Effects of Composition and Processing SEBS OIL PP

Effects of Composition and Processing
Conditions on Morphology and

Properties of Thermoplastic Elastomer
Blends of SEBS–PP–Oil and
Dynamically Vulcanized EPDM–PP–Oil
P. SENGUPTA AND J. W. M. NOORDERMEER*
Faculty of Science and Technology
Department of Rubber Technology
Dutch Polymer Institute (DPI)
University of Twente
PO Box 217, 7500 AE Enschede
The Netherlands
ABSTRACT: This work presents a comparative study of the morphology and

structure-related properties of thermoplastic elastomer blends based on SEBS–
PP–oil and dynamically vulcanized EPDM–PP–oil prepared under identical
conditions. Compositions of each blend type with three different SEBS–PP and
EPDM–PP ratios by weight were made in a co-rotating twin-screw extruder and
a Brabender internal mixer. A comparative study of different electron micro-
scopic techniques for studying the morphology of these oil-extended blends is
reported. Morphological characterization using different microscopic techniques
showed a co-continuous morphology for the SEBS–PP–oil blends and droplet-
matrix morphology for the thermoplastic vulcanizate (TPV) blends. The particle
size distribution of the EPDM-phases in the TPVs prepared in the twin-screw
extruder was wider than for the Brabender mixer. No difference in the morpho-
logy was observed for the SEBS–PP–oil blends prepared in the twin-screw
extruder and Brabender, except for the blend with the highest PP content.
*Author to whom correspondence should be addressed.

E-mail: J.W.M.Noordermeer@ct.utwente.nl
JOURNAL OF ELASTOMERS AND PLASTICS Vol. 36–October 2004 307

0095-2443/04/04 0307–25 $10.00/0 DOI: 10.1177/0095244304042668
ß 2004 Sage Publications
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308 P. SENGUPTA AND J. W. M. NOORDERMEER
The elongation-at-break values were significantly higher for the SEBS–PP–oil

blends as compared to the TPV blends. The gel content of the TPVs was the
main factor determining the stress–strain properties, as influenced by the
preparation method. Also the crystallinity of the PP-phase for both SEBS–PP–
oil and TPV blends was investigated and, although being dependent on the
preparation method for the SEBS–PP–oil blends, did not reflect in the stress–
strain properties.
KEY WORDS: morphology, blends, microscopy, twin-screw extruder, internal

mixer, thermoplastic elastomers.
INTRODUCTION
based on blends of ethylene–

T HERMOPLASTIC VULCANIZATES (TPVs)
propylene–diene rubber (EPDM) and semicrystalline isotactic poly-
propylene (PP), commonly referred to as EPDM–PP TPVs, have a
resemblance in properties and applications with thermoplastic elasto-
meric blends of styrene–ethylene–butylene rubber (SEBS) and PP. Both
are available in a hardness range of 50 Shore A–50 Shore D [1].
Commercial blends of both systems also contain substantial amounts of
paraffinic oil. Although the highly oil-extended TPV blends were already
commercialized somewhere in the 1970s [2], and the SEBS–PP–oil
blends were commercialized in the early 1990s, the scientific under-
standing of their resemblance in properties and how this is controlled by
morphology and rheology, is still incomplete. Previous studies on TPVs
were directed toward understanding the morphology development
during processing [3–5], influence of different curative agents [6–8]
and understanding their deformation behavior [9]. Except for the works
of Ohlsson et al. [10] and Veenstra et al. [11] comparative information
on the SEBS–PP–oil systems are very limited. Most of the earlier works
on these two types of thermoplastic elastomer blends were based on
model formulations with very little or no processing oil, prepared either
on a twin-screw extruder or in a batch mixer. Explicit influences of the
mixing equipment on the morphology of the blends have not been
investigated thoroughly. A comparative study of the interrelationship
between morphology and rheology properties of the two systems is
necessary to fully understand these two blends.
This work presents a comparative study of the morphology and
structure-related properties of thermoplastic elastomer blends based on
SEBS–PP–oil and dynamically vulcanized EPDM–PP–oil prepared
under identical conditions. Compositions of each blend type with three

