Materials and Design 32 (2011) 33613369

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Effect of different curing systems on the mechanical and physico-chemical

properties of acrylonitrile butadiene rubber vulcanizates
Khaled F. El-Nemr
Radiation Chemistry Dept., National Center for Radiation Research and Technology, AEA, P.O. Box 29, Nasr City, Cairo, Egypt

a r t i c l e

i n f o

Article history:
Received 6 October 2010
Accepted 4 February 2011
Available online 26 February 2011
Keywords:
Acrylonitrile butadiene rubber
Curing system
Mechanical properties

a b s t r a c t
In the present study, the effect of different curing systems including sulfur, dicumyl peroxide, dicumyl
peroxide/coagent and radiation/coagent on the mechanical and physico-chemical properties of acrylonitrile butadiene rubber (NBR) was studied. In order to correlate, the effect of curing systems on rubber, the
comparison was carried out at comparable value of volume fraction of rubber in swollen gel (Vr) for NBR
vulcanizates. Mechanical properties like tensile strength, elongation at break, modulus, Youngs modulus,
tearing strength and abrasion loss of vulcanizates have been followed up for comparison. In addition,
physico-chemical properties like swelling ratio, soluble fraction, and cross-link density were investigated.
On the other hand, the effects of fuel, thermogravimetric analysis, and thermal ageing have been studied.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Acrylonitrile butadiene rubber (NBR) has excellent oil resistance. However, shows no self-reinforcing effect, as there is no
crystallinity, but when used in combination with reinforcing llers,
vulcanizates with excellent mechanical properties can be obtained
from NBR [1]. Vulcanization occurs by a chemical agent, such as
sulfur or peroxide. Alternatively, high-energy radiation, such as
electron beam or gamma radiation can be used to vulcanize rubbers [2].
The use of organic peroxide as a cross-linking agent through a
free radical process is also largely developed. The vulcanization
rate is controlled essentially by the decomposition of the peroxide
at a given temperature [3]. Compared with sulfur vulcanization,
crosslinking by peroxides is a relatively simple process, with physical properties such as high modulus, low compression set and heat
ageing properties superior to sulfur cure systems. On the other
hand, the peroxide crosslinking has many disadvantages, such as
low tensile and tear strength, and ex resistance, which have restricted their use in diene rubbers. Many unsaturated rubbers, such
as natural rubber (NR), styrenebutadiene rubber (SBR), butadiene
rubber (BR), and acrylonitrile butadiene rubber (NBR), contain a
varying degree of unsaturation in the polymer backbone or in pendant positions. Peroxide radical could potentially react by addition
to a double bond or by abstraction of an allylic hydrogen, and both
mechanisms occur concurrently in the vulcanization of unsaturated elastomers [4].
National Center for Radiation Research and Technology (NCRRT), 3 Ahmed
El-Zomor St., P.O. Box 29, Nasr City, Cairo, Egypt. Tel.: +20 124114780; fax: +20
222749298.
E-mail address: khaledfarouk65@eaea.org.eg
0261-3069/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2011.02.010

The use of coagents in conjunction with peroxides to cure elastomers has been common practice in the rubber industry for many
years. Coagents are typically multifunctional vinyl monomers that
are highly reactive toward free radicals and readily graft to elastomer chains to form a complex crosslinked network. These coagents
with peroxide are used to improve the physical properties and processability of peroxide-cured elastomers. Also, they increase not
only the crosslinking efciency of the vulcanization process but
the cross-link density as well [5].
During this last decade, the crosslinking of rubbers by means of
electron beams has strongly developed in place of the use of crosslinking agents, such as sulfur or peroxides. NBR belongs to the
crosslinking type rubbers when exposed to high-energy radiation
[6]. Compared with the conventional chemical processes such as
peroxide [7] or sulfur [8] induced vulcanization used for crosslinking rubber, radiation crosslinking has the advantages of being faster and being more versatile, leads to more uniform crosslinking,
consumes less energy, and occupies less oor space for processing.
Inherently waste free nature of the technology makes it less
polluting than the conventional technologies. The disadvantage is
that the physical properties of radiation vulcanized rubber were
adversely affected by the high crosslinking dose required. To overcome this problem, several authors [9] have reported that polyfunctional monomers PFMs (coagents) such as multifunctional
acrylates and methacrylates are useful to obtain optimum mechanical properties at lower dose levels. These PFMs form a network
structure with polymeric materials at a lower dose because of its
higher reactivity [10] and the resulting structure is useful for the
improvement of mechanical properties as well as thermal stability
[11] .
This article is a comparative study between the different techniques to vulcanize NBR rubber.

