Egyptian Journal of Petroleum xxx (2017) xxx–xxx

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Mechanical and physical properties of nanosilica/nitrile butadiene

rubber composites cured by gamma irradiation
H.M. Eyssa a, D.E. Abulyazied b,⇑, M. Abdulrahman c, H.A. Youssef a
a
Radiation Chemistry Dept., National Centre for Radiation Research and Technology (NCRRT), Egyptian Atomic Energy Authority, P. O. Box 29, Nasr City, Cairo, Egypt
b
Polymer Laboratory, Petrochemical Dept., Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
c
Radiation Physics Dept., National Centre for Radiation Research and Technology (NCRRT), Egyptian Atomic Energy Authority, P. O. Box 29, Nasr City, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Nitrile Butadiene Rubber (NBR) nanocomposites are prepared with different contents ranging from 5 to
Received 3 January 2017 20 phr (part per hundred parts of rubber) of Sinai sand nanoparticles and fumed silica micro particles
Revised 8 June 2017 (SiO2) and mixed with other additives to improve its properties. The nanocomposites were irradiated
Accepted 22 June 2017
with gamma irradiation from 25 to 150 kGy. The effect of the silica content and irradiation dose on
Available online xxxx
the morphology, the mechanical and the physical properties of nanocomposites was investigated. The
scanning electron microscope (SEM) showed that there is a fine dispersion of nanoparticles into NBR
Keywords:
matrix, also some aggregates were observed and their size depends on the SiO2 content. The results indi-
NBR
Fumed silica
cated that there was an improvement in tensile strength by increasing irradiation doses up to 50 kGy and
Nano-silica sand by increasing silica loading up to 15 phr. Enhancement of volume fraction by increasing irradiation doses
Nanocomposites and also by increasing silica loading was observed. The thermal gravimetric analysis (TGA) indicated that
Gamma irradiation the thermal stability of NBR increases by increasing silica contents and the increase in irradiated samples
is higher than that in un-irradiated. Finally, it is found that the presence of silica in the nanocomposites
enhances the electrical insulating properties of the NBR.
Ó 2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction and are also employed in a variety of applications, such as electron-

Nowadays, mechanical, physical, and electrical properties of
polymer nanocomposites are improved and developed during
industrial and academic research laboratories. Their concern to
develop such composites is mainly because of the fact that nanopar-
ticles present a high surface-to-volume ratio, which may induct indi-
vidual properties to these nanocomposites as compared to macro-
scale composites [1]. Industrial fillers such as carbon black, calcium
carbonate, mica and talc [2–6] are used for many of the works per-
formed on such systems. The effect of naturally occurring fillers such
as clay [7–9] river mine and beach sand [10] on some properties of
filling polymeric systems is also investigated. Among the naturally
occurring fillers, sand is relatively cheap and is found more abun-
dantly than the aforementioned industries [11].
Among the numerous polymer composites, silica/polymer
nanocomposites are the most commonly reported in the literature
Peer review under responsibility of Egyptian Petroleum Research Institute.
⇑ Corresponding author at: Petrochemical Department, Polymer Laboratory,
Egyptian Petroleum Research Institute EPRI, 1 Ahmed El-Zomor Street, 11727 Nasr
City, Cairo, Egypt.
E-mail address: dalielsawy@hotmail.com (D.E. Abulyazied).
ics, automotive and aerospace industries as well as used in many
industrial products due to their good mechanical characteristics
[12–14].
Nitrile butadiene rubber is a polar rubber, has good resistance
to a wide variety of oils and solvents and hence it is widely used
in products like oil seals, pipe protectors, automotive and aeronau-
tical industries [15]. NBR in the unfilled form has very low tensile
strength and is not electrically conductive. Silica and other fillers
are used for reinforcement. It is found that nitriles exhibited the
highest interaction with silica probably through the hydrogen
bond interaction between the -CN group and silanol groups. Incor-
porating silica to NBR enhances its electrical insulating properties.
Huang et al. consider that inorganic particles may reduce the car-
rier mobility in the composite materials, thereby increasing their
electrical insulating properties [16,17].
Irradiation of polymers causes formation of free radicals and
ions that can react to produce cross linked polymers. The products
exhibit new properties such as better resistance to heat and chem-
ical action and improvement in the mechanical strength. Vulcan-
ization of rubber by irradiation has also been accomplished and
offers some advantages over the conventional methods, such as
the complete control of crosslinking density, the formation of cross

