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New understanding of microstructure formation

of the rubber phase in thermoplastic
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Cite this: Soft Matter, 2014, 10, 1816

vulcanizates (TPV)
Hanguang Wu,b Ming Tian,*ab Liqun Zhang,ab Hongchi Tian,b Youping Wuab
and Nanying Ning*ab

The breakup of the rubber phase in an ethylenepropylenediene monomer (EPDM)/polypropylene (PP)

Received 9th September 2013
Accepted 7th January 2014
DOI: 10.1039/c3sm52375f
www.rsc.org/softmatter
blend at the early stage of dynamic vulcanization is similar to that in an unvulcanized EPDM/PP blend
because of the low crosslink density of the EPDM phase. In this work, the minimum size of the rubber
phase in the unvulcanized EPDM/PP blend was rst calculated by using the critical breakup law of
viscoelastic droplets in a matrix. The calculated results showed that the minimum size of the rubber
phase in the unvulcanized blend was in the nanometer scale (2546 nm), not the micrometer scale as
reported in many works. Meanwhile, the actual size of the rubber phase in the thermoplastic vulcanizate
(TPV) at both the early stage and the nal stage of dynamic vulcanization was observed by using peak
force tapping atomic force microscopy (PF-AFM). The results indicated that the EPDM phase indeed
broke up into nanoparticles at the early stage of dynamic vulcanization, in good agreement with the
calculated results. More interestingly, we rst revealed that the micrometer-sized rubber particles
commonly observed in TPV were actually the agglomerates of rubber nanoparticles with diameters
between 40 and 60 nm. The mechanism for the formation of rubber nanoparticles and their
agglomerates during dynamic vulcanization was then discussed. Our work provides guidance to control
the microstructure of the rubber phase in TPV to prepare high performance TPV products for a wide
range of applications in the automobile and electronic industries.

processability of TPV.211 Therefore, the microstructure of TPV

1 Introduction
Thermoplastic vulcanizates (TPVs) are a particular group of
high performance thermoplastic elastomers produced by
dynamic vulcanization, which consists of the selective cross-
linking of the elastomer and its ne dispersion throughout the
thermoplastic phase under intensive mixing.1 TPVs combine
the excellent resilience of ordinary vulcanized rubbers, and the
high processability and recyclability of thermoplastics. There-
fore, they have attracted considerable attention in the past two
decades, and have been widely used in industries such as the
automotive industry, building, and electronics. Nowadays, for
environmental protection and resource saving, TPV products
comprise the fastest growing rubber market.2
To obtain TPV products with high soness and elasticity, the
content of the rubber phase in TPV should be in the range of 60
80 wt%. The shape and size of the rubber phase in the matrix
has a signicant inuence on the mechanical properties and
a
State Key Laboratory of OrganicInorganic Composites, Beijing University of Chemical
Technology, Beijing 100029, China. E-mail: tianm@mail.buct.edu.cn; ningny@mail.
buct.edu.cn; Fax: +86 10 64433964; Tel: +86 10 64434860
b
Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer
Materials, Beijing University of Chemical Technology, Beijing 100029, China
has attracted much attention in the last two decades. Many
studies have reported that the rubber phase dispersed in the
matrix consists of spherical particles with a diameter of 0.5
3.0 mm.2,8,1218 On the other hand, it has been reported that a
decrease in the size of these rubber particles leads to a signi-
cant increase in the ultimate tensile strength and elastic
recovery of TPV.10 These reports motivate us to ask the following
questions: Can we further reduce the rubber particle size to
improve the performance of TPV? To answer this question, the
formation mechanism of these rubber particles in TPV needs to
be understood.
It has been reported that the breakup of the rubber phase in
ethylenepropylenediene monomer (EPDM)/polypropylene
(PP) TPV only occurs at the early stage of dynamic vulcanization,
when the crosslink density of the EPDM phase is low.13,19,20 In
this case, the breakup of the EPDM rubber phase is similar to
that of unvulcanized EPDM in the EPDM/PP blend, in which the
breakup and coalescence of the dispersed phase (EPDM) in the
PP matrix occur simultaneously under a rotational shear
eld.2128 However, the broken rubber particles in a dynamically
vulcanized blend cannot coalesce because of the in situ vulca-
nization of the rubber phase.13 Thus, the size of the EPDM
particles in a dynamically vulcanized EPDM/PP blend could be