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K.F. El-Nemr / Materials and Design 32 (2011) 33613369

2. Experimental
2.1. Materials
Acrylonitrile butadiene rubber (NBR) of Europrene N3345 from
Enichem company Inc, Italy having (acrylonitrile content-34%,
Mooney viscosity (ML (1 + 4) at 100 C-46). Zinc oxide was supplied from Shijiazhuang Golden Color Chemical Co., Ltd., China,
its concentration 99.7% in appearance of white powder. Stearic acid
obtained from Hebei Liancheng Chemical Co., Ltd., China, it has
small akes shape and melting point 56 C. Dioctyl phthalate
(DOP) was supplied by Henan Tianfu Chemical Co., Ltd., China; it
has acidity 0.01 maximum and ester value 99.5%. Sulfur was supplied by standard chemical company private Ltd., Madras.
Mercapto benzothiazyl disulphide (MBTS) was obtained from
Bayer India Ltd., Bombay. Tetra methyl thiuram disulphide (TMTD)
was supplied by NOCIL, Bombay, India. 1,2-dihydro.2,2,4-trimethyl
quinoline (TMQ) as antioxidant was obtained from Intatrade
Chemicales (GmbH), Germany.Carbon black (N 375). The peroxide
cross-linking agent was dicumyl peroxide [DCP] from Aldrich
(Germany), its purity 99%. The polyfunctional monomer PFM
(coagent) was penta erythritol triacrylate PETRA from Aldrich with
a molecular weight of 298.29 g/mol and a density of 1.167 g/cm3.
2.2. Compounding and curing
The compounding recipes of mixes are given in Table 1, the
codes letters S, P, P-PFM and R-PFM represent the sulfur, dicumyl
peroxide, dicumyl peroxide coupled with coagent and radiation
vulcanized system respectively. The subscript indicates the weight
in phr (part per hundred part of rubber) for sulfur, and dicumyl
peroxide corresponding to each designation code; while subscript
in case of radiation vulcanization indicate the radiation dose.
Mixing was carried out at room temperature using a two-roll
mixing rubber mill having a friction ratio 1:1.4. The compounded
mixes as follow
2.2.1. Sulfur and peroxide curing
The compounded mixes with different amounts of curing system were compression molded using an electrically heated
hydraulic press at 160 C under pressure 120 kg/cm2 for their optimum curing times i.e. 5 min. for sulfur cured system and 20 min
for peroxide and peroxide coupled with coagent cured systems.
2.2.2. Radiation curing
The compounded mixes were compression molded between
aluminum foil at 160 C under pressure 120 kg/cm2. Irradiation
was carried out in air at ambient temperature on the electron beam

accelerator (1.5 MeV, 3 mA) facility installed at the National Center

for Radiation Research and Technology, Cairo, Egypt. The irradiation was performed to give a total dose of 25 kilo gray (kGy) for
each pass. Multiple passes obtained the total irradiation doses
25, 50, 75, 100 and 150 kGy for different measurements.
2.3. Measurements
2.3.1. Mechanical properties
The tensile strength was measured using dumbbell shaped test
pieces at a crosshead speed of 500 mm/min at 25 2 C using tensile testing machine HOUNS FILD, England. The tearing strength
(load at failure/thickness) of the samples was determined using
unnicked 90 C angle test pieces according to ASTM D 624-81.
The experimental conditions for the tear measurements were the
same as that of the tensile testing. The hardness of the samples
was measured according to ASTM D 2240-2000 using durometer
type A, and the units of hardness was expressed in shore A.
2.3.2. Physico-chemical measurements
2.3.2.1. Soluble fraction. Measurements of soluble fraction were carried out as follow, the cured samples, about 0.2 g were accurately
weighed (Wo) and placed in a special stainless grids. The grids containing samples are transferred to special round ask 2/3 lled
with acetone. The heating was carried out under reux for 24 h.
After extraction, the samples were dried to constant weight (W1)
in dry oven at 50 C. The soluble fraction was calculated as follow:

Soluble fraction W o  W 1 =W o

2.3.2.2. Determination of cross-link density (m). The volume fraction

of rubber in swollen network of the vulcanizates Vr, was determined by means of equilibrium swelling in acetone laboratory
grade at 25 C. The equilibrium swelling was used to calculate
the cross-link density, which is the number of network chain density by applying the FloryRehner equation [12] as follow:

m 1=V s

"
#
ln1  V r V r v1 V 2r

V 1=3
 V r =2
r

where, m = cross-link density; v1 = polymersolvent interaction

parameter; Vs = molar volume of solvent; Vr = volume fraction of
rubber in the swollen gel; Vr was calculated using the relation

Vr

Ds  F f Aw qr 1
Ds  F f Aw qr 1 As qs1

where Vr, Ds, Ff, Aw, As, qr and qs are volume fraction of rubber,
deswollen weight of the sample, fraction of insoluble, sample

Table 1
Formulation of the mixes.

Code formulation (phr)*

S1

S1.5

S2

P1

P1.5

P2

P1-PFM

P1.5-PFM

P2-PFM

R25-PFM

R50-PFM

R75-PFM

R100-PFM

R150-PFM

NBR
ZnO
Stearic acid
TMQ
DOP
MBTS
TMTD
Sulfur
HAF
Peroxide (DCP)
PETRA
Irradiation dose (kGy)

100
5
2
1
6
1
0.5
1
30

100
5
2
1
6
1
0.5
1.5
30

100
5
2
1
6
1
0.5
2
30

100
5
2
1
6

30
1

100
5
2
1
6

30
1.5

100
5
2
1
6

30
2

100
5
2
1
6

30
1
5

100
5
2
1
6

30
1.5
5

100
5
2
1
6

30
2
5

100
5
2
1
6

30

5
25

100
5
2
1
6

30

5
50

100
5
2
1
6

30

5
75

100
5
2
1
6

30

100
5
2
1
6

30

5
100

5
150

phr = part per hundred part of rubber.

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K.F. El-Nemr / Materials and Design 32 (2011) 33613369

weight, weight of the absorbed solvent corrected for swelling increment, density of rubber and density of solvent respectively.

3. Results and discussion

3.1. Sulfur vulcanized NBR

2.3.2.3. Number average molecular weight between crosslinks

(MC). The number average molecular weight between crosslinks
(MC) was determined according to FloryRehner equation
as follow

m 1=2MC g1 mol

2.3.2.4. Swelling ratio (Q). The swelling ratio (Q) was calculated and
expressed in terms of the reciprocal of volume fraction of rubber in
swollen gel as follow [13,14]:

Q V 1 =V o 1=V r

where V1 is the volume of swollen rubber, Vo the volume of unswollen rubber, and Vr is the volume fraction of rubber in the swollen
gel.
2.4. Thermogravimetric analysis (TGA)
The thermogravimetric analysis (TGA) technique was applied
using TG-50 instrument from Shmadzu (Japan). The heating was
carried out at temperature to 600 C with a heating rate of 10 C/
min under nitrogen gas atmosphere.
2.5. Effect of fuel
Effect of fuel has been carried out specically for testing the effect of fuels on polymeric materials. The samples in triplicates
were weighed to nearest mg (M1). They were then transferred to
ask 2/3 lled with fuel A (commercial gasoline). Heating has been
carried out at 100 C for 22 h. After that, the ask is allowed to cool
at room temperature. The samples were then blotted lightly with
lter paper to remove the remaining liquid fuel. They were then reweighed again (M2) .The percentage change in weight was then
calculated using the following equation:

Change in weight; %

M2  M1
 100
M1

The physical properties of NBR composites vulcanized by

various ratios of sulfur, keeping accelerator level xed, are given
in Table 2. The results obtained for the modulus at 100% elongation
or tensile modulus (M100), Youngs modulus (Eo) and hardness
show an increasing trend with increase of sulfur to accelerator
ratio, while elongation at break (Eb) as well as tensile strength
(TS) decrease. With increasing sulfur level the number of CASxAC
bonds increases, and is reected in the values of Vr. Moreover,
the results of Q, Mc, and cross-link density conrmed the formation
of crosslink network structure. However, increasing crosslinks over
an optimum level cause localized stresses, which results in lower
values of TS which we can explained as follow. Tensile strength,
unlike the tensile stress at a given elongation and hardness, does
not rise continuously with the number of crosslinks. Instead it rises
with the number of crosslinks until an optimum is reached, after
which if crosslinking is continued (in which case over-crosslinking
takes place), it initially falls steeply.
3.2. Peroxide vulcanized NBR
The physical properties of NBR composites cured by different
concentrations of DCP, namely, 0.5, 1 and 1.5 phr, are given in Table 3. The data have shown that the TS pass through a maximum
and then decrease with the increase of DCP content. While, Eb
diminishes with DCP concentration. Shore A hardness and M100
values increase with the increase of DCP indicating the increase
in cross-link density of the vulcanizates. It is thought that the increase of DCP level leads to an increase in the number of CAC
bonds [15], and this is reected in the values of Vr, Mc and crosslink density. Decreasing the values of TS by increasing cross-link
density, can be explained by the fact that on using DCP the peroxide radicals can act through abstraction and addition mechanisms.
The over-crosslinked domains (or clusters) may experience the
highest forces where the network strand will reach a critical force
and break [16].

6
3.3. Peroxide/coagent cured NBR

2.6. Abrasion measurement

Abrasion loss measurement was performed on samples by using
an abrasion tester of the type AP.40 (MASCHINEBAU GmbH
RAUENSTEIN THURINGEN, Germany).
The testes were carried out under the following conditions:
Load = 1 kg.
Abrasion path = 40 meter which equivalent to 84 revolutions.
The loss in the mass was calculated according to following
equation:

Wi  Wf
Mass loss mg per revolution
 1000
n

where Wi is the original mass of sample (gm), Wf the nal mass of

sample (gm), and n is the number of revolutions (84).
2.7. Thermal ageing measurements
The ageing of samples was carried out by keeping the samples
in a hot air oven for 24 h at 100 C. Then the samples were conditioned at ambient temperature for at least 16 h before mechanical
testing was carried out on tensile testing machine HOUNS FILD,
England.

NBR composites with different contents of DCP at a xed concentration of PETRA, namely, 5 phr was shown in Table 4. The obtained results showed that as DCP increases the M100, hardness and
cross-link density signically increase. On the other hand, coagents
are typically multifunctional vinyl monomers that are highly

Table 2
The physical properties of NBR vulcanized by sulfur.
Formulation

Mechanical properties
Modulus at 100% elongation (M100), MPa
Tensile strength (TS), MPa
Elongation at break (Eb), %
Youngs modulus (Eo)
Hardness, shore A
Physico-chemical properties
Soluble fraction (SF)
Volume fraction of rubber in swollen gel (Vr)
Swelling ratio (Q)
Molecular weight between crosslinks (Mc),
g/mol
Cross-link density  104 (m = 1/2MC), mol/cm3

S1

S1.5

S2

2.12
17.44
1070
0.92
58

2.30
16.00
739
1.24
60

2.42
15.85
659
1.37
60

0.093
0.24
4.17
1154.5

0.081
0.28
3.56
794.33

0.07
0.31
3.24
636.04

4.37

6.3

7.86

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K.F. El-Nemr / Materials and Design 32 (2011) 33613369

Table 3
The physical properties of NBR vulcanized by dicumyl peroxide.
Formulation

Mechanical properties
Modulus at 100% (M100), MPa
Tensile strength (TS), MPa
Elongation at break (Eb), %
Youngs modulus (Eo)
Hardness, shore A
Physico-chemical properties
Soluble fraction (SF)
Volume fraction of rubber in swollen gel (Vr)
Swelling ratio (Q)
Molecular weight between crosslinks (Mc),
g/mol
Cross-link density  104 (m = 1/2MC), mol/cm3

P1

P1.5

P2

2.18
13.41
541
1.23
60

2.53
16.09
481
1.56
63

3.22
13.57
331
2.29
65

0.089
0.27
3.73
885.01

0.079
0.31
3.26
646.82

0.072
0.34
2.94
500.07

5.62

7.73

9.98

Table 4
The physical properties of NBR cured by dicumyl peroxide/coagent.
Formulation

Mechanical properties
Modulus at 100% elongation (M100), MPa
Tensile strength (TS), MPa
Elongation at break (Eb), %
Youngs modulus (Eo)
Hardness, shore A
Physico-chemical properties
Soluble fraction (SF)
Volume fraction of rubber in swollen gel
(Vr)
Swelling ratio (Q)
Molecular weight between crosslinks
(Mc), g/mol
Cross-link density  104 (m = 1/2MC),
mol/cm3

