Ultrasonics 44 (2006) e1439e1445

www.elsevier.com/locate/ultras

Ultrasonic studies on polystyrene/styrene butadiene rubber

polymer blends lled with glass ber and talc
A.A. Higazy a, H. A
b

b,*
,

A.H. Khafagy a, M.A. El-Shahawy a, A.M. Mansour

a
Menoa University, Faculty of Science, Shebeen El-Kom, Egypt
National Institute of Standards, B.O. 136 Giza, Tersa St., El-Haram, Giza, CN 12211, Egypt
c
Technical Institute for Developed Industries, Salam City, Egypt

Available online 30 June 2006

Abstract
The compatibility of solid blends: PS/SBR, PS/SBR lled with glass ber and PS/SBR lled with talc were studied using ultrasonic
pulse echo technique. Measurements were carried out at room temperature (298 K) and a frequency of 3 MHz. The ultrasonic velocity
for the compressional wave and that for shear wave have been measured to obtain the elastic moduli data by knowing of density. The
variation of ultrasonic wave velocities and elastic moduli with weight percent of the blend was found to be linear in PS/SBR blend, indicating some degree of compatibility but the drawback of elastic moduli indicate incompatibility of the system blend, while it deviates
from linearity in blends of PS/SBR lled with glass ber and talc but the increase in elastic moduli indicates that there is an increase
in degree of compatibility between PS and SBR due to adding of glass ber or talc. The ultrasonic absorptions for longitudinal wave
in the temperature range from 298 to 423 K in the studied system were measured using ultrasonic pulse echo technique. Typical results
showing the temperature dependence of the ultrasonic absorption at frequencies of 1, 2, 3 and 5 MHz are illustrated for all samples of the
dierent compositions. The study of compositional and temperature dependence of the ultrasonic absorption in the present studied
blends reveals the same behavior of the compatibility degree of the blends. Density data of the blends conrmed the ultrasonic results.
Also the correlation between hardness and elastic moduli for the present blend systems has been studied.
 2006 Elsevier B.V. All rights reserved.
Keywords: Compatibility; Ultrasonic velocities; Elastic moduli and ultrasonic absorption coecient

1. Introduction
Dierent types of rubbers are often blended in order to
obtain materials with improved mechanical properties,
which are of importance to the technologist for determining how suitable particular rubber is for particular use.
Many experimental and theoretical studies reported in this
eld, extensive work has been recently carried out using the
compositional dependence of the compressional ultrasonic
wave velocities and its attenuation in solution and solid
polymer blends [111]. They concluded that in compatible
blends the ultrasonic velocity varies linearly with composi-

Corresponding author. Fax: +20 202 3867451.

E-mail address: hma@hotmail.com (H. A).

0041-624X/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultras.2006.05.142

tion while it deviates from linearity in incompatible polymer blends. It is also, known that [12] the ultrasonic
absorption in heterogeneous medium may be caused
by dispassion of the particles of the medium, however
Sudhakar and Singh [13] reported that the absorption is
of relaxation nature and not due to scattering of ultrasonic
waves by the domains of the dispersed phase. It has been
also concluded that the ultrasonic absorption increased
with temperature at some compositions which indicates
the presence of thermal relaxation.
There are various techniques of studying the compatibility of polymeric blends [14]. The simple measurements of
ultrasonic velocity reveal various aspects of the compatibility of polymer blends in both highly viscous and solid form.
Sidkey et al. [15,16] concluded that the presence of only one
maximum for attenuationcomposition curve reects the

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A.A. Higazy et al. / Ultrasonics 44 (2006) e1439e1445

compatibility of component rubbers and the formation of

true solution out of them.
Recently, A et al. [17,18] used the ultrasonic velocities
and attenuation coecient to study the compatibility of the
epoxidized natural rubberethylene propylene diene monomer (ENREPDM) blends using pulse echo technique at a
frequency of 2 MHz. The relation between ultrasonic
velocity and composition showed a curvilinear type of S
shape and a region of phase in version was shown. This
S type curve interpreted as a formation of two phases
and consequently incompatible blend system. Density of
the rubber blend was measured as well. Longitudinal modulus, shear modulus, Youngs modulus, bulk modulus,
Poissons ratio, crosslink density, and microhardness, of
the rubber blends were then calculated. The variations of
these parameters with the content of weight percent
of EPDM have been discussed based on the structural
changes of the network.

