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A new approach with prepregs for reinforcing

nitrile rubber with phenolic and benzoxazine resins
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Cite this: RSC Adv., 2014, 4, 12526

S. Rajesh Kumar,a P. M. Asseref,a J. Dhanasekarana and S. Krishna Mohan*b

Acrylonitrile-co-butadiene rubbers (NBR) reinforced with phenolic and benzoxazine resins (NBRPh and
NBRBz respectively) are prepared by a novel method using co-curing. The relative eect of these resin
reinforcements with NBR in comparison to the non-reinforced NBR rubber compound NBRS under the
same conditions has been investigated. It was found that these resins exist in the form of a localized,
interpenetrating network structure in the NBR matrix. For both NBRPh and NBRBz composites, the
tensile strength, tear strength and elongation at break increases compared to NBRS. The tensile
strength in particular was increased by about 91% for NBRPh and by about 109% for NBRBz.
Thermogravimetric analysis (TGA) provides evidence for the superior thermal stability for NBR
Received 9th October 2013
Accepted 3rd January 2014

composites over NBRS. A decrease in the swelling values are observed in the NBR composites and the
retained tensile strength, elongation at break and modulus from thermal aging studies are found to be

DOI: 10.1039/c3ra45684f

superior than NBRS. These results have shown that both the phenolic and benzoxazine resins are

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eective reinforcements for NBR materials.

1. Introduction
Acrylonitrile-co-butadiene rubber (NBR) is used in aircras,
automobiles, tanks, oil drilling industries and other military
applications as seals, gaskets, O-rings etc. due to its excellent oil
and fuel resistances and low gas permeability. However, rubber
compositions based on NBR have limited high temperature
stability, chemical resistance and service life because of the
presence of an unsaturated backbone. The incorporation of
small particle size llers to the elastomer matrix results in
substantially improved mechanical properties.1,2 Results of
small and well-dispersed silica generated by an in situ solgel
process demonstrated the improvement of the rubberller
interactions and better ller dispersion3,4 using a silane
coupling agent.57 The modication of elastomers with carbon
nanobres or nanotubes811 of high aspect ratio and low density
has also been studied.
Recently, polymer reinforced elastomeric composites have
attracted signicant attention due to their outstanding
mechanical properties when compared to conventional elastomers. The polymeric resins are recognized as potential materials for improving the physicalmechanical properties of
elastomers with retention of the aging properties. Studies on
natural llers such as soy protein aggregates and modied
starch for reinforcement with styrene butadiene rubber
a

Advanced Composite Centre, Advanced Systems Laboratory (ASL), Kanchanbagh,

Hyderabad-500 058, India

Propellant and Polymer Divsion, Directorate of Propulsion, Defence Research &

Development Laboratory (DRDL), Kanchanbagh, Hyderabad-500 058, India. E-mail:
kmohan_s@yahoo.com; scientistdrdohyd@gmail.com

12526 | RSC Adv., 2014, 4, 1252612533

(SBR)1214 and lignin with NBR showed good compatibility with

the rubber matrix, and their reinforcement eects were superior
to those of carbon black.15 The reinforcement of synthetic
polymers such as cardinolformaldehyde, ultra high molecular
weight polyethylene (UHMWPE), polyaniline, resorcinolformaldehyde and epoxy resins in various rubbers has been studied
to improve the mechanical properties.1622 The reinforcement of
phenolic resins with chloroprene, ethylene propylene diene
monomer (EPDM) and NBR, and epoxy resin with SBR through
in situ polymerisation has also been discussed.2325 The resin
reinforcements for NBR are prepared by most common
methods such as in situ polymerization, solution, melt mixing,
blending, coating and latex blending. However, detailed studies
are required due to diculties arising in the uniform dispersion
of the resins while incorporating them into the elastomers,
which plays a critical role in the enhancement of the properties.
Benzoxazine resins are a new class of phenolic polymers being
developed as an alternative to traditional high-performance
thermosetting resins for aerospace applications.26 Benzoxazines
have the design exibility for various applications, and they can
be tailored to display a range of properties which cover advanced
epoxy and phenolic resins to bismaleimides and polyimides.
Their distinct advantages are re resistance and superior processability compared with the majority of thermosetting resins
known today. In addition, these materials have high glass transition temperatures (Tg), high moduli, low water absorption,
good electrical properties and no shrinkage upon curing.27 Even
though the applications of benzoxazines are increasing rapidly,
to the best of our knowledge the reinforcement of benzoxazine
resins with nitrile rubbers has not been attempted so far.