http://dx.doi.org/10.1016/j.ejpe.2017.06.004
1110-0621/Ó 2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
2 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx
links in solid state, no need for catalysts or other additives, no heat
treatment and the ability of saturated polymers to crosslink which,
because of the absence of unsaturated groups are largely resistant
to conventional chemical treatment. Moreover, it is cleaner and
more efficient alternative to heat and certain costly chemicals.
Generally, radiation sensitizers are used, which give high yields
of radicals under the influence of radiation, promote the crosslink-
ing at a much lower dose and consequently improve the properties
of the base polymer.
The purpose of this work is to investigate the effect of the silica
type sand and fumed as well as the effect of gamma irradiation on
different properties of NBR.
2. Experimental
2.1. Materials
Nitrile Butadiene Rubber (NBR) has acrylonitrile content 40%,
density 0.97 g/cm3, Mooney viscosity ML1 + 4 (100 °C) = 50. Its
commercial name is KRYNAC40.50 (Bayer Rubber Company
Division France). Antioxidant, chemical name is 1, 2-Hydro.2, 2,
4-Trimethyl quinoline (TMQ), its red pellets’ molecular weight:
173.258, molecular formula: C12H15N, density: 1.05 g/cm3, Sup-
plier: Intatrade chemical (GmbH), Germany. Di-Octyl-phthalate
(DOP) used as plasticizer, it is colorless, oily, liquid, its molecular
weight: 390.6, molecular formula: C24H38O4, density 0.80 g/cm3,
boiling point: 384 °C and supplier: Henan Tianfu Chemical Co.,
Ltd., China. Hexamethylenetetramine (HMTA) used as coupling
agent for reaction, molecular formula: C6H12N4, molecular weight:
140, it is white and has a density of 1.3 g/cm3, its sublimation and
decomposition reach 265 °C, supplier: Heliopolis for chemical
industries, Cairo, Egypt. Polyethylene glycol (PEG) Mn = 600 g/mol,
OH functionality = 2.0, 6-Hexanediol diacrylate (HDDA) as
crosslinking agent (Fluka, Germany). Fumed Silica (Pyrogenic Sil-
ica) used as received, HDKÒ N20, synthetic: hydrophilic amorphous
silica, produced via flame hydrolysis, white colloidal powder of
high purity, SiO2-content > 99.8%, density of SiO2 = 2200 g/l, silanol
group density = 2 SiOH/nm2, Surface area 170–230 m2/g, particle
size >40 mm, supplier: Wacker Chemie AG, Wacker Silicons,
Hanns-Seidel-Platz, and München, Germany. Silica sand originated
naturally from Sinai, Egypt.
2.2. Preparation of silica sand nanoparticle
Silica sand is washed with deionized water to remove any clay
particles followed by drying in an oven at 100 °C for 8 h. The dried
silica sand is sieved to about < 325 lm. The silica sand is grounded
to nanoparticles for 16 h using dry ball milling, (PlanitaryBM 400
type) retsch company, Germany. The chemical composition of sil-
ica sand nanoparticles is analyzed by Energy Dispersive X-ray
(EDX) technique. The nanoparticles’ results are checked micro-
scopically through TEM.
2.3. Preparation of the NBR/silica nanocomposites
Nitrile butadiene rubber (NBR) and the ingredients are mixed
on two-roll mill, the formulations are shown in Table 1. Rubber
is first masticated for 5 min. The other ingredients are mixed well
to ensure homogeneous distribution, and then added to rubber.
Mixing is continued at the rubber mill for another 20 min. Finally,
rubbers containing the ingredients are taken out of the mill and
stored at room temperature for 24 h before molding. The rubber
mixes are pre-heated for 7 min at 160 °C and a pressure of
10 MPa, then full pressed for 12 min using hot press. In order to
ensure predetermined sheet size, the hot pressed sheet is cold
pressed afterward in another press and cooled with water.
Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
2.4. Gamma irradiation of the nanocomposites
The molded samples, in the form of thin sheets, have been irra-
diated by a Cobalt 60 gamma cell source (made in Canada),
installed at the National Centre for Radiation Research and Tech-
nology, Egyptian Atomic Energy Authority, Cairo, Egypt. The sam-
ples are cured by using gamma rays at 25 to 150 kGy.
2.5. Transmission electron microscopy (TEM)
Transmission electron microscopy (TEM) is adopted to charac-
terize the nano-particles modification. TEM is performed by
TEM-1230 with an accelerating voltage of 100 kV (JEOL Co., Japan).
2.6. Scanning electron microscope (SEM)
Scanning electron microscope SEM studies of NBR composites
are carried out by JEOLJSM–5400 high resolution (Japan), at
20 MA and 15 kV. Samples’ film is cut and is sputter–coated with
gold using a microscope sputter coater, viewed through the micro-
scope and also EDX technique is used for analysing elements of
SiO2 through the microscope.
2.7. Measurements for nanocomposites
2.7.1. Swelling properties
All samples of known weight (WO) are immersed in thimbles
containing toluene. The swelling measurements are carried out at
room temperature. The samples were then removed, blotted
quickly to remove the attached solvent on the sample surface
and weighed. The swelling equilibrium is reached after 24 h. Sam-
ples are dried in oven at 50 °C to constant weight for 48 hr.
The volume fraction of the swollen rubber (VF) is calculated
according to the following equation:
 
