Comparison of Physicomechanical

Properties of NBR–PVC Blend Cured

by Sulfur and Electron Beam
M. HAFEZI,1 S. NOURI KHORASANI,2,* F. ZIAEI3 AND H. R. AZIM3
1
Isfahan University of Technology
Isfahan, Iran
2
Polymer Group, Department of Chemical Engineering
Isfahan University of Technology
Isfahan, Iran
3
Yazd Radiation Processing Center
P.O. Box 89175-389, Yazd, Iran

ABSTRACT: In this research, physicomechanical properties including tensile

strength, elongation at break, hardness, resilience, and aging of acrylonitrile
butadiene rubber–poly vinyl chloride (NBR–PVC) blend cured by sulfur and
electron beam are investigated. The Taguchi method is employed in order to
formulate the sulfur curing system. Electron beams in dose rates from 0 to
150 kGy are applied to cure NBR–PVC blends without sulfur curing system.
Results show that the physicomechanical properties, except resilience, of NBR–
PVC blend cured by the electron beam improved by 15% compared with blends
cured by the sulfur system.

KEY WORDS: electron beam, sulfur, NBR–PVC blend, curing system,

physicomechanical properties.

*Author to whom correspondence should be addressed. E-mail: saied@cc.iut.ac.ir

JOURNAL OF ELASTOMERS AND PLASTICS Vol. 39–April 2007 151

0095-2443/07/02 0151–13 $10.00/0 DOI: 10.1177/0095244306067696
ß 2007 SAGE Publications
152 M. HAFEZI ET AL.

INTRODUCTION

butadiene rubber (NBR) and poly vinyl

B LENDS OF ACRYLONITRILE
chloride (PVC), with a density of 0.7–1.2 g/cm3, are commercially
important and have a wide range of industrial applications [1].
Acrylonitrile butadiene rubber–poly vinyl chloride (NBR–PVC) is a
miscible physical mixture of commercial importance. The NBR can act
as a permanent plasticizer for PVC. The presence of PVC improves aging
resistance of NBR as both PVC and NBR are polar and blending NBR
with PVC increases the compatibility [2,3]. The aim in blending plastic
and rubber is to improve the physical, thermal, and mechanical
properties as well as to modify the processing characteristics and cost
reduction of the final product. Some blends, however, are incompatible.
In a blend of rubber–plastic, such as NBR–PVC the rubber must be
vulcanized in the final form [4].Vulcanization occurs when two radicals
produced on neighboring polymer units recombine. These radicals are
produced by a chemical agent, such as peroxide or sulfur. Alternatively,
radiation, such as electron beam or gamma radiation can be used to
vulcanize polymers [5,6].

THEORETICAL

Electron Beam Curing System

It is well known that interaction of electron beam radiation with

a polymer results in the formation of free radicals by dissociation of the
excited state or by ion molecular reaction. The vulcanization reaction
occurs during the irradiation of the polymer [7]. The electron beam
radiation process does not employ chemical agents, such as peroxides
[8]. Using small amounts of coagents, such as ethylene glycol
dimethacrylate (EDMA), trimethylol propane trimethacrylate
(TMPTMA), or trimethyl-propane trimethacrylate (TPTA) can help
reduce the dose required for cross-linking [7,8]. Two factors are
important in irradiation: irradiation dose and temperature.
In this research, the temperature is fixed in both curing systems
(160
C), and the irradiation dose is variable for curing by an electron beam.
The reaction mechanism of electron beam curing system is shown here [9]:

high Eng Irradiation

polymerðPHÞ ! PH  ðsuper excited stateÞ
PH  ðsuper excited stateÞ ! PH þ þ 1e
 Physicomechanical Properties of NBR–PVC Blend 153