P1  PFM

P1.5  PFM

P2  PFM

4.15
11.89
200
3.3
70

4.82
12.73
190
3.76
72

5.90
8.84
133
4.88
75

0.066
0.365

0.064
0.39

0.06
0.42

2.75
420.55

2.56
354.17

2.38
289.84

11.89

14.22

17.25

reactive toward free radicals and graft to elastomer chains to form

complex crosslinked network [17,18]. Because of all common coagents contain terminal unsaturations, it can be concluded that
addition reaction is the principal mechanism by which they react
in the compound; this has been conrmed by observed loss of coagent unsaturation during peroxide curing [19]. The formation of
complex crosslink network has a major impact on decreasing values of TS observed at maximum concentration of DCP. The data obtained for Vr, Q and Mc indicated the increase of cross-link density
by values much more when compared by other cured systems like

sulfur and peroxide. The mechanism consists of reactions in the

elastomer matrix, in the coagent domains, and between the elastmer and the coagent.
The polymerized coagent radicals are incorporated into the network structure by a reaction with the elastomer molecules [20].
3.4. Radiation/coagent cured NBR
An electron beam accelerator was used to generate free radicals
on the carbon atoms of the NBR and coagent. The radicals may
either be reacting with each other or grafting on the coagent forming crosslinks. Table 5 shows the results for radiation curing of
NBR by different radiation doses up to 150 kGy in the presence
of 5 phr of PETRA. The M100 was found to increase linearly with
radiation dose indicating the linear relationship of cross-link density with radiation dose, whereas the latter inversely lowers the
values of Mc. The increase in values of Vr, decrease in Eb, Q and
in solubility were considerable by increasing radiation dose indicating the increase of cross-link density of vulcanizate. Also there
is an increase in TS up to 100 kGy, beyond which there is a very
slight decrease in TS values dose. The leveling off or decrease in
TS by radiation may be explained as follows: TS of a polymer is
a function of cross-link density and energy dissipation, at higher
crosslinking density, i.e. at 150 kGy, the segments of the macromolecule become immobile, the system becomes stiffer and the
elasticity decreases [21]. Also, it can be assumed that the rate of
two processes, namely crosslinking and degradation may then occur with the same rate, hindered mobility of macromolecules due
to increased rate of crosslinking may contribute also to decreasing
the values of TS.
3.5. Physical properties comparison of NBR cured by sulfur, peroxide
and radiation/coagent (100 kGy) at a comparable value of Vr
3.5.1. Mechanical properties
The Vr can be taken as an indicator of cross-link density and
reinforcing ability of ller [22,23]. The data listed in the pervious
Tables 14, show that the values of Vr  0.31, are comparable for
NBR cured by 2 phr sulfur, 1.5 phr DCP and radiation/coagent at
(100 kGy). For comparison Table 6 represents the respective physical data. Obviously the crosslink structure and cross-link density
affect the mechanical properties of NBR vulcanizates depending
on the type of curing system. The tear strength, TS and Eb values
are comparatively the highest in the case of sulfur cured system.
The Eb data can be explained on the basis that the system can
accommodate more stress and elongation via the exible and labile
S-S linkage [24]. The lower tear strength and Eb values of DCP cured
system are attributed to the short and rigid CAC crosslinks

Table 5
The physical properties of NBR cured by radiation/coagent.
Formulation
R25  PFM

R50  PFM

R75  PFM

R100  PFM

R150  PFM

Mechanical properties
Modulus at 100% elongation (M100), MPa
Tensile strength (TS), MPa
Elongation at break (Eb), %
Youngs modulus (Eo)
Hardness, shore A

2.18
11.2
1041
0.55
52

2.68
11.6
633
1.06
55

3.5
13.4
540
1.48
60

4.0
14
359
2.37
65

5.2
13.6
252
3.49
70

Physico-chemical properties
Soluble fraction (SF)
Volume fraction of rubber in swollen gel (Vr)
Swelling ratio (Q)
Molecular weight between crosslinks (Mc), g/mol
Cross-link density  104 (m = 1/2MC), mol/cm3