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similar to the available size of the broken EPDM droplets before Table 2 Composition of premix for use in Haake rheomix
coalescence in an unvulcanized EPDM/PP blend.
Ingredient Content of the ingredients
Therefore, in the present work, the minimum size of the
(wt%)
broken rubber particles in the EPDM/PP blend was rstly
calculated by using the formula about the critical breakup EPDM 59.4
condition of the viscoelastic droplets in a viscoelastic matrix, as PP 39.6
proposed by Wu.29 Meanwhile, the actual size of the rubber 1010 0.15
Resol 0.7
particles in TPV at both the early stage and the nal stage of SnCl2 0.15
dynamic vulcanization was observed by using a new kind of
peak force tapping atomic force microscopy (PF-AFM) for its
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higher resolution. In this study, we explored the mechanism for

the real microstructure formation of TPV during dynamic
vulcanization. Furthermore, we aimed to explore the mecha-
nism to reduce the size of the rubber phase in TPV to provide
guidance for obtaining high performance TPV.
2 Experimental section
2.1 Materials
Table 1 lists the characteristic properties of the injection-grade
PP and the EPDM, which were bought from Basell Co., Ltd.
(Thailand) and Mitsui Chemicals Co., Ltd. (Japan), respectively.
The crosslinking agents were composed of resol and SnCl2
supplied by Xinjiang Karamay Oileld. A commercially available
pentaerythritol tetrakys 3-(3,5-ditert-butyl-4-hydroxyphenyl)
propionate (1010) was used as an antioxidant.
2.2 Preparation of the samples
EPDM/PP TPV was prepared in a Haake internal mixer (HAAKE
Rheomix 600 OS, Thermo Fisher Scientic, America) equipped
with two counter-rotating rotors. Trigonox T101 (DHBP; Akzo
Nobel, Holland) was used as initiator. The premix of the EPDM/
PP blend in the Haake rheomix was prepared by using the two-
roll mill as follows. First, the EPDM rubber and PP were fed into
the two-roll mill in the required mass ratio (60 : 40) at 180
C.
Meanwhile, the antioxidant was added to prevent the aging of
PP. Subsequently, the homogeneous blend was transferred to
another two-roll mill at ambient temperature, and the cross-
linking agents and the antioxidants were added. The composi-
tion of the premix is given in Table 2.
The premix obtained was fed into the Haake rheomix at
170
C and a rotor speed of 80 rpm. In order to follow the
mechanism by which the nal microstructure of the EPDM/PP
TPV is formed, samples were taken at dierent mixing times
and immediately cooled down in liquid nitrogen to stop the
crosslinking reaction and avoid further morphological changes.
2.3 Rheological measurements
The rheological behavior of EPDM and PP was characterized by
dynamic rheological measurements in a stress-controlled rota-
tional rheometer (AR-G2, TA Instruments, America) using
parallel-plate geometry (radius 10 mm; gap 1 mm). The
reason that we use parallel-plate geometry instead of cone-plate
geometry is that the viscosities of EPDM and PP measured in
this study are in the linear viscoelastic range because of the low
shear rate. In addition, the viscosity of EPDM rubber and PP at a
relatively low temperature (170
C) is very high, thus the cone-
plate geometry is not suitable.
EPDM and PP were compression-molded into discs of 10 mm
radius and 1 mm thickness at 170
C by using a 30 000 kilogram
press. Frequency sweep experiments were performed at 170
C
in the range of 150 rad s1. The shear rate between two plates is
not uniform. In order to obtain the relationship between
complex viscosity and shear rate, the average shear rate (g) _
between two plates was calculated according to the formula
below:30
R
: ur
pR2 g 2pr (1)
0 h
where u is the angular velocity, r is the radius at dierent
positions, and h and R are the gap between the two plates and
the radius of a plate, respectively.
2.4 Surface energy measurements
Because of the high melt viscosities of EPDM and PP,
measurement of interfacial tension between them (g12) at the
temperature at which the breakup of the EPDM phase occurs
(170
C) was not possible. Therefore, we calculated the g12
values from the polarities (c) and surface tensions (g) of EPDM
and PP at 170
C. Because the c values are independent of
temperature, the c values of EPDM and PP at 170
C were
determined at room temperature by contact angle method with
a Dataphysics instrument (model DCAT 21; Germany), and the

Table 1 Characteristics of materials used

MFIa Tm Ethylene content Monomer viscosity

(g 10 min1) (
C) (wt%) (ML (1 + 4) 125
C Pa1 s1)

PP 0.5 159
EPDM 66 61
a
At 230
C and 2.16 kg. MFI melt ow index; Tm melting point.