Properties of Thermoplastic Elastomer Blends 309
different SEBS–PP and EPDM–PP ratios by weight were made in a

co-rotating twin-screw extruder and a Brabender internal mixer. The
mechanical properties of the blends at all compositions, prepared with
the two kinds of mixing equipment, were investigated. Interesting
differences in the stress–strain properties of the blends were observed
for both the systems. In order to explain the differences in the stress–
strain properties, the blend morphology was studied using conventional
scanning electron microscopy (SEM), low-voltage scanning electron
microscopy (LVSEM), transmission electron microscopy (TEM), and
atomic force microscopy (AFM). To further investigate the differences
in the stress–strain properties, the gel content of TPVs was analyzed,
and the degrees of crystallinity of the PP-phase in both the systems
were also investigated.
EXPERIMENTAL
Materials
The polymers used in the present work were ethylene–propylene–

diene rubber (KeltanÕ P597; DSM Elastomers B.V.; 63 wt% ethylene,
4.5 wt% 5-ethylidene-2-norbornene (ENB) termonomer, extended with
50 wt% (100 phr) of paraffinic oil) and a styrene–ethylene–butylene-
based block copolymer (KratonÕ G 1651; KratonTM Polymers; with a
styrene to rubber ratio of 32/68 wt%). The PP (StamylanÕ P11E10; DSM
Polypropylenes B.V.) was an extrusion grade with a melt flow index at
230 C, 2.16 kg of 0.3 g/10 min. The oil used was a paraffinic mineral oil
SunparÕ 150 containing primarily paraffinic hydrocarbons. For the
EPDM formulations a phenolic resin, SPÕ 1045 was used as a curing
agent along with stannous chloride dihydrate (SnCl2 2H2O; Merck) as
catalyst and zinc oxide (rubber grade; Merck) as acid scavenger.
Additionally, as stabilizers IrganoxÕ 1076 (primary phenolic type
antioxidant, Ciba Geigy) and IrgafosÕ 168 (secondary phosphite type
antioxidant, Ciba Geigy) were used.
Blend Recipes
Three different compositions of each blend system differing in the

amount of PP at a fixed amount of oil 140 phr – were prepared
using a twin-screw extruder and Brabender internal mixer. The
complete formulations for the TPVs and SEBS–PP–oil blends are

Table 1. TPV and SEBS–PP–oil compositions in phr.
Sample ID BE1/TE1 BE2/TE2 BE3/TE3 BS1/TS1 BS2/TS2 BS3/TS3

EPDM , P597 200 200 200 – – –
SEBS, 1651 – – – 100 100 100
PP, P11E10 120 80 40 120 80 40
Oil, 150 40 40 40 140 140 140
Zinc oxide 2.5 2.5 2.5 – – –
Phenolic resin, SPÕ 1045 5.0 5.0 5.0 – – –
SnCl2 2H2O 1.0 1.0 1.0 – – –
IrganoxÕ 1076 0.5 0.5 0.5 0.5 0.5 0.5
IrgafosÕ 168 0.5 0.5 0.5 0.5 0.5 0.5
Total 369.5 329.5 289.5 361 321 281
Rubber–PP–oil (wt%) 28–33–39 31–25–44 36–14–50 28–33–39 31–25–44 36–14–50

Including 50 wt% of paraffinic oil.
shown in Table 1. For ease of discussion the blends are coded as follows:
First letter: ‘‘B’’ stands for blends made in the Brabender and ‘‘T’’ for
blends made in the twin-screw extruder.
Second letter: ‘‘E’’ stands for TPV blends and ‘‘S’’ for SEBS–PP–oil
blends.
Last digit: corresponds to the composition as shown in the Table 1.
Melt Mixing
BRABENDER MIXER
Ternary blends with a composition of EPDM- or SEBS-rubber–PP–oil

were prepared using a Brabender Plasticorder type 350S, with a mixer
chamber volume of 390 mL and fitted with Banbury-type rotors. A fill
factor of 0.7 was used.
To improve the dispersion of the large quantities of oil during mixing
in the Brabender, it was first preblended with the rubber. Since the
EPDM grade used already contained 100 phr of oil, the extra 40 phr of oil
was added on a two-roll mill; in the case of SEBS, the oil was added to
and spontaneously soaked into the porous SEBS material.
To make the TPVs, the Brabender temperature was set at 180 C and
the rotor speed at 80 rpm. The PP and stabilizers were first added in
order to melt and blend these, which took about 1 min. After this period,
the EPDM–oil and zinc oxide were added. Four minutes later, the
phenolic resin and stannous chloride were added. Mixing was continued
for another 5 min. The total mixing time was 10 min.