v olume of rubber W0
qr
Vf ¼     ð1Þ
v olume of rubber W0
qr þ v olume of solv ent W1W 0
qs
where Wo is original weight, W1 = weight after swelling + solvent,
qr = density of rubber, and qs is the density of solvent.
2.7.2. Mechanical properties
Tensile strength and elongation at break are tested at room
temperature. Every data point is the average of 5 tests. (Mecmesin
tester, Mecmesin Limited, UK.), equipped with software is used,
employing a crosshead speed of 500 mm/min.
2.7.3. Crosslinking density measurements
It has been shown that the true stress (r) in simple extension
can be considered as a sum of two contributions [18]:
r ¼ ro ðkÞ þ Geðk2  k1 Þ ð2Þ
where r is the true stress (nominal stress multiplied by k), k is the
extension ratio, ro depends on the chemical nature of the rubber,
but the Crosslink density, Ge is a parameter that depends on the
degree of crosslinking. Plotting r vs. k2-k1 gives Eq. (2), the slope
of the curve is Ge.
According to Zang et al. [19], Mc (molecular weight between
crosslinks) can be estimated from the value of Ge as follows:
Mc ¼ A/ qRT=Ge ð3Þ
The prefactor Aɸ is assumed to be equal to 1; T is
absolute temperature, q is the density of the specimens, R
(8,314,472 cm3 Pa K1 Mol1) is the gas constant.
2.7.4. Thermal properties
Thermo gravimetric analysis (TGA) is determined by using
Shmadzu-50 (TGA-50H) (Japan) at a heating rate of 10 °C/min in
 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 3

Table 1
Composition of SiO2/NBR.

Ingredients, phra Blank F5 F10 F15 F20 S5 S10 S15 S20

NBR 100 100 100 100 100 100 100 100 100
TMQ 1 1 1 1 1 1 1 1 1
DOP 10 10 10 10 10 10 10 10 10
PEG 2 2 2 2 2 2 2 2 2
HMTA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
HDDA 5 5 5 5 5 5 5 5 5
Fumed silica – 5 10 15 20 – – – –
Silica sand – – – – – 5 10 15 20
a
Part per hundred parts of rubber by weight.