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Soft Matter
g values of EPDM and PP at 170
C were measured with the
pendent-drop method.
2.5 Morphology studies
The samples morphology was examined by using a new type of
peak force tapping atom force microscope (PF-AFM) (Nano-
scope IIIa, Bruker corporation, Germany) because of its higher
resolution, as reported previously.31 Before the observations, the
samples were polished at 130
C by using a cryo-ultramicro-
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tome (Leica EM UC7; Germany). In order to observe the size and
shape of the individual rubber particles, we dissolved the
dynamically vulcanized TPV in hot xylene for 96 hours and
refreshed the solvent every 24 hours to wash o the dissolved
PP. The suspension obtained was then spin coated on a clean
coverslip by using a spin coater (KW-4A; China). The sample
obtained was observed by the PF-AFM as well. The rubber
particle size was determined with the Image-Pro Plus 4.5
soware.32
3 Results and discussion
3.1 Theoretical calculation of critical size of rubber phase in
the matrix
The breakup of the rubber phase in EPDM/PP TPV occurs when
the premix is just fed into the Haake rheomix.13,19 Because of its
extremely low crosslink density, the deformation and breakup
of the rubber phase at this time can be approximated by those of
unvulcanized EPDM in EPDM/PP blend in a rotational shear
eld. For an immiscible polymer blend such as unvulcanized
EPDM/PP blend, the minimum size of the EPDM dispersed
phase can be obtained from the critical breakup law proposed
by Wu.29 The precondition for the breakup of an EPDM spher-
ical viscoelastic droplet with initial diameter a is that the
droplet is rst stretched under a rotational shear eld to be an
ellipsoid droplet with the major semi axis L and short semi axis
B, as shown in Fig. 1. The breakup of an EPDM viscoelastic
droplet continues until its diameter (a) reaches a critical value
(amin), at which the droplet cannot break up any more but
deforms to be an ellipsoid.29 As the volume of the deformed
droplet is constant in the rotational shear eld, the volume of
the spherical droplet is identical to the volume of the ellipsoid
droplet, as shown in the following equation:
Fig. 1 Droplet deformation in uniform shear.
1818 | Soft Matter, 2014, 10, 18161822
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Paper
4 a3 4
p pLB2 (2)
3 2 3
where a is the initial diameter of the spherical droplet, L and B
are the major semi axis and short semi axis of the deformed
ellipsoid droplet, respectively.
Moreover, according to the correlation between the critical
drop deformation (L  B)/(L + B) and the viscosity ratio of
droplet to matrix (p) reported by Grace, the value of L/B can be
obtained from the measured value of p.33
Therefore, the minimum diameter (amin) of the rubber phase
in the EPDM/PP blend at the early stage of dynamic vulcaniza-
tion can be estimated by using the critical breakup law of the
dispersed droplets in an immiscible blend proposed by Wu as
follows:29
:   
ghm 1 1
4 sin2f $ g12 (3)
Fp L B
16p 16
F p (4)
19p 16
where g_ is the shear rate, hm is the viscosity of the matrix, p
is the viscosity ratio of droplet to matrix (hd and hm), F is the
angle between the major axis of the deformed ellipsoid droplet
and the axis perpendicular to the ow direction (see Fig. 1), and
g12 is the interfacial tension between the droplet and the
matrix.
As hm, p, L/B, g,_ g12, and sin(2F) can be obtained from
experimental results, the minimum value of a(amin) can thus be
calculated according to eqn (2)(4).
The temperature at which the rubber phase in the EPDM/PP
blend breaks up should be determined to calculate the value of
amin because the values of hm, p, and g12 depend on the
temperature. As will be interpreted in detail in Section 3.2, the
temperature at the early stage of dynamic vulcanization was set
as 170
C, at which the blend was melted. Therefore, 170
C was
chosen as the temperature to calculate amin in the EPDM/PP
blends.
3.1.1 Determination of g. _ The shear rate in the Haake
rheomix is not a constant value because of the dierent diam-
eters at dierent positions of the rotors. According to the
parameters provided by the manufacturer (Thermo Fisher
Scientic), the shear rate in the Haake rheomix ranges from 7
s1 to 108 s1 at a rotor speed of 80 rpm.
3.1.2 Determinations of hm and p. The viscosities of EPDM
and PP at 170
C as a function of shear rate were measured by
using the rotational rheometer. Fig. 2 shows the measured
viscosities of the uncured EPDM (hd) and PP (hm). The loga-
rithmic plots for both PP and EPDM are approximately linear. It
can be seen that the shear rate has a signicant eect on the
viscosity of a viscoelastic liquid. The values of hd and hm at
dierent shear rates can be obtained from this gure. Addi-
tionally, the corresponding p and F(p) values can also be
obtained.
3.1.3 Determination of g12. The interfacial tension (g12)
between PP and EPDM can be obtained from the well-known
harmonic mean in eqn (5).29
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Fig. 2 Viscosity vs. shear rate for uncured EPDM and PP at 170
C.

