Curing and Mechanical Properties of

Nitrile and Natural Rubber Blends

HANAFI ISMAIL,1 S. TAN AND B.T. POH
School of Industrial Technology
Universiti Sains Malaysia
11800 Minden, Penang, Malaysia

ABSTRACT: The curing and mechanical properties of nitrile (NBR) and natu-
ral rubber (NR) blends were carried out. Two series of blends were prepared,
i.e., NBR/SMR L and NBR/ENR 50 blends. Blends were prepared using a
Brabender at a temperature of 60C. Results indicate that the scorch time, t2
and cure time, t90 increase with increasing NBR content in both blends. In
NBR/ENR 50 blends the increasing content of NBR increases the maximum
elastic torque, torque difference, tan @ MH and viscous torque. However, in
NBR/SMR L blends the opposite trend is observed for maximum elastic torque
and torque difference. In both blends modulus at 100% elongation (M100) and
at 300% elongation (M300) increases with increasing NBR content, whereas
tensile strength and elongation at break show a decreasing trend.

KEY WORDS: acrylonitrile butadiene rubber, natural rubber, blend, curing

characteristics, mechanical properties.

INTRODUCTION

LASTOMER BLENDS ARE widely used in rubber products for a variety of

reasons which include improved physical properties, improved ser-
vice life, easier processing, and reduced product cost [1]. The blending
together of natural rubber (NR) with nitrile rubber (NBR) is intended to
produce a vulcanizate with the best properties from each component,

1Author to whom correspondence should be addressed.

JOURNAL OF ELASTOMERS AND PLASTICS Vol. 33October 2001 251

0095-2443/01/04 0251-12 $10.00/0 DOI: 10.1106/DQN6-QXA0-UC3W-U45H
2001 Sage Publications

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252 HANAFI ISMAIL , S. TAN AND B.T. POH

i.e., NBRs high resistance to swelling of oils and NRs good strength
properties [2]. The acrylonitrile component in NBR provides the rubber
with its oil resisting properties; the higher the acrylonitrile content, the
greater the oil resistance. Epoxidized natural rubber (ENR) is a chemi-
cally modified form of the cis 1,4-polyisoprene rubber, whereby some of
the unsaturation is converted into epoxide groups which are randomly
distributed along the polymer chain [34]. The higher the amount of
epoxidation, the greater the polarity of the rubber. On this basis, NBR
and SMR L differ in polarity. With regard to NBR/NR blends, there is no
report on the comparison of curing and mechanical properties of
NBR/SMR L and NBR/ENR 50 blends. It is thus the aim of this article to
describe some of our findings in this area of interest.

EXPERIMENTAL

Materials

Two different types of NR, i.e., SMR L and ENR 50, having 0 and 50
mol% of epoxidation were blended with NBR in this study at different
ratios. SMR L and ENR 50 were supplied by Guthrie (M) Sdn. Bhd.
Nipol DN 200 grade NBR was supplied by MARDEC (M) Bhd. Their
respective technical specification is shown in Table 1.
Sulfur and N-t-butylbenzothiazole-2-sulphenamide (TBBS) were
used as a vulcanizing agent and accelerator, respectively, throughout
this study. Commercial grade rubber chemicals such as zinc oxide and
stearic acid were also used. For each of the two types of NR, various
ratios of NBR were incorporated in the cure systems. The details of the
blend ratios are shown in Table 2. In each cure system, blends in gum
vulcanizates were prepared with master batches containing 5.0 phr zinc
oxide, 2.0 phr stearic acid, 1.3 phr TBBS (N-t-butylbenzo-
thiazole-2-sulphenamide), 1.3 phr sulfur and 1.5 phr TMQ.

Compounding

The mixing procedure was carried out in accordance with the Amer-

Table 1. Technical specification of SMRL, ENR 50 and NBR.

SMR L ENR 50 NBR
Glass transition temperature (C) 72 20 26
Specific gravity 0.92 1.03 1.00

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 Curing and Mechanical Properties of Rubber Blends 253

Table 2. Blend formulations of SMR L

and ENR 50 with NBR.a
NBR SMR L/ENR 50
100 0
75 25
50 50
25 75
0 100
aCure system: zinc oxide, 5; stearic acid, 2; sulfur, 1.3; TBBS, 1.3; TMQ,
1.5.

ican Society of Testing and Materials (ASTM)Designation D 3184-89

[5]. Mixing was conducted in a laboratory Brabender using a rotor speed
of 35 rpm with the temperature maintained at 60C 5C. The total
mixing cycle time was 5.5 minutes.