are measured (L1) and (L2). Then the ultrasonic absorption

of the samples is given by
a 20log L1 =L2 =2d

The measurements of ultrasonic velocities and ultrasonic

absorptions were repeated three times to check the reproducibility of the data. The estimated accuracies are about
0.04% and 0.08%, respectively.
2.4. Hardness measurements
Hardness measurements were performed using SHIMADZO hardness tester HMV-2. The HMV-2 tester is used to
measure Vickers hardness (Hv) using a Vickers indenter (a
diamond pyramid indenter with 136 angles between opposing faces).
Vickers hardness of the test load (F) is calculated using
the following equation
H v 0:1891F =d 2

2. Experimental section

2.1. Materials

3. Results and discussion

Polymer blends of polystyrene, PS (Petrochema, Saudi

Arabia) and styrene butadiene rubber, SBR (Einy Chem.,
Italy) with SBR wt% ratios of 10, 20, 30 and 40, respectively
were prepared by melt mixing in a HAAKE RHEOCORD
MIXER 90, Germany. The rotator speed was 80 rpm
during a time of processing of 10 min at 200 C.
Another two polymer blend series were prepared. Each
of them is composed of PS/SBR with wt% ratio (90:10),
respectively, lled with a reinforcing ller. The reinforcing
ller was chosen to be either glass bers (E-glass Chopped
Strands, Vetrotex reinforcement, Europe) or talc (3MgO
4SiO2 H2O, Chemajet, Alex., Egypt) with wt% concentrations of 10, 20, 30, 40 and 50. In order to avoid oxidation
of the components during the processing, 0.4 wt% antioxidant (PAN, Bayer, Germany) was added.

The data of PS/SBR blend, PS/SBR blend lled with

glass ber and talc at room temperature (298 K) and low
temperature in the range of 298423 K are tabulated in
Table 1.

2.2. Density and ultrasonic wave velocities measurements

The density was measured using the suspended weight
method based on the Archimedes principle. Repeated density measurements agreed within 0.01%.
The ultrasonic compressional wave velocity and shear
wave velocity measurements were performed using the
pulseecho technique at a frequency of 3 MHz. Measuring
the transit time (t) for sample together with thickness (d),
the ultrasonic wave velocity can be obtained from the
relation,
V 2d=t

2.3. Ultrasonic absorption measurements

For measuring the ultrasonic absorption (a), the amplitude heights of two successive echoes on the screen of CRO

3.1. Room temperature results

The variation of density with weight percent of SBR in
PS/SBR blend is seem to display a linearly decrease as
the weight percentage of SBR increases from 10 to 40
wt%. On the other hand, density results in blends of PS/
SBR lled with glass ber show a hardly linear relation
and density values increase with the weight percentage of
glass ber from 10 to 50 wt%. However, the addition of
the percentage wt% of talc shows a nonlinear relation at
the same contents of the weight percent.
The plot of longitudinal and shear ultrasonic wave
velocities (Vl and Vs) for PS/SBR blend versus the wt%
of SBR showed a comparatively linearly decrease with
increases in wt% SBR.
The elastic moduli (Longitudinal modulus, L, shear
modulus, G, Youngs modulus, E, and bulk modulus, K)
are calculated from ultrasonic velocities and the density
of the isotropic materials as given in Eq. (5) [19].
L qV 2l
G qV 2s
K L  4=3G
E 2G1 r

All the elastic moduli show the same trend as the density
and the ultrasonic wave velocities, Table 1. The linear variation of ultrasonic velocities and elastic moduli versus
composition for the PS/SBR blend may reveal the compat-

A.A. Higazy et al. / Ultrasonics 44 (2006) e1439e1445

e1441

Table 1
Density, ultrasonic velocities (Vl,Vs), elastic moduli (L, G, E, K), hardness (H), peak temperature (Tp), peak loss (a) and activation energy of PS/SBR blend
with GF and talc wt%
Composition %

q
(g/cm3)

Vl
(m/s)

Vs
(m/s)

L
(GPa)
5.588
5.047
4.134
3.600
3.157

G
(GPa)

E
(GPa)