4gd1 gd2 4gp1 gp2
g12 g1 g2   (5)
gd1 gd2 gp1 gp2
where g1 and g2 denote the surface tensions (g) of EPDM and
PP, respectively, and gd and gp are the associated nonpolar and
polar components of g respectively.13 The gd and gp values of
EPDM and PP at high temperatures cannot be measured
directly, but calculated from the c values of EPDM and PP. The
c value is the ratio of the polar component to the total surface
tension and is independent of temperature:13
gp
c (6)
g vulcanization.
EPDM/PP blend is always micrometer scale because of the
coalescence of EPDM droplets aer the shear has stopped.34 For
the vulcanized EPDM/PP blend at the early stage of dynamic
vulcanization, the rapid crosslinking of the EPDM phase could
eectively stop the coalescence of EPDM droplets. Therefore,
theoretically speaking, the minimum size of the EPDM phase in
the vulcanized EPDM/PP blend could be the same as that of an
EPDM droplet in the unvulcanized EPDM/PP blend because of
the in situ vulcanization of the EPDM phase. Thus, the EPDM
phase in the dynamically vulcanized EPDM/PP blend could
break up into rubber nanoparticles at the early stage of dynamic

dc
0 (7) 3.2 Experimental verication: morphology observation
dT
In order to observe the actual size of the rubber phase in the
Table 3 lists the measured c, g, and the calculated gd and gp dynamically vulcanized EPDM/PP blend at the early stage of
values of EPDM and PP at 170
C. According to these values dynamic vulcanization, we need to rst select the sample
listed in Table 3, the interfacial tension (g12) between unvul- according to the torquetime curve. Fig. 3 shows the variation of
canized EPDM and PP at the early stage of vulcanization can be
the mixing torque and temperature as a function of time during
calculated as 5.3 mN m1.
the dynamic vulcanization of the EPDM/PP blend in the Haake
3.1.4 Determination of sin(2F). According to eqn (2) and
rheomix. At the initial stage, the mixing torque decreases with
the results reported by Grace,33 the relation between a and L can the increase in mixing time because of the melting of the blend.
be obtained when the p value is determined. In addition, the Sample A is selected at the inection point A, where the torque
droplet deformation is large in our system. In this case, the reaches a minimum, because the blend has just melted at
value of a/2L is very close to the value of cos F, as can be seen this point. Thus, sample A represents the EPDM/PP blend at the
from Fig. 1. Thus, the value of sin(2F) can be obtained from the early stage of vulcanization. With the rapid vulcanization of the
calculated value of cos F.
rubber phase, the torque rises dramatically until it reaches a
3.1.5 Calculation of amin. According to these measured
maximum before declining slowly until the end of dynamic
_ in the range of 7.1
values of hm, p, and g12 at each shear rate (g)
vulcanization. On the other hand, the temperature increases as
s1 to 108 s1, the minimum diameter of the dispersed EPDM the premix is fed into the Haake rheomix because of the
droplet (amin) is calculated by using eqn (2)(4) and is shown in crosslinking of EPDM. The temperature corresponding to point
Table 4. It can be seen that amin ranges from 2546 nm.
The calculated results indicate that the EPDM phase in the
unvulcanized EPDM/PP blend can break up into rubber nano- Table 4 Measured parameter values and calculated values of amin
scale droplets. However, the EPDM phase in the unvulcanized
g_ hd hm F(p) L/B a/2L sin(2F) amin
(s1) (Pa s) (Pa s) (nm)
Table 3 Surface tension and its components for uncured EPDM and
PP at 170
C 7 4.4  104 3.3  104 0.903 7.70 0.249 0.482 46
20 3.0  104 1.7  104 0.893 9.26 0.220 0.430 37
Material c g gd gp 30 2.8  104 1.6  104 0.894 9.53 0.218 0.426 26
(mN m1) (mN m1) (mN m1) 50 2.3  104 1.2  104 0.890 11.50 0.188 0.369 25
70 1.9  104 9.5  103 0.888 13.71 0.169 0.332 25
EPDM 0.12 23.08 20.31 2.77 90 1.7  104 8.0  103 0.886 14.50 0.168 0.331 26
PP 0.35 32.67 21.24 11.43 108 1.2  104 5.2  103 0.884 15.67 0.170 0.315 35