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In this work, we have explored a novel method for the

preparation of NBR/resin composites for the rst time by using
a co-curing process at high temperature (i.e. 200
C) from resin
prepregs. The co-curing process has many advantageous due to
its simplicity, lower capital investment and eco-friendly nature.
This method is faster, more versatile and produces more
uniform cross linking when compared with the conventional
techniques. The mechanism of reinforcement of the resin to the
nitrile rubber by this method may proceed in two stages. In the
rst stage during co-curing, the resin present in the prepreg
ows in to the rubber compound layer through porous releasing
fabric, and in the second stage this resin forms the reinforcement with the nitrile rubber compound at high temperature.
This study attempts the reinforcement of phenolic and benzoxazine resins with nitrile rubber for the rst time using a cocuring process. The relative eect of these resin reinforcements
to NBR in comparison to the non-reinforced NBR compound
has been also investigated under the same conditions.

2.

Experimental

2.1. Raw materials

The thermosetting resins used for the reinforcement with NBR
are phenolic (resol type, solid content: 61.69%, PR-100) and
bisphenol-F-benzoxazine resins (mp: 65
C85
C; Araldite MT
35700) provided by ABR Organics, India and Huntsman Ltd,
Switzerland respectively. The carbon (rayon-based) and release
(D200 TFP) fabrics were obtained from Aerospace Ltd., Coimbatore, India and De-comp Composites Inc., USA respectively.
Nitrile rubber compound sheet procured from RAP Vijayawada,
India was used as received. Both the breather fabric (AB 1060V)
and vacuum bagging lm (50 micron thick) were obtained from
Aerovac, UK. Methyl ethyl ketone (MEK) solvent was procured
from Fluka, Switzerland. The characteristics of the nitrile
rubber compound sheet, carbon fabric, release and breather
fabrics, vacuum bagging lm are given in Table 1. The chemical
structures of NBR and the thermosetting resins are represented
in Fig. 1.

Fig. 1

Chemical structures of NBR and the thermosetting resins.

mould, and a metallic caul plate was placed over the layers. The
setup was enclosed in breather cloth and a vacuum bag, and
curing was carried out in an oven as per the cure cycle represented in Fig. 2 to obtain non-reinforced NBRS. This material

2.2. Preparation of NBRS

Two plies of release fabric (200  200 mm each) are placed
above and below the 200  200 mm sized 2 mm thick NBR
rubber compound sheet. Four carbon fabric layers of 200  200
mm were plied over the release fabric on both sides of the
layers. The complete setup of plies was placed on a metallic

Table 1

Fig. 2

Cure cycle followed in the co-curing process.

Details of raw materials used

Materials

Characteristics

Nitrile rubber compound sheet (rocasine)

Composition in PPhr: NBR: 100, sulphur: 1.5, ZnO: 5.0, stearic acid: 1.0,
DEG: 2.0, DOP: 10.0, silica: 50.0, pet. resin: 10.0, TTD: 0.2, 2-MD: 1.5
Carbon content: 94%, sp. gravity: 1.8  0.1, thickness: 0.30.4 mm
Porous Teon coated plain wave thickness: 0.003 inches
Heavy weight synthetic 330 g m2 polyester non-woven breather fabric
Capran 518, heat-stabilised nylon 6 tubular bagging lm, 50 microns
thick

Carbon fabric (rayon-based carbon fabric)

Release fabric (D200 TFP)
Breather fabric AB 1060V
Vacuum bagging lm 2.0 M, 518280

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will act as a reference material in studying the reinforcement

eects of both phenolic and benzoxazine resins with NBR.

