The effect of the addition of polypropylene grafted SiO

2
nanoparticle on the crystallization behavior of isotactic
polypropylene
Yoshizo Fukuyama

Takahiko Kawai

Shin-ichi Kuroda

Masahito Toyonaga

Toshiaki Taniike

Minoru Terano
Received: 31 October 2012 / Accepted: 13 December 2012 / Published online: 16 January 2013
Akademiai Kiado, Budapest, Hungary 2013
Abstract The crystallization behavior of isotactic poly-
propylene (iPP)/silica particle (SiO
2
, 26 nm) nanocomposite
has been investigated. In addition to the non surface-modi-
ed SiO
2
, iPP grafted SiO
2
was synthesized and adopted to
this study with an aim to understand the role of grafted
polymer chain on the crystallization process. The crystalli-
zation rate of non surface-modied iPP/SiO
2
composite
stays constant up to 1 vol%. It suggests the very weak
nucleation ability of nano-sized silica particle. While large
acceleration effect was observed for iPP-grafted SiO
2
/iPP
composite. The spherulite density increased with increasing
SiO
2
contents, and more interestingly, the spherulite growth
rate also increased. This nding leads to the conclusion that
the grafted iPP chain has a plasticizing effect that reduces the
chain entanglements at the interface. Further increase in SiO
2
contents, the crystallization rate, the spherulite density, and
the spherulite growth rate showed the steep decreases at
higher SiO
2
content range regardless of the surface modi-
cations of SiO
2
. It was attributed to the connement of matrix
chain since the inter-particle distance of adjacent SiO
2
approaches to the end-to-end distance of matrix chain, which
a large molecular motion is restricted. Moreover, the average
size of SiO
2
aggregation in iPP matrix was successfully
evaluated by analyzing the contents dependence of the
growth rate, assuming that the inter-particle distance with
zero growth rate coincided with end-to-end distance of
matrix iPP chain.
Keywords Polypropylene Nanocomposites Silica
Crystallization
Introduction
Thermoplastic polymers such as iPP are often reinforced by
inorganic llers in order to increase the stiffness, tensile
strength, and dimensional stability at elevated temperatures
[1, 2]. Among many composites being developed and widely
used, iPP/SiO
2
composite has an advantage of low cost
production as well as good mechanical properties. In recent
years, Inorganic particle lled nanocomposites of semi-
crystalline polymers have been explored extensively [3, 4].
It is well accepted that with decreasing particle size,
the ratio of surface/volume increases, so that the surface
properties become crucial. A tenfold decrease in diameter
of particles leads to a 100-fold increase in their surface
areas. It is, thus, easy to understand that the surface prop-
erties of nano-sized particle have a great inuence on the
polymer-nanoparticle composites. It has been reported that
the large specic area of the llers cause the formation of
an interfacial polymer layer (shell) attached to the particle
core [5]. The polymer chains localized in the shell would
have different mobility compared to that in the bulk. The
attractive force between particle and polymer at the inter-
face leads to the decrease in the mobility of polymer in the
shell, resulting in the increase in the glass transition tem-
perature (T
g
). While if there is the repulsive force, the chain
mobility increases yielding to the decrease in T
g
.
The properties of semi-crystalline polymers strongly
depend on the crystalline structure including crystallinity,
Y. Fukuyama T. Kawai (&) S. Kuroda
Department of Production Science and Technology,
Graduate School of Engineering, Gunma University,
29-1 Honcho, Ota, Gunma 373-0057, Japan
e-mail: kawaitakahiko@gunma-u.ac.jp
M. Toyonaga T. Taniike M. Terano
School of Materials Science, Japan Advanced Institute
of Science and Technology, 1-1 Asahidai, Nomi,
Ishikawa 923-1211, Japan
123
J Therm Anal Calorim (2013) 113:15111519
DOI 10.1007/s10973-012-2900-7
crystalline form, and morphology. Since the chain mobility
in the interfacial layer is unequal to the bulk as mentioned
above, the higher-order structure of polymer shall be
altered. In semi-crystalline polymer/nano-particle com-
posites, the adhesion between the polymer and particle
strongly depends on the crystalline structure at the inter-
face. The understanding of the effects of the chemical and/