1.391
1.205
1.060
0.886
0.776

4.642
4.064
3.510
3.967
2.598

H 106
N/m2

Peak
temperature,
Tp (K) at 2 MHz

a peak loss
(dB/cm) at
2 MHz

Activation
energy
kcal/mole

3.733
3.440
2.720
2.417
2.122

26
21.5
18.8
15.5
11.1

352
368
331
323
328

11.1
12.35
10.6
9.29
10

16.68
25.36
17.91
17.91
18.94

K
(GPa)

PS/SBR

0
10
20
30
40

2305
2200
2010
1888
1781

2305
2200
2010
1888
1781

1150
1075
1018
937
883

PS/SBR with GF

0
10
20
30
40
50

2200
2250
2332
2508
2593
2760

2200
2250
2332
2508
2593
2760

1075
1004
1096
1123
1204
1227

5.05
5.61
6.37
7.87
9.03
10.83

1.21
1.12
1.41
1.58
1.95
2.14

4.06
3.91
4.83
5.52
6.72
7.51

3.44
4.12
4.49
5.76
6.43
7.97

21.5
22.47
24.8
25.7
28
29.2

368
368
368
368
365
363

12.35
18.2
20.7
17.89
13.8
17

25.36
25.36
25.36
25.36
24.47
23.76

PS/SBR with talc

0
10
20
30
40
50

2200
2370
2888
3373
3621
4265

2200
2370
2888
3373
3621
4265

1075
1018
1057
887
1023
1831

5.5
6.23
9.88
14.49
18
27.2

1.21
1.06
1.32
1
1.44
5.02

4.06
3.74
4.89
3.86
5.5
7.79

3.44
4.82
8.11
13.16
16.09
20.51

21.5
22.8
23.78
26.8
27.96
30.9

368
366
378
356
350
348

12.35
20.4
27.2
20.55
17.21
17

25.36
28.01
30.73
26.40
24.56
24.38

ibility degree of this blends [13], but it is well known [20]

that when the polymers in a blend system are immiscible,
repel each other and form weak interfaces of poor mechanical properties. Therefore, one can argue that the studied
PS/SBR blend system is immiscible, in spite of the fact that
the ultrasonic wave velocity and the elastic moduli vary linearly with SBR wt%. The linearity decreases of density,
ultrasonic wave velocities and elastic moduli of PS/SBR
blends accompanying the addition of SBR is probably
attributable to the weak interaction between the PS and
SBR resulting an incompatible blend system. This behavior
indicates the presence of two phases.
Also the addition of glass ber to the PS/SBR blend
increases both the longitudinal and the shear ultrasonic
wave velocities. The elastic moduli show the same trend
as ultrasonic wave velocities. The non-linear behavior suggests two phases in the reinforced blend system PS/SBR
lled with glass ber and therefore the incompatibility
behavior of this blend system occurs.
The relation between longitudinal and shear ultrasonic
wave velocities and wt% of talc is shown in Table 1. From
the table one can remark the nonlinear relation, this suggest an incompatible system. All the elastic moduli show
the same trend as the ultrasonic wave velocities indicating
that this studied system is incompatible.
The hardness as well as versus the weight percentage of
PS/SBR blend and PS/SBR blend lled with glass ber and
talc is tabulated. One can observe clearly the linear behavior of this plot in all wt% of SBR range in the studied PS/
SBR blend system. The decrease in hardness probably
attributed to the eect of adding SBR. It was reported that
[21] a high impact polystyrene (PS/SBR blend) may have
seven times the impact strength of ordinary polystyrene,
but about half the tensile strength, a lower hardness and

a softening point 15 C lower. From the above argument,

one may expect that addition of SBR to PS leads to a
decrease in hardness of PS/SBR solid blend system.
The addition of the content of the glass ber from 10 to
50 wt% shows a nonlinear increase of hardness. This is
because the glass ber reinforced PS/SBR blend system
in an incompatible one. It has occasionally been reported
by plastic technologists [20] that the addition of reinforcing
bers can successfully bridge across the weak interfaces
connect the strong individual polymer phases with each
other and thus enhance the mechanical properties. This
also may be decrease domain size and increase the interfacial attraction and adhesion and strengthen the mechanical
properties. The above argument is consistent with the
observed increase in the elastic moduli and the hardness.
In besides, the variation of the measured hardness (H)
with talc wt% for the talc reinforced PS/SBR blend system
shows a nonlinear increase of the hardness which conrms
the incompatibility of talc lled PS/SBR blend system.
The relation between the ultrasonic absorption for longitudinal waves and composition of SBR in PS/SBR blend
and PS/SBR lled with both glass ber and talc were studied at ultrasonic frequencies of 1, 2, 3 and 5 MHz, Table 1
(2 MHz was taken as an example for frequency changes
and other frequencies follow the same trend). It can be seen
that the PS/SBR blend is highly ultrasound absorbing and
it is increased with the increasing frequency. This behavior
indicates that PS and SBR macromolecules in the mixture
are immiscible. This in turn conrms the incompatibility
behavior of this system, in spite of there is no peak was
observed.
On the other hand, one maximum at about 20 wt% glass
ber and one minimum near to 40 wt% glass ber are
obtained, Table 1. This behavior indicates that PS/SBR