For making the SEBS–PP–oil blends, the temperature and rotor speed
settings were the same as for the TPVs. The PP and stabilizers were
first added to the mixer and mixing was continued till they melted after
about 1 min. The preblend of SEBS–oil was then added. The total mixing
time was 30 min.
TWIN-SCREW EXTRUDERS
The TPVs were prepared with a Werner and Pfleiderer ZSK-40

co-rotating twin-screw extruder, operated at 350 rpm. The temperature
profiles were set so that the temperature in the melt ranged from 180
to 210 C. The average residence time was about 1 min [12]. The SEBS–
PP–oil blends were made in ZSK-25 operated at 250 rpm. The SEBS was
first dry-blended with oil at room temperature. The other ingredients
(PP and stabilizers) were dry-mixed with the oil-extended SEBS to
obtain all ingredients in a dry-mixed state. This mixture was then fed into
the extruder at a constant rate of 5–10 kg/h. The extruded strands were
cooled in a water bath and pelletized [13]. Temperature profiles were
similar to those used in the ZSK-40 for the preparation of the TPVs.
Compression Molding
After mixing, the materials were compression-molded using a WLP

1600/5*4/3 Wickert laboratory press at 200 C for 3 min under a pressure
of 10 MPa and then cooled under pressure to about 30 C. Sheet
thickness was 2 mm. The sheets were punched into dumbells (ISO-37,
type 2) for tensile measurements.
Mechanical Properties
Tensile properties were determined at room temperature according to

ISO-37 using a Zwick Z020 universal testing machine equipped with a
500 N load cell. A crosshead speed of 50 mm/min was used to measure
the E-modulus and 500 mm/min to measure the tensile strength and
elongation-at-break. The reported results of each blend are the average
of at least four measurements. The standard deviations in the experi-
ments were less than 10%.
Gel Measurements on TPVs
In order to estimate the degree of cross-linking of the EPDM-phase in

the TPVs, the samples were subjected to a series of solvent extractions.

About 1.5 g of TPV samples were extracted for 24 h through a stainless

steel pouch in boiled acetone to remove the oil and stabilizers, followed
by extraction for 48 h with boiling xylene to remove the PP and the
soluble rubber. The amount of gel content was calculated from the
weight of the residue after xylene extraction [14].
Solvent Extraction on SEBS–PP–Oil Blends
In order to estimate the degree of co-continuity of the SEBS-phase in

the SEBS–PP–oil blends, about 1.5 g of SEBS–PP–oil samples were
immersed in toluene at room temperature for 24 h. The change in
sample weight after extraction was compared to the amount of
extractable phase originally present in the sample. This fraction is the
degree of co-continuity of the SEBS-phase.
Degree of Crystallinity of the PP-phase by Thermal Analysis
The thermal behavior of the blends was studied by means of a Perkin

Elmer DSC 7 differential scanning calorimeter (DSC). The samples,
about 5–10 mg were heated at a rate of 10 C/min from 25 C up to 200 C,
maintained at this temperature for another 5 min and then cooled
down to 100 C at the same rate. At 100 C they were kept for another
5 min and then reheated to 25 C at a rate of 5 C/min. The crystallization
temperatures and enthalpy of fusion of PP were obtained from the
cooling curve. The standard deviations in the experiments were less
than 5%.
Morphological Characterization
After the blends had been compression-molded, small samples were

taken for electron microscopic examination. Three different microscopic
methods – SEM, LVSEM, and TEM were used to study the morphology
of both the blend systems. For SEM and TEM, the samples were
microtomed at 130 C using a diamond knife. For LVSEM the samples
were fractured in liquid nitrogen. In all the cases the samples were
vapor-stained with ruthenium tetraoxide. SEM studies were performed
using Hitachi S-800 field emission scanning electron microscope.
LVSEM studies were performed using a Leo 1550 scanning electron
microscope. TEM studies were performed using a Philips CM30
transmission electron microscope. For SEM and LVSEM samples the
staining time was 30 min. The staining time for TEM samples was
10 min. The particle size distribution in the TEM images was analyzed

using NIH imaging software [15]. For SEBS–PP–oil blends, AFM was
also used to study the blend morphology in combination with SEM,
LVSEM, and TEM. The AFM measurements were performed in tapping
mode using a Nanoscope III scanning probe microscope (Digital
instruments). The instrument was equipped with an E-scanner.
Commercially available silicon nitride cantilevers were used.
RESULTS
Stress–Strain Properties
Interesting differences were obtained in the stress–strain properties

of the TPV and SEBS–PP–oil blends at identical compositions and
mixing conditions. First the properties of the individual systems are
reported. An overall comparison of the two systems is given afterwards.
TPV BLENDS
The stress–strain properties of the TPV blends prepared in two types

of mixing equipment are shown in Table 2. The values of E-moduli,
tensile strength, and elongation-at-break increase with increasing
amount of PP. The blends prepared in the twin-screw extruder show
consistently higher E-moduli and tensile strengths than the blends
prepared in the Brabender.
SEBS–PP–OIL BLENDS
The stress–strain properties of the SEBS–PP–oil blends prepared in

the two types of mixing equipment at three different SEBS–PP–oil
compositions are shown in Table 3. The values of E-moduli and tensile
Table 2. Stress–strain properties of TPV blends.
E-modulus Tensile Strength Elongation at