or physical interactions on the crystalline structure, as well
as its crystallization behavior, is of great importance for the
development of polymer nanocomposites.
Nitta et al. [6, 7] have studied the crystallization
behavior of homogeneously dispersed iPP/SiO
2
nanocom-
posite. The spherulite growth rate of iPP was found to
decrease with increasing SiO
2
content due to the immobi-
lization of polymer chains in the shell. Interestingly, they
also found that the critical distance between adjacent par-
ticles, at which the spherulite growth rate of polymer
becomes zero, coincided with the end-to-end distance of
matrix polymer, hr
2
0
i
1=2
. It demonstrates that the crystal
growth of a polymer, which requires large molecular
motion to transport into growing surface of polymer crys-
tal, is strongly affected by the inter-particle distance, i.e.
the size and the contents of particle in the composite.
The surface modication also affects the chain mobility at
the interface and the crystallization of polymer matrix as well
as the dispersibility of the particles. A great number of
modication methods have been reported [813]. In addition
to the use of a surfactant and/or silane coupling agents that is
the most common method for industries [10, 11], grafting of
oligomers/polymers has been attracting much attention in
recent years [12]. The surface grafting is, however, very
complex since the end-grafted polymer forms various sur-
face morphologies depending on the surface coverage. It has
been reported that the mushroom, brush, and hyperbrush
structures can be formed according to the distance between
the adjacent grafted polymer chains, S
b
[1416]. The dif-
ferent interfacial structures lead to the various physico-
chemical interactions with matrix polymer even though the
chemical structure is identical. It is thus expected that the
interactions affect the chain mobility at the interface, and
consequently the crystallization of matrix polymer. Our co-
authors have recently developed a method for grafting iPP
onto nano-sized SiO
2
to obtain a novel iPP/SiO
2
composite
[17, 18]. In addition to the fact that the aggregation of SiO
2
became smaller according to its superior interaction at the
surface, the crystallization behavior was also reported to be
different compared to the iPP/SiO
2
nanocomposite without
surface modication. The crystallization of the composites
is, however, not fully understood especially for the role of
grafted iPP chains during crystallization.
Our aim is to understand the role of grafted polymer
chain, which has the identical chemical structure to that of
the matrix polymer, on the crystallization process. In this
study, we report the crystallization behavior of iPP/g-SiO
2
composite investigated by means of differential scanning
calorimetry and polarized optical microscopy. iPP with the
number average molecular mass of 12 K was directly
grafted onto SiO
2
particle with a diameter of 26 nm. The
effects of the surface grafting and the content of SiO
2
particles on the crystallization behavior are to be discussed
in terms of overall crystallization rate, nucleating ability,
and spherulite growth rate of iPP.
Experimental
Materials
iPP pellet purchased from Aldrich was used as a matrix
polymer. The mass average molecular mass (M
w
) and
molecular mass distribution (MWD) were 250,000 g mol
-1
and 3.73 respectively. NanoTek silica with an average par-
ticle size of 26 nm and surface area of 110 m
2
g
-1
obtained
from Kanto Chemical Corporation was used as ller.
Synthesis of iPP-OH and iPP grafted SiO
2
iPP-OH was synthesized with rac-ethylenebis(1-inde-
nyl)zirconium dichloride, MMAO, and triethylaluminium
in toluene solvent at 0 C for 1 h with propylene ow in
nitrogen ambient atmosphere. Oxygen gas was bubbled in
the reactor at 0 C for 1 h, followed by the addition of
MeOH and 35 % H
2
O
2
aqueous solution. The number
average molecular mass, M
n
, of iPP-OH was controlled
by the concentration of triethylaluminium (TEA), which
was estimated as 12,000 g mol
-1
. iPP-OH has an isotac-
ticity (mmmm) about 86 mol % and the molecular mass
distribution was about 2.5. iPP-OH was then reacted with
silanol group of silica at 200 C in tetradecane for 6 h. iPP
grafted SiO
2
(g-SiO
2
) was washed by hot ltration with
o-dichlorobenzene at 140 C for 1 h.
Preparation of nanocomposites
Nanocomposites were prepared by melt mixing using a two