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Fig. 5 AFM phase images of dynamically vulcanized EPDM/PP blend

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(sample B) taken at the end of dynamic vulcanization with dierent

magnications: (a) 20 mm  20 mm, (b) 3 mm  3 mm.

Fig. 3 Variations of temperature (
C) and torque (N m) of EPDM/PP

an irregular sea island structure is dispersed in the continuous
TPV in the Haake rheomix. A is the point at the initial stage of the
dynamic vulcanization, and B is the point at the end of the dynamic PP matrix. In addition, the EPDM phase appears as particles
vulcanization. with diameters between 0.5 and 3 mm uniformly dispersed
in the PP matrix, consistent with the results reported in
previous studies.13,19 However, by using the PF-AFM, a high-
magnication image of the morphology of the EPDM phase in
A is 170
C. Hence, 170
C is chosen as the temperature to
the PP matrix is obtained and shown in Fig. 5(b). It can be
estimate the formation of rubber nanoparticles in Section 3.1.
observed that the micrometer-sized rubber domains are
The morphology of sample A was then observed by using the
actually the agglomerates of many EPDM nanoparticles with
new PF-AFM, and the image is shown in Fig. 4, where the lighter
diameters in the range 4060 nm, suggesting that the rubber
regions represent the PP phase and the darker regions represent
nanoparticles formed at the early stage of dynamic vulcani-
the crosslinked EPDM phase. It can be seen that the EPDM/PP
zation do not further break up into smaller rubber particles
blend exhibits a co-continuous structure at this stage of
but form micro-sized agglomerates upon further vulcaniza-
dynamic vulcanization. The agglomerates of a great many
tion. In addition, compared with the rubber particles at the
rubber nanoparticles can be observed from this gure. The
early stage of dynamic vulcanization (see Fig. 4), the rubber
diameters of these rubber nanoparticles are in the range of 25
nanoparticles at the end of dynamic vulcanization are more
70 nm (see Fig. 4(b)). This indicates that the EPDM phase
densely agglomerated. The mechanism will be discussed in
indeed breaks up into nanoparticles at the early stage of
Section 3.3.
dynamic vulcanization, in good agreement with the calculated
In addition, the continuous phase (PP) in sample B was
results (see Section 3.1).
washed o with hot xylene to observe the morphology of indi-
Do these nanoparticles further break up into smaller
vidual rubber nanoparticles. Fig. 6 shows the AFM images of the
rubber particles during the subsequent dynamic vulcanization
sample spin coated on a clean coverslip. The dark area repre-
process? What is the microstructure formation mechanism of
sents the crosslinked rubber phase, and the light area repre-
EPDM/PP TPV? To answer these questions, we select sample B
sents the glass substrate. It can be observed that the single
at the end of dynamic vulcanization (B point) according to the
rubber nanoparticles are uniformly dispersed in the suspension
torquetime curve shown in Fig. 3. The morphology of sample
spin coated on the coverslip, and the diameters of these nano-
B was also observed by using the PF-AFM, and the image is
particles are in the range 50120 nm, which are larger than
shown in Fig. 5. From Fig. 5(a), it can be observed that sample
those indicated by in Fig. 5 because of the swelling eect of hot
B, dierent from sample A taken at the early stage of dynamic
xylene, again suggesting that the micrometer-sized rubber
vulcanization, has a two-phase structure where EPDM with
domains in TPV are agglomerates of rubber nanoparticles.

Fig. 4 (a) AFM phase image of un-vulcanized EPDM/PP blend taken at

the early stage of dynamic vulcanization and (b) corresponding size Fig. 6AFM phase images of dissolved blend (sample B) with dierent
distribution of rubber nanoparticles. magnications: (a) 5 mm  5 mm and (b) 1 mm  1 mm.