0.174
0.183
5.47
2073
2.41

0.14
0.235
4.251
1196.5
4.18

0.11
0.285
3.513
776.2
6.48

0.08
0.313
3.13
584
8.48

0.06
0.37
2.7
402.7
12.4

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K.F. El-Nemr / Materials and Design 32 (2011) 33613369

Table 6
The physical properties of NBR cured by sulfur, peroxide and radiation/coagent.
Formulation

Mechanical properties
Modulus at 300% elongation (M300), MPa
Modulus at 100% elongation (M100), MPa
Tensile strength (TS), MPa
Elongation at break (Eb), %
Youngs modulus (Eo)
Hardness, shore A
Tearing strength, N/mm
Physico-chemical properties
Soluble fraction (SF)
Volume fraction of rubber in swollen gel (Vr)
Swelling ratio (Q)
Molecular weight between crosslinks (Mc),
g/mol
Cross-link density  104 (m = 1/2MC),
mol/cm3

S2

P1.5

R100-PFM

5.81
2.42
15.85
659
1.37
60
43

7.82
2.53
16.09
481
1.56
63
38

10.57
4.00
14
359
2.37
65
27

0.07
0.31
3.24
636.04

0.079
0.31
3.26
646.82

0.08
0.313
3.13
584

7.86

7.73

8.48
Fig. 2. TGA curves of NBR cured by sulfur, peroxide and radiation/coagent.

between macromolecules chains [24]. The hardness results show

slightly higher values in the case of radiation curing system than
the others as a result of the associated higher cross-link density.
Meanwhile, the lowest tensile strength values compared to those
of the peroxide and sulfur cured systems can be related to the loss
and isomerization of less relaxed network. On the other hand, the
highest reported values of M100 and M300 for the radiation/coagent
cured system compared to the other systems can be attributed to
the cross-link density.
3.5.2. Stressstrain behavior
The stressstrain behavior of NBR demonstrates a remarkable
dependence on the applied curing system as shown in Fig. 1. The
initial modulus is almost the same in sulfur and DCP cured systems, however, the DCP system exhibits higher tensile modulus
than sulfur though TS values are comparable. Radiation/coagent
cured system can accommodate less strength at rupture but exhibits higher modulus values at any given elongation as a result of the
established cross-link density.
3.5.3. Thermal analysis
Fig. 2 shows the TGA thermograms of the NBR composites cured
by sulfur, S2, peroxide, P1.5, and radiation/coagent, R100-PFM. The
rst weight loss stage 150350 C is due to the loss of a highly

Fig. 1. Stressstrain curves of NBR cured by sulfur, peroxide and radiation/coagent.

volatile matter, consists of the amount of oil added as a processing

agent and a small amount 12% of decomposed fragments of the
vulcanizing agent (sulfur or peroxide) vulcanization accelerator
and antioxidant [25]. The second fraction 350550 C represented the medium volatile matter, the amount of decomposed
polymer. Evidently, the radiation curing system exhibits higher
thermal stability than the others as conrmed by the data shown
in Table 7.
The differential thermal gravimetric (DTG) curves demonstrate
for the three curative systems, only one peak indicating a single
stage decomposition in the NBR composite, Fig. 3, with a consistent

Table 7
Decomposition temperature of NBR cured by sulfur, peroxide and radiation/coagent
at different weight losses.
Composition

Temperature (C)

Weight loss, %

S2

P1.5

R100-PFM

T10
T30
T50
T60
T65
T70
DTG

415.14
460.00
484.00
497.00
563.00
590.00
484.00

427.00
465.50
486.00
506.00
569.00
590.00
484.00

428.70
461.00
484.00
560.00
580.00
590.00
484.50

Fig. 3. DTG of NBR cured by sulfur, peroxide and radiation/coagent.

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K.F. El-Nemr / Materials and Design 32 (2011) 33613369