N2 atmosphere, a temperature range from room temperature up to 2.7.5. Electrical properties

600 °C.
The thermal stability was estimated by calculating the activa-
tion energy (Ea) for the thermal decomposition of all the compos-
ites according to Horowitz and Metzger method [20].
Ln Ln½1=ð1  aÞ ¼ ðEh=RT2s Þ
The electrical measurements are carried out using a DC voltage/
current generator, along with a precision digital electrometer
(Keighley 6517A) to determine the current generated on the appli-
cation of a known voltage to fill polymer. The measurements are
made at different temperatures for each filled sample.
ð4Þ 3. Results and discussion

where, a = [(W0-Wf)/(Wt-Wf)], W0 and Wf are the initial and
final weights of the samples, respectively, Wt is the weight of
the sample at temperature T.h = T-Ts, T is the temperature of
the sample and Ts is the reference temperature (the tempera-
ture at the maximum degradation rate), where R denotes the
gas constant (R = 8.314 J K1mol1). In this method, a plot of
Ln Ln [1/(1-a)] against h yields a straight line, its slope is
E/RT2s. R and T were known, therefore the value of E is
determined.
3.1. Morphology study
3.1.1. EDX analysis of nano-silica sand
EDX analysis of the silica sand, shown in Fig. 1, reveals the pres-
ence of high SiO2 content without any amount of other metals.
3.1.2. TEM of nano-silica sand
Fig. 2 shows the TEM images of the silica sand before and after
grinding. The image indicates that the SiO2 particles before

Fig. 1. EDX analysis of the nanosilica sand.

Fig. 2. TEM micrographs of sand silica; (a) before grinding and (b) after grinding.

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
4 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 3. SEM images for (a) Neat NBR, (b, d, f and h) NBR/ silica nanocomposites un-irradiated and (c, e, g and i) irradiated samples at 50 kGy.

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 5

grinding are forming a big cluster. However, after grinding 16 h the
SiO2 particles become spherical, reasonably uniform in size, and
have an average diameter of 45–90 nm.
3.1.3. SEM of nanocomposites
Fig. 3a, displays the images of neat NBR surfaces. It is shown in
the figure that the surface of the NBR is smooth. The images of the
NBR/silica nanocomposites (fumed and nano-silica sand) are
shown in (Fig. 3, b–i), the dark phase represents the NBR matrix
and the bright phase corresponds to the SiO2 particles. It is
observed from the figure that the silica dispersed well in the NBR
matrix, also the amounts of nano-silica on the unit area gradually
increase with increased silica loading (Fig. 3f–i). Before irradiation,
NBR composite surface is nearly rough due to the presence of the
silica (Fig. 3b, d, f, h) whereas after irradiation, the surface becomes
smooth as shown in Fig. 3(c, e, g and i) due to increasing crosslink-
ing density. In addition silica to silica attraction is high due to the
hydrophilic silanol group. Addition of HMTA is necessary to reduce
particles aggregates size, therefore, mixing become feasible. HMTA
reduces hydrogen bonding, consequently silica is converted to
hydrophobic and becomes compatible with rubber i.e. its disper-
sion is enhanced. Also, NBR has CN group which induces its basicity
leading to make a strong interaction with the silica which has
acidic surface [21]. The influence of the irradiation process on the
silica surface induces the crosslinking, therefore surface becomes
smoother than that of un-irradiated.
3.2. Effect of sand and fumed silica on the properties of NBR
3.2.1. Volume fraction determination
The volume fraction of swollen NBR composites loaded with
different fumed and sand, silica contents as a function of irradia-
tion doses is shown in Fig. 4. From the figure, it follows that, the
neat NBR has lower volume fraction than loaded with silica. Addi-
tion of coupling agent (HMTA) together with silica enhances the
compatibility between silica and NBR matrix. Therefore, the adhe-
sive between the filler and rubber matrix is improved due to good
usability and high surface area of silica. This may explain the low
solvent absorption of the composites when the silica content
increases due to the increase in silica–rubber interaction [22].
Upon irradiation, the crosslinking is remarkably increased due
to irradiation in the presence of crosslinking agent (1,4-
hexanediol diacrylate). The difference in volume fraction between
the irradiated and un-irradiated specimens is highly significant.
Generally increasing irradiation dose is accompanied by an
increasing volume fraction. The increase in volume fraction is an
evidence of increasing crosslinking density of the composites. On
the other hand, the volume fraction of the samples loaded with
fumed silica is slightly lower than that of loaded silica sand.
3.2.2. Mechanical properties
The mechanical properties of NBR/silica nanocomposites were
improved by good dispersion and adhesion of nanoparticles with

Fig. 4. Volume fraction for swollen NBR nanocomposites with different loading of silica curing by gamma irradiation, (a) Fumed silica, (b) Nano sand silica.

