPa)

Hardness
(Shore A)

ACM/Mica
100/0
100/10
100/20
100/30
100/40
100/50

0.3
0.5
0.5
0.8
0.7
1.1

(0.5)
(0.09)
(0.02)
(0.07)
(0.05)
(0.10)

19
22
26
28
32
36

(1.0)
(1.0)
(0.5)
(1.0)
(1.0)
(0.5)

ACM/Carbon black
100/10
100/20
100/30
100/40
100/50

0.5
0.8
0.9
2.4
4.0

(0.04)
(0.12)
(0.13)
(0.54)
(0.29)

25
29
36
45
54

(0.5)
(0.5)
(0.5)
(0.5)
(0.5)

with 40 phr of mica and 20 phr of carbon black show comparable results.
The increase in these property values can be related to the molecular
stiffness increase of composites, and can be compared with the
maximum torque (MH) obtained by ODR. Carbon black as a filler has
the best performance with ACM, which is as an indication of good
rubberfiller interaction solely because of its own characterisitics.

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

71

Characteristics of Acrylic Rubber Composites

0.33

Mica

0.30
Carbon black

0.28
0.25
0.23
0.20
Vr

0.18
0.15
0.13
0.10
0.08
0.05
0.03
0.00
100/0

100/10

100/20

100/30

100/40

100/50

ACM/Filler composites (phr)

FIGURE 2. Volume fraction of rubber in the swollen vulcanizates (Vr) for ACM without
and with mica and carbon black as fillers.

The swelling study was performed as an effort to quantify filler

matrix interaction. The results are shown in Figures 2 and 3. In Figure 2
the values for volume fraction of rubber in the swollen vulcanizates (Vr)
of ACM, with and without mica and carbon black can be seen. An
increase of Vr values means that crosslink densities increase thus
resulting in less swelling [14]. It could be seen that on increasing the
mica content, Vr values do not show an increase, which suggests a poor
ACMmica interaction. On the other hand, carbon black in 50 phr
content seems to be more effective, as far as the interaction with ACM is
concerned.
Polymerfiller interaction was also evaluated by using Kraus
equation:
Vro =Vrf 1  m1  ,
where Vro is the volume fraction of rubber in the gum vulcanizate, Vrf is
the volume fraction of rubber in the filled vulcanizate,  is the volume
fraction of filler in the vulcanizate, and m is a parameter calculated from
the slope of the straight line.

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

72

R. M. B. FERNANDES

ET AL.

Figure 3 shows Kraus plots for acrylic rubber filled composites where
it can be seen that for the carbon black filled vulcanizates, Vro/Vrf values
are lower than 1, which indicates some polymerfiller interaction.
Acrylic rubber composites filled with mica muscovite show a different
behavior, since Vro/Vrf values are close to 1, thus suggesting a weak
polymerfiller interaction.

CONCLUSIONS

Despite its mineral character and the large particle size used in this
work, mica may still be classified as a semi-reinforcing filler for acrylic
rubber composites. Compared with carbon black, an effective reinforcing
filler for ACM, the interaction between ACM and mica, investigated by
swelling methods, was found to be weak. However, the presence of either
carbon black or mica does not affect cure characteristics but increases
the stiffness of the composites.
As for mechanical properties, corroborating
M cure parameter,
compounds with 20 phr and 30 phr of carbon black have showed
behavior that were found to be similar to the compounds with,

2.0
Mica
Carbon black

Vro/Vrf

1.5

f (1 f)
1.0

0.5

0.0
FIGURE 3. Relationship between filler concentration and equilibrium volume swelling in
acetone of ACM/filler network plotted in the form of Kraus equation.

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

Characteristics of Acrylic Rubber Composites

73

respectively, 40 phr and 50 phr of mica. These results are industrially

significant since mica is less expensive than carbon black, easier to
process, and the composites are light colored.

ACKNOWLEDGMENTS
o
The authors would like to thank CNPq and FUJB (Fundaca
ria Jose Bonifa
cio) for the financial support, Petroflex
Universita
stria e Comercio S.A for supplying the acrylic rubber and the
Indu
stria e Comercio Ltda. for
other additives, and Brasilminas Indu
supplying mica.