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2.3. Preparation of carbonphenolic/carbonbenzoxazine

prepregs
Carbonphenolic prepregs were prepared by spreading
phenolic resin (55 g) uniformly on the carbon fabric manually
by hand. Prior to the preparation of the carbonbenzoxazine
prepregs, benzoxazine resin (100 g) was added to a vessel and
MEK solvent (30 g) was added, and the mixture was heated at
70
C to obtain a clear solution of benzoxazine resin. From the
prepared resin, 55 g was taken and was uniformly spread on the
carbon fabric. The prepared prepregs were dried at room
temperature until they became tacky.
2.4. Preparation of NBRPh and NBRBz by a co-curing
process
The above prepared prepregs (carbonphenolic/carbonbenzoxazine) were used for the preparation of the NBR composites
NBRPh and NBRBz, respectively. They were prepared by a
similar procedure as used for the preparation of NBRS, but
instead of carbon fabric, carbonphenolic and carbonbenzoxazine prepregs were used for NBRPh and NBRBz respectively.
The co-curing was carried out using a similar cure cycle (Fig. 2).
The sample codes and formulations of NBR and the NBR
composites are given in Table 2. A schematic representation of
the co-curing process is given in Fig. 3, and the ow chart is
represented in Fig. 4.
2.5. Instrumentation

Samples of 25 mm  25 mm of weight approx. 1 g (w1) were cut

from the central portion of the moulded sheet and allowed to
swell in various solvents and turbine fuel (ATF) at ambient
conditions. Aer 72 h, the swollen samples were removed,
wiped dry and weighed again (w2). The degree of swelling is
calculated using the following equation:
Swelling (%) (W2  W1)/W1  100.
2.7. Aging studies
The accelerated aging test was carried out at 100  2
C for 72 h
in a heat oven as per ASTM 537-67. The samples were allowed to
rest at room temperature for 24 hours before determining the
percentage retention in the mechanical properties.

Sample codes and formulations of NBRS and reinforcements

Sample code

NBR (area, mm)

NBRS
NBRPh
NBRBz

200  200
200  200
200  200

samples was determined with a Wallace model 1 HT 16A digital

Shore-A durometer as per ASTM D 2240.
Thermogravimetric analysis curves were recorded with a TA
Instruments, model no. SDT 2960 instrument as per ASTM E
2550. The TGA measurements were conducted with a heating rate
of 10
C min1 under nitrogen gas ow between 30 and 600
C.
Morphological characterization was performed using Scanning
Electron Microscopy (SEM, JEOL JSM 5800 Digital). Fractured
surfaces of the tensile test specimens were cut carefully without
touching the surface, and the fracture topography was studied.
2.6. Swelling studies

ATR-FTIR spectra were recorded using an Agilent 640 series

FTIR equipped with the Ge-ATR accessory. All samples were
examined with a spectral resolution of 4 cm1 and scanned
from 400 to 4000 cm1 in the transmission mode.
The tensile strength, modulus and elongation at break were
carried out on dumbbell-shaped samples using a DAK Systems
INC, model no: 9052 Universal testing machine (UTM) operated
at room temperature with a gauge length of 25 mm and a
crosshead speed of 500 mm min1 as per the ASTM D 412. The
tensile values reported herein are the average of the results of
tests run on at least six specimens. The tear strength (type C) of
the samples was also determined with the DAK Systems INC
UTM by using no-notched 90 degree angled tear test pieces as
per ASTM D 624-48. Tensile set was determined as per ASTM D
412. The hardness of the reference and reinforced rubber

Table 2

Fig. 3 Schematic representation of the co-curing process. (a) NBR

compound layer, (b) layering of NBR with releasing fabric and fabric/
prepreg layers, (c) layering with metallic and coul plates, (d) nal setup
with breather and vacuum bag, (e) nal setup in oven, (f) separated
layers including reinforced NBR, (g) reinforced NBR.

Phenolic resina (content, %)

Benzoxazine resina (content, %)

40

40

Carbon fabric
(area, mm)
200  200
200  200
200  200

MEK (mL)

100

Resin content is determined as per ASTM D 3171-09.