(Tmax) located at 484 C. The relatively higher thermal stability

exhibited by the radiation/coagent and peroxide systems is due
to the formation of CAC linkages which are more thermally stable
than CASAC and CASxAC linkages in sulfur vulcanization [26]. Furthermore, the CAC linkage in both cured systems possesses a higher bond energy of 85 k cal mol1 whereas the bond energy of the
SAS crosslink is only 57 k cal mol1 [27].
3.5.4. Effect of fuel
NBR rubber is applied specically as fuel and oil resistant. The
resistance can be followed up by measuring the change of weight%,
by immersing in fuel A (commercial gasoline) and then plotted as a
function of different curing systems, as shown in Fig. 4. It can be
seen that the NBR cured by radiation/coagent gave the best results
for swelling resistance in commercial gasoline compared to the
sulfur and peroxide systems at the same Vr value. The resistance
to swelling can be argued on the basis of the chemical crosslinking
magnitude induced in the rubber component by radiation with respect to the other methods of curing.
3.5.5. Abrasion resistance
Fig. 5 illustrates the dependence of the abrasion loss in the NBR
composite samples on the implemented curing system. Generally,
it can be seen that the abrasion loss decreases by the increase in
cross-link density. These data indicate that the abrasion resistance

slightly enhanced in case of radiation/coagent followed by sulfur

then peroxide cured systems.
3.6. Physical properties comparison of NBR cured by peroxide/coagent
and radiation/coagent (150 kGy) at a comparable value of Vr
3.6.1. Mechanical properties
Depending on the data obtained before, Tables 14, comparison
can be established between NBR cured by DCP/coagent, (P1  PFM)
with that cured by electron beam radiation/coagent, (R150  PFM)
at comparable values of Vr  0.37. The physical properties of the
vulcanizates are illustrated in Table 8. Comparable values for hardness, Eb, tearing strength, soluble fraction SF, Q, Mc and cross-link
density were recorded for these two vulcanizates, whereas the vulcanizate samples cured by radiation/coagent gave higher values of
TS and tensile modulus. The behavior of the latter is due to the increase in cross-link density.
3.6.2. Stressstrain behavior
Fig. 6 shows the stress against strain for NBR cured by DCP/coagent and radiation/coagent systems. It can be observed that the
radiation/coagent cured samples revealed higher TS and tensile
modulus values, the increase in values of TS can be related to the
increase in cross-link density.

Table 8
The physical properties of NBR cured by peroxide/coagent and radiation/coagent.
Formulation
P1-PFM

R150-PFM

Mechanical properties
Modulus at 100% elongation (M100), MPa
Tensile strength (TS), MPa
Elongation at break (Eb), %
Youngs modulus (Eo)
Hardness, shore A
Tearing strength, N/mm

4.15
11.89
200
3.3
70
29.2

5.2
13.6
252
3.49
70
30

Physico-chemical properties
Soluble fraction (SF)
Volume fraction of rubber in swollen gel (Vr)
Swelling ratio (Q)
Molecular weight between crosslinks (Mc), g/mol
Cross-link density  104 (m = 1/2MC), mol/cm3

0.066
0.365
2.75
420.55
11.89

0.06
0.37
2.7
402.7
12.4

Fig. 4. Effect of fuel A on the NBR cured by sulfur, peroxide and radiation/coagent.

Fig. 5. Abrasion loss of NBR cured by sulfur, peroxide and radiation/coagent.

Fig. 6. Effect of peroxide/coagent and radiation/coagent curing systems on stress

strain behavior of NBR vulcanizates.

K.F. El-Nemr / Materials and Design 32 (2011) 33613369

Fig. 7. TGA curves for NBR cured by peroxide/coagent and radiation/coagent.

3367

Fig. 8. DTG curves for NBR cured by peroxide/coagent and radiation/coagent.

Table 9
Decomposition temperature of NBR cured by peroxide/coagent and radiation/coagent.
Composition

Temperature (C)