REFERENCES
1. Wootthikanokkhan, J. and Tunjongnawin, P. (2003). Investigation of the
Effect of Mixing Schemes on Cross-link Distribution and Tensile Properties of
Natural-acrylic Rubber Blends, Polym. Test., 22: 305312.
2. Datta, S. (2004). Special-purpose Elastomers, In: Rodgers, B. (ed.), Rubber
Compounding Chemistry and Applications, New York, USA, Taylor and
Francis, Marcel Dekker, Inc., pp. 105132.
3. Hashimoto, K., Maeda, A., Hosoya, K. and Todani, Y. (1998). Specialty
Elastomers for Automotive Applications, Rubber. Chem. Technol., Rubber
Rev., 71: 449518.
4. Kubota, I., Tsugawa, D. and Nishimura, K. (2004). Acrylic Rubber
Composition, Crosslinkable Acrylic Rubber Composition, and Crosslinked
Object Obtained Therefrom, United States Patent 2004. Patent No.:
US6,689,843 B2.
5. Wootthikanokkhan, J. and Tongrubbai, B. (2003). Compatibilization Efficacy
of Poly(isoprene-butyl acrylate) Block Copolymers in Natural/Acrylic Rubber
Blends, J. Appl. Polym. Sci., 88: 321927.
6. Kader, M.A. and Bhowmick, A.K. (2003). Acrylic Rubber-fluorocarbon
Rubber Miscible Blends: Effect of Curatives and Fillers on Cure, Mechanical,
Aging and Swelling Properties, J. Appl. Polym. Sci., 89: 14421452.
7. Jha, A. and Bhowmick, A.K. (1997). Thermoplastic Elastomeric Blends of
Poly(ethylene terephtalate) and Acrylate Rubber: 1. Influence of Interaction
on Thermal, Dynamic Mechanical and Tensile Properties, Polymer, 38:
43374344.
8. Wootthikanokkhan, J. and Tunjongnawin, B. (2002). A Study on Morphology
and Physical Properties of Natural-acrylic Rubber Blends, J. Appl. Polym. Sci.,
86: 15321539.
9. Hancock, M. and Rothon, R.N. (1995). Principal Types of Particulate Fillers,
In: Rothon, R.N. (ed.), Particulate-filled Polymer Composites, Harlow,
Longman, Vol. 2, pp. 4787.

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013

74

R. M. B. FERNANDES

ET AL.

10. Claramma, N.M., Varghese, L. and Mathew, N.M. (1999). Effect of Fillers on
the Properties of Prevulcanized Natural Rubber Latex Film, J. Elastom.
Plast., 31: 130142.
11. Escocio, V.A., Martins, A.F., Visconte, L.L.Y., Nunes, R.C.R. and Costa,
nicas e Dina
micoD.M.R. (2003). Influencia da Mica nas Propriedades Meca
nicas de Composicoes de Borracha Natural, Polim. Cienc. Tecn, 13:
meca
130134.
12. Shell, H.R. (1967). Micas Natural and Synthetic, In: Kirk-Othmer,
Encyclopedia of Chemical Technology, New York, USA, Interscience
Publishers, John Wiley & Sons, Vol. 13, pp. 398424.
13. Stickney, P.B. and Mueller, W.J. (1969). Influence of Carbon Black on
Swelling Rate of Polymer in Filled Vulcanizates, Rubber Chem. Technol.,
42: 604612.
14. Kraus, G. (1963). Swelling of Filler-reinforced Vulcanizates, J. Appl. Polym.
Sci., 7: 861871.
15. Kraus, G. (1978). Reinforcement of Elastomer by Particulate Fillers,
In: Eirich, F.R. (ed.), Science and Technology of Rubber, Chap. 8, New
York, Academic Press, pp. 387416.
16. Lapa, V.L.C., Visconte, L.L.Y., Affonso, J.E.S. and Nunes, R.C.R. (2002).
Aluminum Hydroxide and Carbon Black Filled NBR/PVC Composites
Vulcanization and Processability Studies, Polym. Test., 21: 443447.
17. Escocio, V.A., Visconte, L.L.Y., Oliveira, M.G. and Nunes, R.C.R. (2008).
Rheology and Processability of Natural Rubber Composites with Mica,
Int. J. Polym. Mater, 57: 19.
18. Leblanc, J.L. (2002). Rubber-filler Interactions and Rheological Properties
in Filled Compounds, Prog. Polym. Sci., 27: 627687.

Downloaded from jep.sagepub.com at SAINT LEO UNIVERSITY LIBRARY on November 27, 2013