12528 | RSC Adv., 2014, 4, 1252612533

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Fig. 4 Flow chart of the co-curing process.

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3.

Results and discussion

In this study, low molecular weight phenolic and benzoxazine

resins were incorporated in the NBR compound. Reinforcement
of the NBR matrix with these resins occurs during the co-curing
process. The porous Teon-coated release fabric placed between
the resin prepregs and the NBR compound sheet not only allows
the resins to ow from the prepregs to the NBR during heating,
but also separates the reinforced NBR compound from the
prepregs once the co-curing process is completed. The reinforced
NBRPh and NBRBz materials were inspected with reference to
NBRS in terms of their mechanical, thermal, swelling and aging
properties. The physico-mechanical and swelling properties of
NBRS, NBRPh and NBRBz are depicted in Table 3.

curing. This further supports the formation of a localised

interpenetrating network structure between the NBR matrix and
the phenolic25 or benzoxazine resins. The presence of sharper
and higher absorption peaks (increased concentration of peaks)
in NBRPh and NBRBz than NBRS in the region between 1800
and 800 cm1, and also the absence of negative peaks, shows
the enhancement of the resinmatrix interactions. The absence
of negative peaks further indicates that the reinforcement did
not cause any chain scission in both the matrix and the resin.
The schematic representation of NBR (without an interpenetrating network, IPN) and the interpenetrating network of
NBR with benzoxazine (NBRBz) and phenolic resin (NBRPh)
are shown in Scheme 13 respectively.

3.2. Mechanical properties

The phenolic and benzoxazine resins were transferred and
absorbed with NBR, resulting in cross linking in the presence of

3.1. FT-IR
ATR-FTIR analysis was carried out before studying the bulk
properties of the reinforced composites in order to verify the
presence of interactions between the rubber matrix and the
reinforced resins. The infrared spectra of NBRS and the reinforced NBR composites are shown in Fig. 5. The characteristic
infrared absorption peaks of NBRS are found at 967 cm1 and
2230 cm1 due to the trans double bond of butadiene and the
nitrile group of NBR respectively. The absence of any change to
these absorption peaks in NBRPh and NBRBz compared to
NBRS indicates the absence of the in situ polymerisation
reaction between the NBR matrix and reinforced resins during

Table 3

Infrared spectra of NBRS and the reinforced NBR samples

(NBRPh & NBRBz).

Fig. 5

Physico-mechanical and swelling properties of NBRS, NBRPh and NBRBz

Property

NBRS

NBRBZ

NBRPh

Tensile strength (MPa)

Modulus at 100% elongation (MPa)
Modulus at 200% elongation (MPa)
Modulus at 300% elongation (MPa)
Elongation at break (%)
Tear strength (kg cm1)
Hardness (Shore A)
Tensile set (%)
Cross linking density (mmol cm3) (benzene)

9.68
2.3
4.46
8.08
403.47
44.51
74.5
10.8
0.40

21.14
2.58
4.65
8.41
573.63
46.15
74.5
13.2
0.50

17.72
2.25
3.28
5.31
668.38
56.84
72
16.6
0.41

Volume swelling in % aer 72 h

a. Toluene
b. MEK
c. Ethanol
d. ATF
Density, g cm3

1.45
2.22
0.043
1.82
1.197

This journal is The Royal Society of Chemistry 2014

1.16
2.07
0.029
1.61
1.191

1.13
1.86
0.023
1.60
1.191

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Scheme 3

Scheme 1

NBRS.