roll mixer. iPP pellet as matrix polymer and 0.1 wt% of
stabilizer (AO-50 ADEKA) were kneaded at 185 C for
5 min and then the specic amount of silica was added into
the kneaded iPP. The samples were kneaded at 185 C for
another 10 min. The composites with various SiO
2
con-
tents ranging from 0 to 15 % in volume were prepared. In
addition to the iPP-grafted SiO
2
(g-SiO
2
) described above,
non-surface-treated SiO
2
(n-SiO
2
) was also utilized for a
comparison.
1512 Y. Fukuyama et al.
123
Thermogravimetry
The mass loss of SiO
2
particles was measured by means of
ThermogravimetryDifferential Thermal Analysis (TG
DTA; SII TG/DTA6200). n-SiO
2
and g-SiO
2
particles with
the mass of ca. 10 mg were subjected to the heating to
500 C with a rate of 20 C min
-1
.
Transmission electron microscopy
The distribution of 26-nm-sized silica particles, embedded
in iPP was observed by transmission electron microscopy
(TEM) (JEOL JEM-1200EX). The lms of iPP/n-SiO
2
(1.8 vol%) and iPP/g-SiO
2
(1.2 vol%) were hardened by
epoxy. The cross-section of the lms was then cut to a
thickness of 70 nm using a diamond knife controlled by an
Ultracut S microscope (Reichert). The thin samples were
then laid on a 150 mesh copper grid and dried for 1 day in
a desiccation chamber. The silica nanoparticle image was
examined using an accelerating voltage of 100 kV. TEM
images were analyzed by mean of image analysis software
(Multi Gauge V3.0; FUJIFILM) to quantify the aggrega-
tion size of silica nanoparticles.
Differential scanning calorimetry
Crystallization of iPP nanocomposites was performed in a
Perkin Elmer DSC7 differential scanning calorimeter (DSC)
instrument under nitrogen atmosphere (40 ml min
-1
).
Samples of 56 mg were used. The samples were initially
melted at 200 C for 5 min in order to erase all previous
thermal history. Isothermal crystallization was performed at
128 C and crystallization was carried out until it was
completed.
Polarized optical microscopy
Polarized optical microscope (POM; Olympus BX-50) was
employed for the observation of the spherulites formed
during the crystallization at 135 C. The samples were
sandwiched by cover glasses and subjected to the heat
treatment by means of custom-built hot stage, which
enables the temperature jump with a cooling rate faster
than 1,000 K min
-1
.
Results and discussion
Characterization of interfacial structure in iPP/SiO
2
composites
Figure 1 shows the TG curves of n-SiO
2
and g-SiO
2
during
heat treatment. Mass of SiO
2
stays constant during heating
for n-SiO
2
, whereas it decreases for g-SiO
2
. The mass
reduction is attributed to the degradation of iPP grafted
onto SiO
2
surface. The change in the mass can be con-
verted to the number density of iPP per area (chains/nm
2
)
by following equation:
r
W N
A
q
f
r 10
21
3 M
n
W
f
1
where W is the mass loss of the grafted iPP, N
A
is the
Avogadro number, q
f
is the density of silica, r is the radius of
silica particle, M
n
is the number-average molecular mass and
W
f
is the mass of silica. The number of grafted chains per unit
surface area of SiO
2
was evaluated to be 0.03 chains/nm
2
. It
means that the distance, S
b
, between adjacent grafted chains
was approximately 6.5 nm. The number of iPP chains on a
single SiO
2
particle was thus calculated to be 60 chains. It is
known that the grafted polymer chains form various types of
interfacial morphologies depend on the relationship between
S
b
and the radius of gyration, R
g
, i.e. the size of the coil of
grated polymer chain [1924]. If S
b
[2R
g
, grafted polymer
chains are isolated and form mushroom type morphology on
the solid surface. While if S
b
( 2R
g
, the chain forms high
density brush structure which is extraordinary stretched to
a direction normal to the surface. This structure is obtained
via surface initiated living radical polymerization (LRP)
[2124], which recently has attracted much attention due to
its superior interfacial properties [23, 24]. In the middle
range where S
b
* R
g
and S
b
\R
g
, grafted chains are
overlapped and form semi-dilute brush structure. The R
g
of
iPP is reported to have molecular mass dependence as
follows [25]:
R
g
0:022 M
0:56
w
2
In this study, R
g
is evaluated to be 7.1 nm. By comparing
S
b
(6.5 nm) and R
g
, it is concluded that the adjacent grafted
0 5 10
Time/min
15 20 25 30
0
100
200
300
400
500
600 101
100
99
98
97
96
95
94
M
a
s
s
/
%
T
e
m
p
e
r
a
t
u
r
e
/