Testing

The cure characteristics were assessed by Monsanto Moving Die

Rheometer (MDR 2000). The various rubber blends were compression
molded into 2 mm-thick test specimen sheets at 150C according to their
respective optimum cure times. Dumbbell-shaped specimens were cut
from the molded sheets with a width of 6.3 mm 0.1 mm. Tensile
testing procedure was carried out in accordance with ASTM 412-98a [6]
using an Instron Universal Testing Machine (Model 1011) operating
with a crosshead speed of 50 cm/min.

RESULTS AND DISCUSSION

Curing Characteristics

Figures 1 and 2 show the effect of NBR content on the scorch time, t2
and cure time, t90 of the NBR/SMR L and NBR/ENR 50 blends. It can be
seen that the t2 and t90 of these blends increases with increasing NBR
content. NBR is a copolymer of acrylonitrile and butadiene and also is a
polar rubber. As the content of NBR in the blends is increased, the cura-
tive agent, i.e. sulphur, becomes less soluble in NBR compared to SMR L
and ENR 50. Consequently the curing rate of the blend decreases with
increasing content of NBR. Lewan [7] reported that for blends of two
rubbers differing in polarity, such as NR and NBR, maldistribution of
crosslinks can arise through preferential solubility of the curatives and
vulcanization intermediates.

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254 HANAFI ISMAIL , S. TAN AND B.T. POH

FIGURE 1. Variation of scorch time with % NBR at 150C for NBR/SMR L and
NBR/ENR 50 blends.

FIGURE 2. Variation of cure time with % NBR at 150C for NBR/SMR L and NBR/ENR
50 blends.

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 Curing and Mechanical Properties of Rubber Blends 255

It can be seen also in Figures 1 and 2 that at a similar NBR content, t2

and t90 of NBR/ENR 50 blend is shorter than NBR/SMR L blend. Poh
and Wong [8] reported that owing to the activation of an adjacent double
bond by the epoxide group, the scorch and cure times of ENR 50 are
shorter than those of SMR L. Probably more activated precursors to
crosslinks [9] are formed and will accelerate the vulcanization process.
The effect of NBR content on the maximum elastic torque (S @ MH)
is shown in Figure 3. It can be seen that the S @ MH increases with
increasing NBR content in the NBR/ENR 50 blend. Figure 3 also shows
that above about 14% of NBR, S @ MH of NBR/ENR blends has higher
values than NBR/SMR L blend as a result of the presence of epoxide
group in NBR/ENR 50 blend.
The relationship between the torque difference, S @ MH S @ ML
(max. elastic torque min. elastic torque) and content of NBR is shown
in Figure 4. It is known that the torque difference shows shear dynamic
modulus which indirectly relates to the crosslink density of the blends
[10]. This figure clearly shows that NBR/ENR 50 blend is a more
compatible blend than NBR/SMR L blend. The decreasing torque differ-
ence for NBR/SMR L indicates that a maldistribution of crosslink
occurred which results in an over-crosslinked phase and a poorly
crosslinked one.

FIGURE 3. Maximum elastic torque versus % NBR at 150C for NBR/SMR L and
NBR/ENR 50 blends.

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256 HANAFI ISMAIL , S. TAN AND B.T. POH

FIGURE 4. Torque difference versus % NBR at 150C for NBR/SMR L and NBR/ENR
50 blends.

Again at a similar NBR content, NBR/ENR blend exhibits higher S @

MH S @ ML than NBR/SMR L blend for NBR content greater than
about 10%. Gelling and Morrison [11] reported that with normal
sulphur vulcanizing systems, the efficiency of ENR vulcanization
seemed to be improved. The isolated double bonds in ENR inhibit the
formation of intramolecular sulphide links thus resulting in the
increase of the crosslinking rate.
Figures 5 and 6 show the effect of NBR content on the viscous torque
(S @ MH) and tan @ MH for all blends studied. Results indicate that
both properties increase with increasing NBR content in the blends.
Nagdi [12] reported that as the acrylonitrile content is increased, the
low-temperature flexibility, rebound resilience, compression set and gas
permeability of the NBR vulcanizates decrease correspondingly.
It can be seen also that at a similar NBR content, NBR/ENR 50 blend
has lower S @ MH and tan @ MH than NBR/SMR L blend. This could
be due to the increased crosslink density in NBR/ENR 50 blend
compared to NBR/SMR L blend. The damping behaviour (S @ MH) is a
very sensitive indicator of crosslinking [13]. Damping decreases with an
increased degree of crosslinking for lightly crosslinked rubbers. Nielsen
[14] also reported the similar observation.

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 Curing and Mechanical Properties of Rubber Blends 257

FIGURE 5. Viscous torque versus % NBR at 150C for NBR/SMR L and NBR/ENR 50
blends.