(MPa) (MPa) Break (%)
Composition
EPDM–PP–oil Brabender Twin-screw Brabender Twin-screw Brabender Twin-screw
(wt%) Blend Mixer Extruder Mixer Extruder Mixer Extruder
28–33–39 1 50.0 64.0 9.0 11.0 500 500

31–25–44 2 25.0 30.0 6.2 7.0 380 390
36–14–50 3 5.0 6.0 4.0 5.0 300 340

Table 3. Stress–strain properties of SEBS–PP–oil blends.
E-modulus Tensile Strength Elongation at

(MPa) (MPa) Break (%)
Composition
SEBS–PP–oil Brabender Twin-screw Brabender Twin-screw Brabender Twin-screw
(wt%) Blend Mixer Extruder Mixer Extruder Mixer Extruder
28–33–39 1 60.0 49.0 12.0 12.0 550 550

31–25–44 2 25.0 16.0 7.0 7.4 550 550
36–14–50 3 5.0 5.0 5.0 6.0 600 600
strength increases with increasing amount of PP content. The elonga-

tion at break values remained more or less constant. The stress–strain
properties of the blends are practically the same for both the types of
mixers, except for the values of E-moduli, which are higher for
compositions 1 and 2 for the blends made in the Brabender.
COMPARISON OF THE TPVS AND SEBS–PP–OIL BLENDS
The E-moduli of the SEBS–PP–oil blends are lower than the corres-
ponding TPV blends at all compositions when mixed in the twin-screw
extruder. For blends made in the Brabender the E-moduli are the same
for both the blend types with the exception of BE1 versus BS1. All
tensile strengths are higher for the SEBS–PP–oil blends than the TPVs.
The most striking difference is seen in the elongation-at-break values of
these two systems. All elongation-at-break values are higher for the
SEBS–PP–oil blends and remains more or less constant with increasing
PP content. The elongation-at-break values for the TPV blends are
comparatively less and they increase with increasing PP content. For
composition 1, the values are almost comparable for both the systems.
Representative stress–strain plots for both systems at compositions
TE2 and TS2 are shown in Figure 1. At low strains of 0.15–0.25% used
for the E-modulus determination, the TPV appears to be stiffer than the
SEBS–PP–oil blend. At higher strains, the SEBS–PP–oil blend shows a
more pronounced strain hardening effect with higher tensile strength
and elongation-at-break as compared to the TPVs.
To explain the differences observed in the stress–strain properties of
the two blend systems, the following aspects were studied: (a) differ-
ences in degree of cure of the EPDM-phase by gel measurements;
(b) differences in the degree of crystallinity of the PP-phase by DSC;
(c) differences in the morphology due to different compositions and
mixing conditions by TEM, SEM, LVSEM, and AFM.

FIGURE 1. Stress–strain plot for blends TE2 and TS2.
Table 4. Gel measurements for TPVs.
Gel Content (%)
Composition Brabender Twin-screw

EPDM–PP–oil (wt%) Blend Mixer Extruder
28–33–39 1 96 98
31–25–44 2 96 96
36–14–50 3 96 99
Gel Measurements of TPVs
In order to judge the level of cross-linking of the EPDM-phase in the

TPVs, results from the gel measurements are given in Table 4. In all the
cases the gel content is higher than or equal to 95%. Taking into account
the experimental scatter in the gel measurement, the results show a
tendency to higher gel contents obtained for the TPVs made in the twin-
screw extruder than for those made in the Brabender. At high gel con-
tent values, small differences in gel content relate to large differences
in the degree of cross-linking [16]. This implies that the cross-link
density of the EPDM-phase in TPVs made in the twin-screw extruder
was considerably higher – which contributes to a higher E-modulus

and possibly tensile strength – than in the case of TPVs made in the
Brabender.
Crystallinity of the PP-phase
From the DSC measurements on all samples, the degree of crystal-

linity Xc of the PP-phase was calculated by applying the equation [17]
100 H ðPPÞ
Xc ðPPÞ ¼ ð1Þ
H 0 ðPPÞ
where H ðPPÞ is the apparent enthalpy of fusion per gram of PP in the

blend; H 0 ðPPÞ is the heat of fusion per gram of 100% crystalline PP
i.e., 209 J/g [17].
The degrees of crystallinity of the TPVs and SEBS–PP–oil blends are
given in Table 5. Except for composition 1, the values are grossly
comparable for TPVs made in the two instruments. Thus, we conclude
that the differences in the stress–strain properties of the TPVs having
compositions 2 and 3 are not due to different crystallinity of the PP-
phase. The SEBS–PP–oil blends made in the twin-screw extruder show
significantly higher degrees of crystallinity than the blends made in the
Brabender at all compositions, but this does not correlate with the
tensile properties of these blends. This implies that the PP crystallinity
does not have an effect on the differences in the stress–strain properties
of the SEBS–PP–oil blends either.
Morphological Characterization of EPDM–PP TPVs and