Weight loss, %

P1-PFM

R150-PFM

T10
T30
T50
T60
T65
T66
DTG

428.00
466.00
488.00
526.00
593.00
600.00
486.80

428.00
463.35
487.00
566.75
593.00
600.00
485.00

3.6.3. Thermal analysis

Fig. 7 and Table 9 shows the TGA thermograms and data,
respectively, of DCP/coagent and radiation/coagent cured NBR vulcanizates. At temperature up to 500 C both vulcanizates demonstrated similar thermal stability. It can be observed that the
decomposition temperatures are nearly comparable for both two
cured systems except at 60% decomposition (T60). The temperature
of degradation obtained for radiation/coagent cured system is
higher than that of the DCP/coagent cured system, 566.75 C and
526 C respectively. Meanwhile, both cured systems exhibited
the same decomposition temperature for 50% loss (T50) which is
fairly close to Tmax of both vulcanizates, 485 C, as shown by
the DTG curves, Fig. 8.
The slight enhancement in thermal stability of radiation/coagent cured vulcanizates may be related to a slight increase in
cross-link density which is a factor affecting the thermal stability
that leads to higher values of activation energy needed for thermal
decomposition of vulcanizates [28,29].
3.6.4. Effect of fuel
The impact of the two different curing systems, peroxide/coagent and radiation/coagent (150 kGy) on the change in weight%
of NBR samples soaked in commercial gasoline is illustrated in
Fig. 9. Evidently, the nal weight of the samples cured by radiation/coagent is slightly lesser than that of the other ones cured
by peroxide/coagent. The results are clearly in good agreement
with the results of cross-link density and Mc, i.e. the greater the
cross-link density, the higher the fuel resistance.
3.6.5. Abrasion resistance
Abrasion resistance of NBR rubber cured by peroxide/coagent
and radiation/coagent (150 kGy) is shown in Fig. 10. It can be

Fig. 9. Effect of fuel A on the NBR cured by peroxide/coagent and radiation/coagent.

Fig. 10. Abrasion loss of NBR cured by peroxide/coagent and radiation/coagent.

noticed that the abrasion resistance of radiation/coagent cured

NBR composites is relatively higher than that of those cured by
peroxide/coagent system and this behavior may be attributed to
the increase in crosslinks induced by radiation.

3368

K.F. El-Nemr / Materials and Design 32 (2011) 33613369

3.7. Effect of thermal ageing

The effect of thermal ageing on the mechanical properties,
namely TS, Eb and hardness of NBR vulcanizates cured by sulfur,
peroxide, peroxide/coagent and radiation/coagent is shown in Figs.
1113, respectively. The values of TS for sulfur and radiation/coagent (150 kGy) cured systems at 150 kGy were found slightly reduced on ageing while the other cured systems were not
affected. On the other hand, only the values of Eb for sulfur cured
system decreased on ageing. Meanwhile, the hardness values for
all NBR vulcanizates encountered a slight alteration on ageing.
The decrease in values of TS and Eb in case of sulfur vulcanized
samples may be attributed to the fact that the polysuldic crosslinks cleave and rearrange into shorter crosslinks [30]. Also, the decrease in values of TS of NBR vulcanizates cured by radiation/
coagent may be attributed to chain scission by thermal ageing.
Moreover, compared to sulfur vulcanized samples, radiation/coagent vulcanized samples are more resistant to heating due to the
nature of networks, as CAC linkage is more stable possessing higher bond energy than CASAC linkage. It is also well known that
polysuldic linkage is of relatively low bond strength, i.e. poorer
thermal ageing resistant.

Fig. 11. Effect of thermal ageing on tensile strength of NBR cured by sulfur,
peroxide, peroxide/coagent and radiation/coagent.

Fig. 13. Effect of thermal ageing on hardness of NBR cured by sulfur, peroxide,
peroxide/coagent and radiation/coagent.

4. Conclusions
The cross-link density of NBR composites increases with
increasing the content of sulfur, peroxide, or radiation dose. The
cross-link density greatly affects the mechanical properties of vulcanizates, tensile strength go through maximum for every cured
system by increasing the vulcanizing agent concentration, thereafter decrease by the over cure. Hardness, Youngs modulus, and
modulus at given elongation increased by increasing the cross-link
density, while elongation decreased. The physico-chemical properties; like swelling ratio, soluble fraction and Mc have been decreased by increasing the cross-link density. The cured systems
of sulfur, 2 phr, peroxide, 1.5 phr and radiation/coagent (100 kGy)
for NBR elastomer gave comparable values of Vr, 0.31. The sulfur
and peroxide cured systems when compared by the radiation/coagent system gave slightly higher in values of tensile strength,
though of lesser cross-link density and thermal stability. On the
other hand, higher values of swelling in fuel and abrasion loss were
reported. The radiation/coagent (100 kGy) cured system gave higher results in thermal stability, thermal ageing, youngs modulus,
modulus at given elongation, abrasion resistance and fuel resistance than those of the sulfur cured system. The cured systems
peroxide/coagent and radiation/coagent (150 kGy) gave comparable values of Vr, 0.37, and similar values for the physcio-chemical
and mechanical properties, except tensile strength reported
slightly higher values as a result of irradiation.
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Fig. 12. Effect of thermal ageing on elongation at break for NBR cured by sulfur,
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