FIGURE 6. Loss tangent at maximum torque versus % NBR at 150C for NBR/SMR L
and NBR/ENR 50 blends.

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258 HANAFI ISMAIL , S. TAN AND B.T. POH

Mechanical Properties

Figure 7 shows the variation of M100 with % NBR in the two NBR
blends. It is obvious that as the percent of NBR increases, M100 also
increases correspondingly. This means that the incorporation of NBR in
the blend would enhance crosslinking as M100 is a measure of degree of
crosslinking. NBR/ENR 50 blend gives a higher M100 value than the
NBR/SMR L blends. This observation may be attributed to greater
enhancement effect of NBR on ENR 50. In fact, the maximum
crosslinking density is observed at 75% NBR content for ENR 50 blend.
As in the case of NBR/SMR L blend, the lower M100 is attributed to the
non-enhancement effect of NBR which is a polar polymer compared to
SMR L, a non-polar rubber. Thus, the NBR/SMR L blend has a lower
crosslinking density than ENR blends.
The variation of M300 with NBR content is indicated in Figure 8. In
this case, NBR/SMR L blend consistently shows a higher M300 than
ENR blends. This observation may be explained by the greater amount
of strain-induced crystallization in SMR L [15] compared to ENR 50
[16]. Maximum values of M300 occur at 50% NBR for NBR/SMR L
blend, whereas for NBR/ENR 50, the maximum value lies between
5075% NBR content. The existence of maximum values indicates that

FIGURE 7. Variation of M100 with % NBR in the blends.

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 Curing and Mechanical Properties of Rubber Blends 259

FIGURE 8. Variation of M300 with % NBR in the blends.

NBR reinforces NR and ENR blends: the degree of reinforcement is

greatest in SMR L, followed by ENR 50 as the degree of crystallization
decreases with increasing epoxidation.
Figure 9 shows the dependence of tensile strength of the two rubber
blends on % NBR. Again, SMR L blend consistently indicates a higher
tensile strength than the ENR 50 blend as observed for M300. However,
in this case, tensile strength decreases gradually with increasing % NBR
for all the blends studied. This observation is associated with the
decreasing effect of strain-induced crystallization as NBR content is
increased. As discussed earlier in M300, SMR L exhibits the greatest
strain-induced crystallization, followed by ENR 50. This sequence of
decreasing crystallization is reflected by the decreasing value of tensile
strength for the respective single component rubbers. In the case of
NBR, it has the lower tensile strength due to the non-crystallizable
nature of the rubber. Figure 9 also shows that for NBR content greater
than 50%, greater drop in tensile strength for the blends is observed.
This finding may be ascribed to the dominant effect of NBR at higher
loading of NBR.
The effect of NBR in SMR L and ENR 50 blends on elongation at
break is shown in Figure 10. The effect, in fact, is very similar to that of
tensile strength, i.e., elongation at break decreases gradually with
increasing NBR content. Owing to the higher strength of SMR L, its

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260 HANAFI ISMAIL , S. TAN AND B.T. POH

FIGURE 9. Variation of tensile strength with % NBR in the blends.

FIGURE 10. Variation of elongation at break with % NBR in the blends.

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 Curing and Mechanical Properties of Rubber Blends 261

blend gives a much higher elongation at break compared to ENR 50

blend. For the single component NBR, its elongation at break is the
lowest among the rubbers studied due to the non-crystallizable property
of NBR.

CONCLUSIONS

1. The incorporation of NBR in NBR/SMR L, and NBR/ENR 50 blends

increases the scorch time, t2 and cure time, t90. At a similar NBR con-
tent, NBR/ENR 50 blend exhibits shorter t2 and t90 than NBR/SMR L
blend.
2. The incorporation of NBR in NBR/ENR 50 blend also increases the
maximum elastic torque (S @ MH), torque difference (S @ MH S
@ ML), tan @ MH and viscous torque (S @ MH). However for
NBR/SMR L blend the maximum elastic torque and torque difference
decrease with incorporation of NBR, an observation which is attrib-
uted to the maldistribution of crosslink between the two rubber
phases.
3. M100 and M300 increase with increasing NBR content in both
blends. The former increase is attributed to the enhancing effect of
NBR and the latter increase is associated with strain-induced crystal-
lization of the respective rubbers.
4. Tensile strength and elongation at break of the blends decrease grad-
ually with % NBR, an observation which is ascribed to the decreasing
effect of strain-induced crystallization of SMR L and ENR 50 as NBR
content is increased in the respective blends.

ACKNOWLEDGEMENT

The authors acknowledge the research grant provided by Universiti

Sains Malaysia, Penang that has resulted in this article.

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