SEBS–PP–Oil Blends
The blends were first characterized by using conventional SEM after

coating the microtomed surfaces with gold. The images obtained using
Table 5. Degree of PP crystallinity of TPVs and SEBS–PP–oil blends.
Degree of Crystallinity of Degree of Crystallinity of

TPV Blends (%) SEBS–PP–oil Blends (%)
Composition
Rubber –PP–oil Brabender Twin-screw Brabender Twin-screw
(wt%) Blend Mixer Extruder Mixer Extruder
28–33–39 1 42 48 41 46
31–25–44 2 40 39 41 46
36–14–50 3 42 40 49 52

The rubber is EPDM for TPV formulations and SEBS for SEBS–PP–oil blends.

secondary electrons and taken at an operating voltage of 3–6 keV were of

poor quality due to sample charging. Charging effects such as bright
spots in the image arise due to build up of an electric negative charge on
the specimen surface. This occurs at high acceleration voltages, if the
number of electrons leaving the surface is not sufficient to compensate
for the incoming ones. Charging can be avoided by applying a conductive
coating or working at low acceleration voltages (LVSEM), also known as
crossover voltages, where the charges balance each other [18].
In our experiments charging occurred even after applying gold coating
to the samples. Hence LVSEM was used instead of SEM. Comparative
images of blend BE1 made with the two techniques are given in Figure 2.
With the use of LVSEM over SEM, the following advantages were
obtained:
– gold coating was not necessary.
– charging effects could be avoided due to low operating voltages.
– significant improvement in the resolution, the more so in the case of
TPVs.
Under similar compositions and blend preparation conditions, the
morphologies of the two systems were completely different. The TPVs
showed droplet-matrix morphology in which EPDM particles were
FIGURE 2. Morphology of BE1 as revealed by (a) conventional SEM and (b) LVSEM.
The image in (a) is blurry due to sample charging. This can be avoided in LVSEM (b).

FIGURE 2. Continued.
dispersed in the PP matrix. On the other hand, the SEBS–PP–oil blends

showed co-continuous morphologies in which SEBS–oil and PP–oil
formed co-continuous phases. Further details of the blend morphology
for each system are described below.
TPV BLENDS
Differences in the morphology of the TPV blends were seen more as a

consequence of changes in mixing conditions (twin-screw extruder vs.
Brabender) than due to changes in blend composition. Figure 3(a)
and (b) shows the TEM images of TPV blends BE1 and TE1,
respectively. The TEM images for other blend compositions are not
shown due to similar morphologies. In all the cases the observations
obtained from TEM were reconfirmed using LVSEM. In some blends the
morphology was better revealed using LVSEM e.g. blends BE2 and TE2
(Figure 4). By combining TEM and LVSEM it was seen, that for all
compositions of the TPVs, the EPDM are dispersed as particles in the
PP matrix. The particle shapes are quite complicated. In TPVs prepared
in the twin-screw extruder, the EPDM particles are more elliptical in
shape. Similar elliptical shapes of EPDM particles were reported by

Jayraman [19] in EPDM–PP TPV blends. For TPVs prepared in the

Brabender the particles are more uniform and spherical in shape. The
particle size distributions for two extreme PP–EPDM compositions
reveal that, with the exception of sample BE1, the largest amount of
EPDM particles is in between 1 and 2 mm, irrespective of the preparation
method used (Figure 5). The particle size distribution is wider for the
twin-screw extruded blends than for the TPVs produced in the
Brabender mixer.
The droplet-matrix morphology of a TPV is more or less independent
of composition. This can be seen in the particle size analysis of the
blends prepared with the twin-screw extruder spanning the whole
composition range (Figure 6).
SEBS–PP–OIL BLENDS
In comparison to the differences in the morphology observed in the

TPVs, the differences of morphology in the SEBS–PP–oil system were
FIGURE 3. TEM of TPV blends (a) BE1 and (b) TE1.

less conspicuous. Figure 7(a) and (b) shows the TEM images of different
SEBS–PP–oil blends BS1 and TS1, respectively. The TEM images for
other compositions are not shown due to similar morphologies. The dark
regions correspond to the clusters of styrene blocks in the SEBS-phase.
The brighter phase is made up of PP, oil, and ethylene–butylene blocks
of the SEBS-phase.
At all compositions, the TEM images show the SEBS- and PP-phases
to form a co-continuous morphology. Detecting co-continuity differences
with a single technique is difficult. The TEM images alone are
insufficient for unambiguous determination of the blend morphology.