Fig. 5. Tensile strength of irradiated NBR using different silica contents, (a) fumed, (b) nano sand.

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
6 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 6. Elongation at break as a function of irradiation doses and silica contents, (a) fumed, (b) sand.

the polymer matrix. Highest mechanical properties are due to
excellent control of the interface morphology of polymer
nanocomposites. Fig. 5 shows the relation between irradiation
doses and tensile strength for NBR loaded with different contents
of silica fumed or sand. It is obvious that, increasing irradiation
dose increases the tensile strength up to 50 kGy then decreases
at higher doses up to 150 kGy. The decrease in tensile strength
may be attributed not only to degradation reaction that takes place
at high irradiation doses but also to excessive crosslink density. At
a high crosslinking density, the specimens become easy, brittle and
fracture at low elongation [23]. This result correlates well with the
high volume fraction or higher Crosslink density of the composites.
Also, it is found that the values of tensile data increase up to 15 phr
of silica, then decrease at higher silica content 20 phr over all irra-
diation doses. The increase in tensile strength by increasing silica
content up to 15 phr may be due to relatively good silica disper-
sion. On the contrary, a reduction in tensile strength is seen for
nanocomposites containing 20 phr of SiO2 due to the formation
of large SiO2 agglomerate, which is in agreement with SEM micro-
graphs [24]. Therefore, as homogenous dispersion of SiO2 nanopar-
ticles increases in NBR matrix, the reaction between the silica and
NBR becomes stronger. Also, from Fig. 5 it can be seen that, the
increases in tensile data for silica sand are higher than those of
fumed silica and the irradiated samples have a tensile strength
higher than un-irradiated one. Furthermore, it is noticed that the
rate of decreasing tensile strength at irradiation dose higher than
50 kGy is higher for micro fumed silica than for nano-silica sand
(see Fig. 6).

3.2.3. Crosslinking density

Fig. 7. True stress (r) as a function of (k2-k1) for NBR/nano sand silica composites.
The determination of crosslinking density by swelling measure-
ments that varies with concentration, molecular weight (Mc), and
temperature has been reported by [25]. From the swelling, the
sample is also often subjected to threedimensional extensions. In
addition, weak polymer–solvent interaction and contribution due
to entanglements are lost upon straining of elastomers [26]. Thus,
at best, only a poor representative of the original state (un-
swollen) of the rubbery sample is obtained by swelling. On the
other hand, the determination of Mc according to the stress-
strain relationship offers the simplest method of characterizing

16000 16000
(a) Fumed silica Neat NBR
14000 14000 (b) Nano sand silica
F5
12000 F10 12000 Neat NBR
F15 S5
10000 F20 10000 S10
Mc
Mc

S15
8000 8000
S20
6000 6000

4000 4000

2000 2000

0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Irradiation dose, kGy Irradiation dose, kGy

Fig. 8. Effect of irradiation dose and different contents of silica on the molecular weight chain between crosslinks (a) Fumed silica (b) Nano sand silica.

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 7

Table 2 Table 3
Mc values for the neat NBR and NBR/silica composites (un-irradiated samples). Thermal activation energy and some thermal parameters.