PH  ! P
þ H

PH þ þ PH ! P
þ PH2þ

P
þ PH2þ þ 1e! P
þ P
þ H2
P
þ P
! P  P ðcross-linked polymerÞ

P1 H  þ P2 H ! P1 H þ P2 H  ðenergy transferÞ
H
þ PH ! P
þ H2

Taguchi Method

Taguchi’s approach provides the designer with a systematic and

efficient approach for conducting experiments to determine near-
optimum settings of design parameters for performance and cost. The
method emphasizes pushing quality back to the design stage, seeking
to design a product/process, which is insensitive to quality problems.
The Taguchi method utilizes orthogonal arrays to study a large number
of variables with a small number of experiments. Using orthogonal
arrays significantly reduces the number of experimental configurations
to be studied. It should be noted that this design reduces 81  (34)
configurations to nine experimental evaluations. The conclusions drawn
from small-scale experiments are valid over the entire experimental
region spanned by the control factors and their settings. This method
can reduce research and development costs by simultaneously studying
a large number of parameters [10,11]. In order to analyze the results,
the Taguchi method uses a statistical measure of performance called
signal-to-noise (SN) ratio. The SN ratio takes both the mean and the
variability into account. The SN ratio equation depends on the criterion
for the quality characteristic to be optimized. After performing the
statistical analysis of SN ratio, an analysis of variance (ANOVA) needs
to be employed for estimating error variance and for determining the
relative importance of various factors.
The SN ratio characteristics can be divided into three categories when
the characteristic is continuous [12,13]:
a. Nominal is the best characteristic:

Pr
i¼1 ðY1  MÞ2
SN ¼ 10 log
r
154 M. HAFEZI ET AL.

b. Smaller the better characteristics:

Pr
i¼1 Y12
SN ¼ 10 log
r

and
c. Larger the better characteristics:

Pr
i¼1 ð1=Y12 Þ
SN ¼ 10 log
r

M is the average of the observed data, r is the number of observations,

and Y is the observed data. For each type of characteristic, with the
above SN ratio transformation, the higher the SN ratio, the better
the result.

EXPERIMENTAL

Material

A fixed master batch formulation was used in this study for both
curing systems. The fixed master batch formulation and their suppliers
is shown in Table 1. Table 2 shows the specification of the NBR–PVC
blend. All materials were used as supplied.

Table 1. Fixed master batch formulation.

Material Phra Manufacturer

NBR–PVC (60/40) 100 Bayer Co., Germany

Carbon black N330 40 Ahvaz Factory, Iran
Zinc oxide 3 Gostar Jam, Iran
Stearic acid 1 Minko, Malaysia
a
part per hundred of rubber.

Table 2. Specification of the NBR–PVC blend.

Grade Ratio NBR–PVC Mooney viscosity (ML1 þ 4, 100
C) Density (g/cm3) Shape

866/20 60/40 20  5 1.04 Sheet

 Physicomechanical Properties of NBR–PVC Blend 155

Table 3. Sulfur curing system.

Material Phr Manufacturer

Sulfur 1–2 RPCa, Iran

MBTSb 1–2 Bayer Co., Germany
CBSc (vulkacit cz) 0.3–0.7 Bayer Co., Germany
a
Razi Petrochemical Co.,
b
dibenzothiazyl disulfide, and
c
N-Cyclohexy-2-benzothiazole sulfonamide.

Table 4. Irradiation dose for electron beam curing system.

Irradiation dose (kGy) 0 25 50 75 100 125 150

Table 3 shows the sulfur curing system and their amounts and
suppliers. Table 4 shows the irradiation dose for electron beam curing.

Compounding and Cure Characteristics

Mixing was carried out in a laboratory size two-roll mill according to

ASTM D3182.

For Electron Beam Curing

In the first series of experiments, fixed formulation of master batch

compounds were compression molded between aluminum foil at 160
C
under pressure (120 kg/cm2) in an electrically heated press to prepare
sheets of 2  0.05 mm thickness. Dumbbell shaped test specimens were
cut from the sheets. The samples were marked 0–150 referring to
radiation dose in kGy.
The irradiation was carried out at Yazd Radiation Proccessing Center
using an electron beam accelerator RHODOTRON TT200. The
specification of the electron beam accelerator is given in Table 5.
In order to investigate the effects of electron beam energy on
vulcanization of NBR–PVC blend, samples of NBR–PVC blend were
irradiated with 10 MeV electron beam at an air temperature of 160
C.