FIGURE 4. LVSEM images of TPV blends (a) BE2 and (b) TE2.
For this reason the TEM images were supplemented with LVSEM and
AFM images. Representative LVSEM and AFM images are shown in
Figures 8 and 9, respectively for the blends BS1 and TS1. By combining
the information from all the three microscopic techniques it appears
that at composition 1, the blends made in the twin-screw extruder are
less co-continuous than the corresponding blends made in the
Brabender. For blends with lower amount of PP no differences in the

70
TE1
BE1
No. of particles (%)
60 TE3
50 BE3
40
30
20
10
0
0-1 1-2 2-3 3-4 4-5
particle size (mm)
FIGURE 5. Particle size distribution for TPV blends TE1, BE1, TE3, and BE3.
80 TE1
No. of particles (%)
60 TE2
40 TE3
20
0
0-1 1-2 2-3 3-4 4-5
particle size (mm)
FIGURE 6. Particle size distribution for three different TPV blends made in the twin-
screw extruder.
degree of co-continuity between the SEBS- and PP-phases could be

detected.
To further confirm the co-continuous morphology observed with TEM
and LVSEM, the blends were kept in toluene at room temperature for
24 h. This resulted in complete extraction (over 90%) of the SEBS and oil
from all the blend compositions. The remaining PP structure was self-
supporting after extraction (Table 6). This proves that almost all of
the SEBS-phase was accessible to the solvent, which is only possible if
the SEBS-phase is co-continuous.
DISCUSSION
The results show that the TPVs made in the twin-screw extruder have
a wider particle size distribution than the corresponding blends made in

the Brabender. The largest amounts of EPDM particles are in between

1 and 2 mm. Important differences between the mixing conditions in a
twin-screw extruder and Brabender mixer are:
(a) Shear rate – which is higher in a twin-screw extruder than in an
internal mixer.
(b) Residence time – being higher for the Brabender mixer. The
difference depends on the mixing time used for the Brabender. In
the case of TPVs the residence time in the Brabender (10 min) was
roughly about 10 times longer than the residence time in the twin-
screw extruder (about 1 min).
(c) Temperature profiles 180–210 C for TPV blends made in the twin-
screw extruder; in the Brabender the temperature of the mixing
chamber was in between 180 and 190 C.
On the basis of higher shear rate, a smaller particle size for the
dispersed phase in blends made in the twin-screw extruder is expected.
FIGURE 7. TEM of SEBS–PP–oil blends (a) BS1 and (b) TS1.

However this is not always the case. In experiments with low-density

polyethylene–polystyrene blends [20] and polycarbonate–polypropylene
blends [21] it was found that at lower viscosity ratios the phase
sizes and size distributions were identical for the two kinds of mixing
equipment.
Our experiments with TPVs show that there is a difference in
phase-size distribution for the blends prepared in twin-screw extruder
and Brabender. The particles of EPDM are more uniform in a
Brabender. The greater uniformity is related to the larger residence
time of the blends in the Brabender as compared to the twin-screw
extruder. The larger residence results in larger total shear (shear
rate residence time) in the Brabender mixer, responsible for further
breakdown of remaining larger EPDM domains into smaller uniform
domains.

FIGURE 8. LVSEM of blends (a) BS1 and (b) TS1.

FIGURE 9. AFM of blends (a) BS1 and (b) TS1. The left image in each case is the height
image and the right image is the phase image.
The study of the gel content, crystallinity, and morphology of the

TPVs show that the differences in the stress–strain properties of the
TPVs made in the twin-screw extruder and Brabender internal mixer
are primarily governed by the cross-link density of the PP-phase. The
blend morphology and crystallinity are grossly comparable in both the
mixing equipment.

Table 6. Extraction of SEBS–PP–oil blends.
Amount of SEBS Extracted (%)

Composition
SEBS–PP–oil (wt%) Blend Brabender Mixer Twin-screw Extruder
28–33–39 1 99 95
31–25–44 2 96 100
36–14–50 3 98 97
While the rubber-phase was dispersed in the TPVs, the SEBS-phase in