Concentration, wt% Fumed silica Silica sand Irradiation dose T10%°C Tmax °C Ea (kJ/mol) Char residue
0 14927.957 14927.957 Rubber 0 kGy 260 445 19.7 9.9
5 12263.413 12291.7945 F5 270 450 21.0 19.5
10 8793.326 8531.604 S5 309 446 22.9 11.2
15 6418.868 7561.5414 F20 264 466 24.6 20.6
20 9614.316 9779.188 S20 270 453 26.6 17.3
Rubber 50 kGy 260 450 24.3 9.9
F5 268 453 25.1 14.1
the crosslinking density of polymer network. A representative S5 290 452 26.0 5.5
F20 286 467 25.5 20.2
curve for the relation between true stress r and (k2-k1) is shown S20 317 456 27.9 24.3
in Fig. 7. The relation yields a straight line, its slope is Ge. Mc can be
calculated by substituting Ge value in Eq. (3). Fig. 8 shows the
effect of irradiation dose and different contents of silica (micro
degradation of the samples. The thermal degradation behavior of
fumed & nano sand) on the Mc for NBR composites.
un-irradiated and irradiated samples (50 kGy) of NBR composites
It should be observed that Mc data corresponding to NBR are
at two silica contents for fume & sand are shown in Fig. 9. The
very high and are included in Table 2. From the figure, it is clear
onset of degradation temperature, the temperature at which 10%
that the Mc values decrease with increasing irradiation dose for
degradation occurred (T10), and the char residue were calculated
all the specimens under investigation. It can also be noticed that
from the TGA plots and are listed in Table 3. It is observed from
the increase in loading silica contents up to 15 phr is accompanied
the table that T10 of the un-irradiated composites is higher than
by a decrease in Mc values, which indicates high crosslinking den-
that of the neat NBR. Also, T10 of irradiated composites is higher
sity. On the other hand, it can be seen that Mc values at 20 phr is
than neat NBR. Thereby, probably the T10 increases in the case of
higher than other loading contents. The higher Mc values at
NBR/silica composites than the neat NBR are due to an increase
20 phr are due to the formation of larger aggregates which lead
in cross-link density. Cross linking increases the rigidity of the sys-
to weak interaction between NBR and silica, consequently cross-
tem, which in turn increases the thermal stability [27]. The
linked density relatively decreased. The decrease in Mc with
increase in the degradation temperature may be due to the dis-
increasing irradiation dose proceeds with different degrees
persed micro and nano-silica that hinders the permeability of vola-
depending on the silica content whereby the composites contain-
tile decomposition products out of the material [28].
ing high silica content (20 phr) is less influenced by irradiation.
Fig. 10 illustrates the weight derivative of the thermo gravimet-
Based on these results, it can be proposed that not only Mc con-
ric analysis, curve (DTGA) against temperature. From the figure,
tributes to matrix properties, but also physical crosslinks as chain
the temperatures at maximum weight loss rate values (Tmax),
entanglements (chain interlocking), van due walls between poly-
before and after irradiation for NBR nanocomposites at two silica
mer chain and the interaction of the CN group with silica func-
concentrations (5 and 20 phr) are listed in Table 3. From the table,
tional groups on the surface. Low Mc values of nano sand, silica
it is found that there is an increase in the Tmax of un-irradiated than
compared to fumed silica (micro), may be due to low particle size
the neat NBR. The char residue is found to be higher for the
of nano sand.
nanocomposites than that of the neat NBR due to the presence of
silica. All these results indicate that high dispersion of micro or
3.2.4. Thermal properties nano silica gives high thermal stability of NBR nanocomposite
The thermal stability of polymers is usually studied by thermo- compared with neat NBR.
gravimetric analysis (TGA). The weight loss due to the formation of The activation energy (Ea) for NBR composites loaded with two
volatile products after degradation at high temperature is moni- silica contents for un-irradiated and irradiated at constant irradia-
tored as a function of temperature. When heating occurs under tion doses, namely, 50 kGy are listed in Table 3. It can be seen that
an inert gas flow, a non-oxidative degradation occurs, while the the values of (Ea) increase with increasing silica loading for fumed
use of air or oxygen allows oxidative degradation of the samples. and nano sand up to 20 phr. Increasing silica loading enhances
The thermal degradation behavior of un-irradiated and irradiated adhesion between silica and rubber matrix in presence of hexam-
samples (50 kGy) of NBR composites at two silica contents for ethylenetetramine. Also, the data show that (Ea) for un-irradiated
fume & sand are shown in Fig. 9. Air or oxygen allows oxidative samples are lower than that for irradiated. This is due to irradiation

Fig. 9. The initial TGA thermograms of NBR nanocomposites at two contents silica (Fumed & sand) for un-irradiated and irradiated samples.

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
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8 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 10. The rate derivative of NBR nanocomposites for unirradiated and irradiated samples at two contents silica (fumed & sand).

Fig. 11. r versus 1000/T for control samples with different silica contents (a): Fumed silica, (b): Silica sand.