For Sulfur Curing

In the second series of experiments, an L9 orthogonal array was

employed to determine the effect of three process parameters.
156 M. HAFEZI ET AL.

Depending on the number of factors and level needed, 4 factor and

3 level, L9 orthogonal array of Taguchi method were used. The L9
orthogonal array is given in Table 6, which consists of nine experiments
corresponding to the nine rows and four columns. That is, for any pair of
columns, all combinations of factor levels occur and they occur an equal
number of times. It should be noted that this design reduces 81  (34)
configurations to nine experimental evaluations.
Cure characteristic of mixes, i.e., scorch time, t2 and cure time, t90
were determined using a Hiwa Rheometer model 100 according to
ASTM D2084. Various NBR–PVC blends with different amounts of
curing system were compression molded at 160
C under pressure
(120 kg/cm2) in an electrically heated press to prepare sheets of
2  0.05 mm thickness. Dumbbell test specimens were cut from the
sheets.

Table 5. Specification of RHODOTRON TT200 electron beam accelarator.

Beam energy 10 MeV

Beam power at 10 MeV 70 kW

Energy dispersion at 10 MeV 300 keV
Scanning range 30–100 cm
Total power consumption <300 kW
RF 107.5 MHz
RF power output 200 kW
Electron gun average current 0–10 mA
Resolution 50 mA

Table 6. L9 orthogonal array of Taguchi method.

Experiment no. A B C e

1 1 1 1 1
2 1 2 2 2
3 1 3 3 3
4 2 1 2 3
5 2 2 3 1
6 2 3 1 2
7 3 1 3 2
8 3 2 1 3
9 3 3 2 1

e: Empty column is denoted by d.

 Physicomechanical Properties of NBR–PVC Blend 157

Measurements

The tensile strength (TS) and elongation at break (EB) were

measured using dumbbell type specimens according to ASTM D412.
Tensile tests were carried out on a Hiwa 200 tensometer at 500 mm/min
cross-head speed at room temperature. Hardness tests were carried out
using a shore type A Durometer according to ASTM D2240. The other
physicomechanical tests were resilience (ASTM D1054) and abrasion
(DIN5356). All tests were carried out at room temperature (25
C). In
order to study the aging behavior of NBR–PVC blend cured by sulfur
and electron beam samples were left in an oven at 100
C for 48 h. Then
the samples were conditioned at ambient temperature for at least 16 h
before testing according to ASTM D573. At least three samples were
used for all tests carried out.

RESULTS AND DISCUSSION

The results of the electron beam curing system are summarized

in Table 7 and the results of the sulfur curing system are summarized
in Table 8.
When the best levels for both curing systems were compared,
radiation cured samples demonstrated higher TS both before and after
aging (see Tables 7 and 8 and Figure 1). This is due to higher cross-link
density of NBR–PVC blend cured by electron beam than NBR–PVC
blend cured by sulfur. It was established that in addition to the type of
cross-link, the cross-link density also plays an important role in
determining the physicomechanical properties. The nature of cross-
link of sulfur–MBTS–CBS of NBR–PVC blend are –C–Sx–C– but the
cross-link nature of electron beam are –C–C– so the TS is higher in
NBR–PVC blend cured by electron beam.
Comparing the results for NBR–PVC blend cured by electron beam
and sulfur curing system, tensile properties of samples cured by electron
beam increased 7% before aging and 6% after aging. Figure 2 shows an
EB of 30% before aging and 23% after aging is improved for NBR–PVC
blend cured by electron beam. It is because of higher cross-linking
density and –C–C– bond existed in cross-linked NBR–PVC blend cured
by electron beam.
Hardness before aging and after aging (Figure 3) and percentage
resilience (Figure 4) for cured NBR–PVC blend by electron beam is 10%
higher than NBR–PVC blend cured by the sulfur system.
 158

Table 7. Physicomechanical properties of NBR–PVC blend cured by electron beam system.