NBRPh.

properties of NBRS, NBRPh and NBRBz are shown in Fig. 6,

and the stressstrain curves are shown in Fig. 7. Fig. 6a displays
the tensile strength, elongation at break and tear strength of
NBRPh and NBRBz when compared with NBRS, and Fig. 6b
compares the modulus and hardness. Due to reinforcement
with phenolic resin, the tensile strength, elongation at break,
tear strength and tensile set of NBRPh increased by about 91,
83, 64 and 77% respectively in comparison with NBRS, whereas
the modulus (100%) remains almost the same. Similarly, the
reinforcement with benzoxazine resin increases the tensile
strength, elongation at break, tear strength, tensile set and
modulus (100%) of NBRBz to about 109, 71, 52, 63 and 56%
respectively in comparison with NBRS. The Shore A hardness
of NBRPh decreased slightly, but no change was observed for
NBRBz when compared to NBRS.
It was observed that the resin-reinforced composites showed
a remarkable enhancement in the ultimate tensile strength.
Resins being polar and chemically reactive causes good wetting
with improved rubberresin interactions. The rise in tensile
strength might also be related to the ability of these resins to
contribute to the stress transfer process of the reinforcement
phase due to sucient interaction with NBR, and also because
of the improved compatibility. Hence, the applied load during
the tensile testing of NBR was therefore partially shared by the
resin matrix, which shows better strength properties.28
3.3. SEM analysis

Scheme 2

NBRBZ.

heating during the curing process. Aer reinforcement,

enhancement of the tensile strength, tear strength, tensile set
and elongation at break were observed. The mechanical

12530 | RSC Adv., 2014, 4, 1252612533

The exceptional reinforcement behaviour of the phenolic and

benzoxazine resins on NBR was further studied by microstructure analysis. Fig. 8a shows a SEM image of the tensile fractured
surface of NBRS which shows that the vulcanised NBR without
resin modication displayed a smooth fracture surface without
pores. Well dispersed ne silica particles could be easily

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Fig. 8 SEM images of (a) NBRS, (b) NBRBz and (c) NBRPh.

(a) Tensile, elongation and tear of NBRS, NBRPh and NBR

Bz; (b) 100%, 200%, 300% modulus and hardness of NBRS, NBRPh
and NBRBz.

Fig. 6

mechanical properties of NBR were signicantly enhanced, as

shown in Table 3. The brittleness of the NBR composites and
failures in separate planes are clearly visible (Fig. 8). This
justies the formation of a separate resin phase which is closely
adhered to the rubber matrix and takes part in sharing the
applied stress.15
3.4. Thermogravimetry
The results of thermogravimetric analysis of the NBRS and
NBR composites are shown in Fig. 9. The nature of the curve is
similar for all of the components. The major weight loss
observed at the temperature range of 370 to 510
C is due to the
degradation of the NBR component. The next weight loss at the
temperature range of 520 to 585
C is due to the decomposition
of carbonaceous residue.29 The onset temperature of major
degradation starts at a higher temperature for NBRPh and
NBRBz in comparison to NBRS. The values of onset temperature and thermal stability (Tmax) obtained from the DTG curves
are shown in Table 4. It was observed that the Tmax of NBRPh
and NBRBz in the major degradation step occurs at an elevated
temperature when compared with NBRS, which indicates the
greater thermal stability of NBR composites over that of NBRS.
The value of Tmax is slightly higher for NBRBz than NBRPh.

Fig. 7 Stressstrain curves of NBRS, NBRPh and NBRBz.

3.5. Aging resistance

identied in the NBR matrix, with many bright spots indicating
the presence of rubber chemicals such as zinc oxide, stearic acid
etc. Fig. 8b and c represent SEM images of NBRPh and NBRBz
respectively. The phenolic25 and benzoxazine resins formed a
localised interpenetrating network structure within the NBR.
Also, these resins have higher strength than that of rubber,
therefore the long discontinuous bres formed within the
rubber matrix could behave as strengthening materials, and the

This journal is The Royal Society of Chemistry 2014

The thermal aging resistance of NBR is limited because of the

presence of an unsaturated backbone. The eect of thermal
aging was investigated at 100
C for 72 h for NBRS and the NBR
composites. The thermal aging of NBR will be faster at the
beginning of the aging due to the higher level of oxygen uptake
for oxidation followed by cross-linking.3032 The oxidation
results in partial degradation of the polymer chain, which leads
to a reduction of the tensile strength. Fig. 10 compares the

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Percentage of retention of the mechanical properties after
aging at 100
C for 72 h

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Table 5

Property

NBRS (%)

NBRBz (%)

NBRPh (%)

Tensile strength
Elongation at break
Modulus at 100%

74.38
77.28
84.34

88.12
80.56
86.43

85.55
83.28
94.54

Fig. 11 Swelling ratios of NBRS, NBRBz and NBRPh in solvents

and ATF.
Fig. 9

DTG curves of NBRS, NBRPh and NBRBz.