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Paper
3.3 Formation mechanism of rubber nanoparticles and their
agglomerates during dynamic vulcanization
Fig. 7 shows the formation mechanism of rubber nanoparticles
and their agglomerates during dynamic vulcanization. The
breakup of the EPDM phase at the early stage of dynamic
vulcanization is similar to that of the unvulcanized EPDM in
the EPDM/PP blends because of the low crosslink density of the
EPDM phase at the early stage of dynamic vulcanization. In the
unvulcanized EPDM/PP immiscible blend, the breakup and
coalescence of the EPDM phase occur simultaneously in the
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rotational shear eld. As reported in previous studies, the
breakup of the EPDM phase dominates at the beginning of
the sample preparation because of the sustained shearing
stress, leading to the formation of a large number of EPDM
nanodroplets according to our calculated results, as shown in
Fig. 7(a). The size of an EPDM droplet remains constant when
the speeds of breakup and coalescence reach a dynamic equi-
librium.2128 Aer the shear has stopped, the coalescence of the
EPDM phase dominates, leading to the formation of the
micrometer scale EPDM dispersed phase or co-continuous
phase in the unvulcanized EPDM/PP immiscible blend, as
reported in previous studies.13,35 In the vulcanized EPDM/PP
blend, the EPDM nanodroplets formed by the breakup of the
EPDM phase under the sustained shearing stress at the begin-
ning of the sample preparation transform into EPDM nano-
particles because of the in situ vulcanization at high
temperatures. These rubber nanoparticles will not coalesce
again but form agglomerates of rubber nanoparticles during
further dynamic vulcanization. Therefore, the EPDM phase in
the dynamically vulcanized EPDM/PP blend is the agglomera-
tion of a great many rubber nanoparticles formed at the early
stage of dynamic vulcanization, when the EPDM/PP blend is in a
co-continuous structure, as shown in Fig. 7(b).
On the other hand, the size of the rubber nanoparticles in
sample A is almost the same as that in sample B, indicating that
the breakup of the rubber phase is completely accomplished at
the early stage of dynamic vulcanization (point A in Fig. 3).
During the subsequent dynamic vulcanization, these rubber
nanoparticles do not further break up, but their agglomerates
gradually disintegrate from a continuous phase to a dispersed
Fig. 7 Schematic illustration of (a) breakup and coalescence of the
EPDM rubber phase in the unvulcanized blend and (b) breakup of
rubber particles and their agglomerates in the dynamically vulcanized
blend.
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Soft Matter
phase (sea island structure). In addition, these agglomerates
become much denser than those at the early stage of dynamic
vulcanization because of the increased interfacial energy caused
by the increase in crosslink density and modulus of EPDM
particles. Based on the mechanism, we can control the diameter
of rubber nanoparticles and their agglomerates through
controlling the components of TPV as well as the processing
conditions. This study provides guidance for controlling the
size of the rubber phase in TPV to prepare high performance
TPV products.
4 Conclusion
The minimum size of the broken rubber particles in the EPDM/
PP blend was calculated by using the critical breakup law of
viscoelastic droplets in a viscoelastic matrix. The calculated
results showed that the minimum size of the broken rubber
particles was in nanometers (2546 nm). On the other hand, the
morphology of the actual size of rubber particles in TPV at both
the early stage and the nal stage of dynamic vulcanization
observed by using PF-AFM indicated for the rst time that the
micrometer-sized rubber particles in TPV obtained at the end of
dynamic vulcanization were actually agglomerates of rubber
nanoparticles with a diameter of about 4060 nm, in agreement
with the calculated result. This work provides guidance to
control the microstructure of the rubber phase in TPV to
prepare high performance TPV products for a wide range of
industrial applications.
Acknowledgements
We gratefully acknowledge the National Basic Research
Program of China (Grant no. 2011CB606003) and the National
Natural Science Foundation of China (Grant no. 51221002) for
nancial support. Dr Deng L. Qiu from Bruker Scientic Tech-
nology, Co. Ltd., Beijing, is also acknowledged. In addition, we
would like to thank Dr Tung W. Chan from the Department of
Materials Science and Engineering in Virginia Polytechnic
Institute and State University for improving the written English.
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1822 | Soft Matter, 2014, 10, 18161822 This journal is The Royal Society of Chemistry 2014