e1442

A.A. Higazy et al. / Ultrasonics 44 (2006) e1439e1445

lled with glass ber is an incompatible system. Such

observation is very interesting since it conrms the justication of the ultrasonic method used in this study to examine the degree of compatibility of polymer mixtures.
Moreover, one maxima at about 20 wt% of talc is
obtained when the talc reinforced the PS/SBR blend. The
relation is not linear and such behavior is evidence that this
talc lled PS /SBR blend system is an incompatible one.
3.2. High temperature results
The data of the temperatures dependence of the ultrasonic absorption coecient for longitudinal waves at fre-

quencies of 1, 2, 3 and 5 MHz in the temperature ranges

from 298 to 423 K in PS/SBR blend and PS/SBR blend
lled with both glass ber and talc are shown in Figs. 13.
3.2.1. PS/SBR blend
From inspection of Fig. 1 one can observe that for sample compositions 20, 30 and 40 wt% SBR one ultrasonic
absorption peak (peak loss) is obtained. However for samples 0 and 10 wt% SBR, two peak losses are observed. As
they shifted mostly to higher temperatures with increasing
frequency, it is natural to attempt an interpretation of these
losses in terms of relaxation type process which can be
attributed to standard linear solid type behavior with low

20
Attenuation (dB/cm)

18
16

0% SBR

14
12
10
8
1MHz
2MHz
3MHz
5MHz

6
4
2
40

Attenuation (dB/cm)

30

10% SBR

25
20
15
1MHz
2MHz
3MHz

10
5

Attenuation (dB/cm)

0
19
17
15

20% SBR

13
11
1MHz
2MHz
3MHz
5MHz

9
7
25
Attenuation (dB/cm)

Ultrasonic absorption coefficient (dB/Cm)

35

20
30% SBR
15
10

1MHz
2MHz
3MHz
5MHz

Attenuation (dB/cm )

5
0
25
23
21
19
17
15
13
11
9
7
5
3
293

40% SBR

1MHz
2MHz
3MHz
5MHz
303

313

323

333

343

353

363

373

383

393

403

413

423

433

Temperature (K)

Fig. 1. Ultrasonic absorption coecient (a) versus temperature for 0%, 10%, 20%, 30% and 40% SBR in PS/SBR blend samples at dierent frequencies.

A.A. Higazy et al. / Ultrasonics 44 (2006) e1439e1445

e1443

28
10% GF
23
18
13
1MHz
2MHz
3MHz
5MHz

8
45
40

20% GF

35
30
25

Ultrasonic absorption coefficient (dB/Cm)

20
1MHz
2MHz
3MHz
5MHz

15
10
30
25

30% GF

20
15
1MHz
2MHz
3MHz
5MHz

10
5
29

40% GF

24
19
14
1MHz
2MHz

3MHz
5MHz

50
45

50% GF

40
35
30
25
20
1MHz

15

2MHz

10

3MHz

5
0
285

5MHz

305

325

345

365

385

405

425

445

Temperature (K)

Fig. 2. Ultrasonic absorption coecient (a) versus temperature for 10%, 20%, 30%, 40% and 50% of glass ber (GF) in reinforced PS/SBR blend samples
at dierent frequencies.