SEBS–PP–oil blends is co-continuous with the PP-phase at similar
compositions for both mixing devices. The reason for this must reside in
the block copolymer structure of SEBS. The condition for the formation
of such co-continuous morphologies is the existence of stable, elongated
SEBS structures that do not show breakup or retraction in the melt.
Experiments with block copolymer blends, like SEBS–PP and SEBS–
PMMA, by Veenstra et al. [11] have shown that with physical cross-links
present in the system during mixing, breakup and retraction of
co-continuous structures can be severely limited or even totally stopped.
The low interfacial tension between PP and SEBS and the high
yield stress of SEBS further helps to stabilize these co-continuous
structures.
Our experiments with the SEBS–PP–oil blends have shown that
at composition 1 the blend made in the twin-screw extruder was less
co-continuous than the blend made in the Brabender mixer. Such
differences in the degree of co-continuity did not exist for other
compositions. Possible reasons for such observations, specially relevant
for SEBS–PP compositions with the lowest amount of SEBS-phase i.e.,
for composition 1, are again related to the differences in residence time
of the blend in the twin-screw extruder. The residence time of SEBS–
PP–oil blends in the Brabender was 30 min, which implies about a
30-times larger residence time than for the twin-screw extruder.
A schematic representation of the process of morphology development
in twin-screw extruder and internal mixer as discussed by Scott and
Macosko [22] is given in Figure 10. The process of morphology devel-
opment is governed by dispersion of generally highly viscous SEBS in
low-viscous molten PP. With combined effect of time, temperature,
and, shear the SEBS-phase will soften and will be stretched into sheets
in the molten PP. The morphology at this point is co-continuous. At the
same time there will be a breakdown of sheets by hole formation due to
shear and elongational forces in the twin-screw extruder and Brabender.
Thus, there is a dynamic equilibrium between the process of breakup of

Breaking of lace Tcoalescence > Tresidence time

structure
Twin-screw extruder
220 °C
Temp Brabender
Extruder
curve
curve
Brabender
Sheets of softened rubber in PP
Tcoalescence << Tresidence time

Solid rubber
180 °C
in molten PP
Time
FIGURE 10. Schematic representation of the morphology development in SEBS–PP–oil
blends in the melt showing the dynamic equilibrium between coalescence and breakdown
of SEBS particles in PP matrix.
the phases and coalescence. If the residence time of the blends is less
than the coalescence time, the blend will be less co-continuous as
compared to the morphology of a similar blend prepared in the
Brabender. This process is also composition dependent. The effect will
be more manifested in blends with less SEBS content due to lower
probability of coalescence.
The stress–strain properties of the SEBS–PP–oil blends are mostly
similar for both twin-screw extruder and Brabender and independent of
the differences in crystallinity. We have seen that at higher strains, the
SEBS–PP–oil blend shows a more pronounced strain hardening effect
with higher tensile strength and elongation-at-break as compared to the
TPVs. The reason for this effect lies in the mechanism of tensile
deformation of the PP-phase that occurs in combination with the
deformation of the SEBS-phase. Modeling experiments by Lee et al. [23]
showed that the strain hardening response is in fact dominated by the
molecular orientations of the amorphous domains in the PP-phase and
upon very large strains, whereupon the amorphous orientation has
nearly locked the crystallographic texture, begins to significantly
contribute to the strain hardening. This may account for the higher
elongation-at-break values for the TPV blends having composition 1

(having highest PP content) as compared to TPV blends having

compositions 2 and 3.
For SEBS–PP–oil blends the orientation of the PP-phase occurs along
with the orientation of the co-continuous SEBS-phase. The mechanism
of block copolymer tensile deformation has been studied using TEM by
Beecher et al. for SBS block copolymers [24]. Three distinct stages of
deformation were observed. At first, strings of polystyrene spheres are
seen to become aligned perpendicular to the direction of the applied
force. Subsequently, these strings of beads tend to orient in the force
field and form V-shaped patterns. At high force fields the connections
between the particles break and the particles become ellipsoidal in
shape. The high strength of these materials is thought to originate from
this orientation and subsequent inelastic deformation of polystyrene
spheres or cylinders embedded within a continuous rubbery matrix,
a process that dissipates a large amount of strain energy and allows the
remaining strain to be distributed more evenly throughout the mass.
CONCLUSIONS
In this study different microscopic techniques were used to study the

morphology in ternary thermoplastic elastomer blends of SEBS–PP–oil
and dynamically vulcanized EPDM–PP–oil. TEM and LVSEM were
found to be more suitable than conventional SEM. With LVSEM no gold
coating is necessary on the samples, the problem of charging can be
avoided, and the resolution is significantly higher than the images
obtained with conventional SEM.
The stress–strain properties of the TPV blends at identical composi-
tions depend on the mixing equipment used. Using a twin-screw
extruder a higher degree of cross-linking can be obtained resulting in
higher E-modulus as compared to the blends made in a Brabender
mixer. The crystallinity of the PP-phase in the TPV blends is more or
less comparable for both the types of mixing equipment. The particle
size distribution of the TPV blends made in the twin-screw extruder is
wider than those made in the Brabender. This can be explained from the
differences in total shear for the blends in the two instruments, being
much larger for the Brabender than for the twin-screw extruder.
The stress–strain properties of the SEBS–PP–oil blends at identical
compositions are quite independent of the mixing equipment used. For
compounds with a high amount of PP, the blends made in the twin-
screw extruder appear to be less co-continuous than the blends made in
the Brabender. Similar to the TPVs, this can also be explained on the