Hardness Hardness
TS before TS after %EB before %EB after before aging after aging
Dose (kGy) aging (MPa) aging (MPa) aging aging % Abrasion % Resilience (Shore A) (Shore A)

0 5.4 7.9 203 211 13.8 20.4 81 83

25 12.7 16.2 425 337 6.0 19.9 83 84
M. HAFEZI

50 17.9 21.3 369 276 4.6 19.1 85 86

75 20.2 23.3 314 204 7.0 18.7 75 88
ET AL.

100 21.1 23.2 251 161 7.3 18.4 87 89

125 21.5 22.1 206 129 7.4 17.2 87 90
150 21.8 21.8 160 111 6.5 16.4 89 91
 Table 8. Mean value for physicomechnical properties of NBR–PVC blend cured by sulfur system.

TS before TS after %EB before %EB after Hardness before Hardness before
Experiment no. aging (MPa) aging (MPa) aging aging % Abrasion % Resilience aging (Shore A) aging (Shore A)

1 19.1 20.2 328 207 7.9 15.5 64 82

2 19.8 20.6 317 206 7.4 15.0 68 84
3 20.1 21.1 285 192 7.2 14.9 70 86
4 19.6 20.6 278 185 7.0 15.0 73 86
5 19.8 20.8 270 190 5.6 14.9 75 87
6 20.2 21.3 277 186 6.1 14.6 77 87
7 20.4 21.5 259 178 5.8 14.8 79 88
8 20.4 21.5 258 174 6.3 14.8 79 88
9 20.5 21.8 221 170 5.7 14.7 81 89
Physicomechanical Properties of NBR–PVC Blend
159
160 M. HAFEZI ET AL.

24
23.5 23.3
Before aging
23 After aging
Tensile strength (MPa)

22.5
22 21.7 21.8

21.5
21
20.5
20.5
20
19.5
19
E.B. cure Sulfur cure
FIGURE 1. Comparison of tensile strength of sulfur and electron beam cured NBR–PVC
blend.

250
221 Before aging
After aging
200
170
% Elongation of break

160
150
111
100

50

0
E.B. cure Sulfur cure

FIGURE 2. Comparison of elongation at break of sulfur and radiation cured NBR–PVC

blend.

Abrasion resistance of NBR–PVC blend cured by electron beam

is 20% higher than that of NBR–PVC blend cured by the
sulfur system (Figure 5). It is because of the higher cross-link density
and –C–C– bond that existed in NBR–PVC blend cross-linked and
cured by electron beam.
 Physicomechanical Properties of NBR–PVC Blend 161
94
92 91 Before aging
After aging
90 89 89
Hardness (shore A)

88
86
84
82 81
80
78
76
74
E.B. cure Sulfur cure
FIGURE 3. Comparison of hardness of sulfur and electron beam cured NBR–PVC blend.

17

16.5 16.4

16
% Resiliance

15.5

15
14.6
14.5

14

13.5
E.B. cure Sulfur cure
FIGURE 4. Comparison of percentage of resilience of sulfur and electron beam cured
NBR–PVC blend.

CONCLUSIONS

1. NBR–PVC blend cured by electron beam has better physicomech-

anical properties compared to sulfur-cured counterparts.
2. NBR–PVC blends irradiated to 75 kGy possess the best physico-
mechanical properties compared to other dose rates.
162 M. HAFEZI ET AL.

6 5.7

5 4.6
% Abrasion
4

0
E.B. cure Sulfur cure
FIGURE 5. Comparison of percentage of abrasion of sulfur and electron beam cured
NBR–PVC blend.

3. The advantages of using the electron beam curing system over

conventional techniques, such as thermal or chemical processing vary
with the application, but advantages include one or more of the
following: reduced cure time and energy investment; higher process
throughput; operation at ambient temperatures with no effluent;
more uniform product; unique product properties; and better control
on curing process. Therefore high energy electron beam is a suitable
method for cross-linking of NBR–PVC blend.

ACKNOWLEDGMENTS

The authors would like to thank the group of operators of

RHODOTRON electron beam accelerator of Yazd Radiation
Processing Center for irradiation of samples and management of
Isfahan Latex Co., Isfahan, Iran for their helpful assistance.

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