dispersion and Arrhenius type relaxation times of the form

s = s0 exp(U/KT), where U is the average activation
energy. Sudhakar and Singh [13] concluded that the
absorption in polymer blends is of relaxation nature and
not due to scattering of ultrasonic waves by domains of
the dispersed phase.
A comparatively big shift of peak temperature for some
samples are observed, for example specimen 10% SBR
shows a shift in peak temperature Tp (taking for example
the second peak loss) from 363 to 380 K while the frequency changes from 1 to 5 MHz and as the same attitude
for specimen 40% SBR shows a shift in peak temperature
from 320 to 338 K. The ultrasonic absorption at peak temperature increases rapidly with the frequency that could be

observed for all samples especially for 10 and 40 wt% of

SBR.
3.2.2. PS/SBR blend lled with glass ber
High temperature results showing the temperature
dependence of the ultrasonic absorption at 1, 2, 3 and
5 MHz which are seen in Fig. 2 in the temperature ranges
from 298 to 423 K for PS/SBR lled with glass ber, 10
50 wt%.
From inspection of the Figure one can see that for
all compositions of glass ber reinforced PS/SBR
blend system one strong loss peak is observed. The
peak losses showed a maximum at 20 wt% glass ber,
Table 1.

e1444

A.A. Higazy et al. / Ultrasonics 44 (2006) e1439e1445

30
25

10%Talc

20
15
10

1MHz
2MHz
3MHz
5MHz

5
35
0
30

20%Talc

25
20

Ultrasonic absorption coefficient (dB/Cm)

15
p

10

1MHz
2MHz
3MHz
5MHz

5
30
0
25

30%Talc

20
15
10

1MHz
2MHz
3MHz
5MHz

5
40
0
35

40%Talc

30
25
20
15

1MHz
2MHz
3MHz
5MHz

10
5
350
30

50%Talc

25
20
15
1MHz
2MHz
3MHz
5MHz

10
5
0
285

305

325

345

365

385

Temperature (K)

405

425

445

Fig. 3. Ultrasonic absorption coecient (a) versus temperature for 10%, 20%, 30%, 40% and 50% of talc in PS/SBR blend samples at dierent frequencies.

However, the peak losses are observed nearly at the

same peak temperature Tp with increasing the contents of
glass ber up to 30 wt% and then decrease to 50 wt%.
It is also found that the peak losses are shifted to higher
temperatures with increasing frequency for the samples 10,
20, 30, 40 and 50 wt% glass ber. It is natural to attempt an
interpretation of these losses in terms of relaxation type
process and thermal activated relaxation time.
3.2.3. PS/SBR blend lled with talc
From inspection of Fig. 3 one can see that for polymer
composition 10, 20 and 30 wt% talc two peak losses are
observed. However, for polymer compositions 40 and
50 wt% talc, one peak loss is observed.
The two peak losses are shifted to higher temperatures
and higher peak losses with increasing the contents of talc

up to 20 wt%, and then decrease while the contents of talc

increases from 30 to 50 wt%, Table 1.
It is also found that the peak losses are shifted to higher
temperature with increasing frequency for the polymer
samples 10, 20, 30, 40 and 50 wt% talc. It is natural to
attempt an interpretation of these losses in terms of relaxation type process and thermal activated relaxation time.
For all blends, the average activation energy of the second peak loss was obtained due to plots of log F against
inverse peak temperature (1000/Tp), Table 1. The plots
yield straight lines conrm that the strong absorption
peaks are indeed consistent with a standard linear solid
(Zener type behavior with low dispersion).
The activation energy for PS/SBR blend increases from
0% SBR to 10% SBR and then decrease at 20% SBR and
nally slightly increases up to 40% SBR and ranges from

A.A. Higazy et al. / Ultrasonics 44 (2006) e1439e1445

16.7 Kcal/mole (for 0 wt% SBR) to 18.9 Kcal/mole (for

40 wt% SBR).
On the other hand, the values of the average activation
energy of PS/SBR blend lled with glass ber show nearly
constant data up to 30 wt% glass ber and then decrease to
50 wt%. Their ranges from 25.36 to 23.76 Kcal/mole in the
range from 0 to 50 wt% glass ber.
Moreover, the values of the average activation energy of
PS/SBR blend lled with talc show one maxima at 20 wt%
of talc. The average activation energy ranges from
24.38 kcal/mole (for 50 wt% talc) to 30.73 kcal/mole (for
20 wt% talc). It has occasionally been reported by plastic
technologists [20] that the addition of reinforcing talc can
successfully bridge across the weak interfaces connect the
strong individual polymer phases with each other and thus
enhance the mechanical properties. This also may be
decrease domain size and increase the interfacial attraction
and adhesion and strengthen the mechanical properties.
The above argument is consistent with the observed
increase in the elastic moduli and the hardness.
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