basis of residence time differences for the blends in the two instruments.
In general the elongation-at-break values of the SEBS–PP–oil blends
having co-continuous morphology is higher as compared to the TPVs
with dispersed EPDM-phase. This is due to concerted orientation of
the co-continuous SEBS, and PP-phases and subsequent breakup of
the polystyrene domains at high strains.
ACKNOWLEDGMENTS
The authors wish to acknowledge the financial support from the

Dutch Polymer Institute (DPI), The Netherlands. The production of the
extruder blends was done by collaborators of Kraton Polymers and DSM
Elastomers. The DSC measurements were done by Mr. W. Sengers,
Technical University Delft. They are also indebted to the Industrial
User Committee members from DSM Elastomers, Kraton Polymers, Océ
Technologies, Akzo Nobel, and TNO Institute of Industrial Technology
for providing them with samples and for useful discussions. They
are also grateful to M. Smithers from Central Material Analysis Lab
(CMAL), University of Twente, for the LVSEM and TEM images and to
Mr. C. Padberg from Material Science and Technology of Polymers
(MTP), University of Twente, for the AFM experiments.
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Encyclopedia of Industrial Chemistry, Electronic Release, 6th edn,
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Effects of Composition and Processing SEBS OIL PP

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Effects of Composition and Processing SEBS OIL PP

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Effects of Composition and Processing

Conditions on Morphology and

ABSTRACT: This work presents a comparative study of the morphology and

*Author to whom correspondence should be addressed.

JOURNAL OF ELASTOMERS AND PLASTICS Vol. 36–October 2004 307

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The elongation-at-break values were significantly higher for the SEBS–PP–oil

KEY WORDS: morphology, blends, microscopy, twin-screw extruder, internal

based on blends of ethylene–

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different SEBS–PP and EPDM–PP ratios by weight were made in a

The polymers used in the present work were ethylene–propylene–

Three different compositions of each blend system differing in the

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Table 1. TPV and SEBS–PP–oil compositions in phr.

Sample ID BE1/TE1 BE2/TE2 BE3/TE3 BS1/TS1 BS2/TS2 BS3/TS3

Ternary blends with a composition of EPDM- or SEBS-rubber–PP–oil

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The TPVs were prepared with a Werner and Pfleiderer ZSK-40

After mixing, the materials were compression-molded using a WLP

Tensile properties were determined at room temperature according to

Gel Measurements on TPVs

In order to estimate the degree of cross-linking of the EPDM-phase in

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About 1.5 g of TPV samples were extracted for 24 h through a stainless

Solvent Extraction on SEBS–PP–Oil Blends

In order to estimate the degree of co-continuity of the SEBS-phase in

Degree of Crystallinity of the PP-phase by Thermal Analysis

The thermal behavior of the blends was studied by means of a Perkin

After the blends had been compression-molded, small samples were

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Interesting differences were obtained in the stress–strain properties

The stress–strain properties of the TPV blends prepared in two types

The stress–strain properties of the SEBS–PP–oil blends prepared in

Table 2. Stress–strain properties of TPV blends.

E-modulus Tensile Strength Elongation at

28–33–39 1 50.0 64.0 9.0 11.0 500 500

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Table 3. Stress–strain properties of SEBS–PP–oil blends.

E-modulus Tensile Strength Elongation at

28–33–39 1 60.0 49.0 12.0 12.0 550 550

strength increases with increasing amount of PP content. The elonga-

COMPARISON OF THE TPVS AND SEBS–PP–OIL BLENDS

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FIGURE 1. Stress–strain plot for blends TE2 and TS2.

Table 4. Gel measurements for TPVs.

Gel Content (%)

Composition Brabender Twin-screw

Gel Measurements of TPVs

In order to judge the level of cross-linking of the EPDM-phase in the

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Crystallinity of the PP-phase

From the DSC measurements on all samples, the degree of crystal-

where H ðPPÞ is the apparent enthalpy of fusion per gram of PP in the

Morphological Characterization of EPDM–PP TPVs and

The blends were first characterized by using conventional SEM after

Table 5. Degree of PP crystallinity of TPVs and SEBS–PP–oil blends.

Degree of Crystallinity of Degree of Crystallinity of

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secondary electrons and taken at an operating voltage of 3–6 keV were of