Fig. 12. r versus 1000/T for 50 kGy irradiated samples with different silica contents (a): Fumed silica, (b): Silica sand.

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 9

Fig. 13. The dependence of the dc conductivities on the silica content (phr) (a): control samples, (b): irradiated samples (50 kGy).

process which induces crosslinking between chains of polymer and

silica.

3.2.5. Electrical properties

Figs. 11 and 12 shows the variation of d.c. electrical conductiv-
ity with temperature for the NBR/Fumed silica and NBR/sand, silica
composites for the un-irradiated and irradiated samples (at
50 KGy) respectively over the temperature range 289 to 403 K. It
can be seen from two figures that the r increases with the temper-
ature for the un-irradiated and the irradiated samples with differ-
ent silica content. Increasing r may be due to the thermal
activation according to the well-known Arrhenius law [8], also
raising the temperature may lead to an increase in the mobility
of the partially crosslinked segmental chains and hence, there is
an increase to some extent.
Fig. 13 shows the variation of the d.c. conductivity values at the
room temperature for the NBR/fumed silica composites and NBR/
silica sand nanocomposites respectively versus the contents of sil-
ica (phr) in the nanocomposites. The Figure elucidates that the r of
the nanocomposites is lower than that of the neat NBR; also it
decreases with increasing silica content in the nanocomposites.
The silica surface contains hydroxyl groups, which makes its sur- Fig. 14. The dependence of the dc conductivities on irradiation dose for the 15 phr
face polar. According to Wolff and Wang [29], the surface energies samples.
of silica are characterized by a lower dispersive component and a degradation, which affect its chemical and physical structure,
higher specific the surface energies of silica are characterized by depending on the type of polymer and the dose of irradiation
a lower dispersive component and a higher specific component. [34,35].
The lower dispersive components cause weak rubber–filler At low irradiation doses, lower molecular weight species exists
interactions while higher specific component leads to strong inter- as a result of scission of some side groups, which lead to an
actions among the silica particles. Moreover, at the same time, the increase in the mobility of the partially cross linked segmental
polar surface of silica enhances filler–filler interactions also result- chains and hence, the r increases to some extent. In contrast,
ing in strong intermolecular hydrogen bonds between hydroxyl increasing the irradiation dose, may increase the crosslinking den-
groups of silica [30,31]. Due to such strong interactions, it can sity, which in turn leads to an increase in the intermolecular inter-
aggregate tightly, resulting in its poor dispersion in the rubber actions of the kinetic units of the neighboring chains, thereby
compound which explains the decrease in the r with the increase contributing to decrease the intensity of the molecular motion,
in silica filler contents especially in the case of nano-silica sand leading to a decrease in r [36].
particles [32]. The results obtained confirmed that the addition of
the nano-silica improves the insulating properties of NBR rubber
[33]. 4. Conclusions
The effect of the irradiation dose on the d.c. conductivity, r, in
Fig. 14 shows an increase in r at 25 kGy only then a decay occurs According to the previous results it found that the addition of
up to 150 kGy. When a polymer is subject to ionizing radiation HMTA improves the dispersion of silica and increases the surface
many processes take place simultaneously, e.g. crosslinking and area of silica of interaction with NBR, whereas 1,6-Hexanediol

Please cite this article in press as: H.M. Eyssa et al., Mechanical and physical properties of nanosilica/nitrile butadiene rubber composites cured by gamma
irradiation, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.004
10 H.M. Eyssa et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx
induces crosslinking of the rubber matrix during irradiation. Also,
it is noticed that irradiation of the rubber composites positively
influences most of the properties. In addition, the improvement
in the properties continues up to 15 phr silica contents, whereas
at 20 phr, the properties decrease. Comparing silica sand with
fumed silica reveals that the properties of silica sand (nano-
silica) are higher than fumed silica (micro silica). The Scanning
electron microscope (SEM) reveals that there is a fine dispersion
of nanoparticles into NBR matrix. Moreover, the increasing silica
contents in samples improve thermal stability of NBR nanocom-
posites. Finally, it is shown that the presence of silica in the com-
posites enhances the electrical insulating properties of the NBR.
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