Table 4 Thermogravimetric analysis of the rubber composites

Sample

Onset temperature (
C)

Tmax (
C)

NBRS
NBRPh
NBRBz

379
390
424

439
466
469

NBRPh and NBRBz are superior when compared to NBRS.

The more than 85% retained tensile strength of NBRPh and
NBRBz shows that the detrimental inuence of heat was more
than equalized by the protective inuence of the benzoxazine
and phenolic resins. The cured resin layers may have acted as
barriers for the diusion of degradation products into the
interior of the rubber matrix. However, the loss in the elongation at break aer aging may be due to the increase in crosslinking density, which leads to restriction for chain extension
and decreases the chain length between cross-linking points.32
3.6. Swelling properties

Fig. 10 Comparison of the mechanical properties of unaged and aged

samples of NBRS, NBRPh and NBRBz (UA: unaged, A: aged).

percentage retention of the tensile strength, elongation at break

and modulus of the NBRPh and NBRBz materials with NBRS
which were aged at 100
C for 72 h, and the retention values are
given in Table 5. From the gure it is clearly evident that the
retained tensile strength, elongation at break and modulus of

12532 | RSC Adv., 2014, 4, 1252612533

The reinforcement eect of the phenolic and benzoxazine

resins with the NBR matrix on the cross-link density is estimated from the swelling experiment data given in Table 3. The
swelling ratios of the NBRS and NBR composites in solvents
such as MEK, toluene, ethanol and turbine fuel (ATF) are shown
in Fig. 11. Due to the higher degree of cross linking, a decrease
in the swelling values of the reinforced samples NBRPh and
NBRBz was observed when compared with NBRS. The
percentage of solvent uptake was considerably decreased for
NBRPh and NBRBz. The reinforcement of these phenolic and
benzoxazine resins in the NBR matrix restricts the extensibility
of the rubber chains induced by swelling, which makes it
dicult for these solvents and ATF to penetrate into the gaps
between rubber molecules, and thus the swelling percentage
was decreased.33,34 Hence, the reinforced compounds NBRPh
and NBRBz possessed higher barrier properties compared to
NBRS. The volume swelling percentages for the phenolic and
benzoxazine resins were more or less the same.

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4. Conclusions
NBR was reinforced with phenolic and benzoxazine resins to
form NBRPh and NBRBz composites by a co-curing process. It
was found that both these resins existed in the form of a
localized interpenetrating network structure in the NBR matrix.
For the NBRPh composite, the tensile strength, tear strength,
tensile set and elongation at break were improved, whereas the
modulus remained almost the same when compared with NBR
S. Similar results were observed for NBRBz, except for a slight
improvement in the modulus. In particular the tensile strength
of NBRPh and NBRBz has increased nearly twofold when
compared to NBRS. The Shore A hardness of NBRPh is slightly
aected, but no change was observed for NBRBz. The occurrence of Tmax of NBRPh and NBRBz in the major degradation
step at elevated temperature indicates their greater thermal
stability over NBRS. The aging studies at 100
C for 72 h
showed that the retained tensile strength, elongation at break
and modulus of NBRPh and NBRBz are superior to NBRS.
Further, due to the higher degree of cross linking, a decrease in
the swelling values is observed in the reinforced samples NBR
Ph and NBRBz when compared with NBRS. The investigation
has clearly demonstrated for the rst time that benzoxazine
resin, similar to phenolic resin, could be an eective additive
for strengthening various rubber materials. The study has also
demonstrated a practical co-curing process to reinforce thermosetting resins with NBR which can be possibly extended to
other resins and rubber matrices.

Acknowledgements
The authors wish to thank Director, DRDL and Director, ASL for
supporting this study.

Notes and references

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