C
n-SiO
2
g-SiO
2
Fig. 1 TG curves of n-SiO
2
and g-SiO
2
particle during heat
treatment. The temperature is also indicated in the gure
Crystallization behavior of isotactic polypropylene 1513
123
iPP chains are slightly overlapped and form semi-diluted
brush structure.
Among various methods to estimate the interfacial layer
thickness in composites [4, 2630], dynamic mechanical
analysis (DMA) was employed in this study. The effective
thickness of the interfacial layer can be evaluated by
rationing the loss modulus of homopolymer E
00
0
_ _
and the
composite E
00
c
_ _
measured at room temperature as follows
[4, 27]:
E
00
c
E
00
0

1
1 /
f
B
3a
B 1
Dr
r
_ _
3
3b
Here /
f
and r are the volume fraction and the radius of
the particle, respectively. Dr indicates the effective
interfacial layer thickness. Dr was estimated as 21 nm.
The summary on the interfacial structure of g-SiO
2
is listed
in Table 1, and the structure of grafted iPP on the SiO
2
particle is schematically illustrated in Fig. 2.
Figure 3 shows the transmission electron microscope
(TEM) images of iPP/n-SiO
2
(1.8 vol%) and iPP/g-SiO
2
(1.2 vol%) composites quenched from the melt. The dark
circles indicate the nano-sized SiO
2
particles in the matrix
iPP. It is clearly seen that the SiO
2
particles are aggregated
regardless of the surface treatment. The size of the aggre-
gation was analyzed over the wide range of the sample.
The radiuses being averaged over 300 aggregates were
determined to be 118 nm for iPP/n-SiO
2
and 104 nm for
iPP/g-SiO
2
. Although it is reasonable that the aggregation
becomes smaller for iPP/g-SiO
2
due to the enhancement
in the wettability on SiO
2
surface, the difference of the
dispersibility of SiO
2
is not much obvious in our study.
Crystallization behavior of iPP/SiO
2
nanocomposites
Figure 4 shows the DSC curves of iPP/n-SiO
2
(a) and iPP/
g-SiO
2
(b) composites during isothermal crystallization at
128 C from the melt. Exothermic peak corresponding to
the half time of crystallization show almost no change in
the iPP/n-SiO
2
, while shows a shift to shorter time with
increasing SiO
2
contents in iPP/g-SiO
2
. It indicates that the
grafting of iPP onto SiO
2
surface accelerates the crystal-
lization of matrix iPP. Figure 5 shows the overall crystal-
lization rate (V) of the composites, estimated by the inverse
half time of crystallization, plotted against SiO
2
contents.
In the contents range lower than 1 vol%, V stays almost for
constant both in iPP/n-SiO
2
and iPP/g-SiO
2
, which means
that the surface treatment of SiO
2
has no or quite limited
effect on the crystallization of matrix iPP. While in iPP/g-
SiO
2
, crystallization rates are increased drastically above 1
vol%. Considering that the difference in the dispersity of
SiO
2
is not much differed as seen in Fig. 3, the acceleration
effect on iPP crystallization is due to the role of grafted iPP
chains. It is also important to mention that V falls at higher
contents. Since the trend is the same regardless the surface
modications, it seems to be the characteristics of the
crystallization of polymer with high contents of llers,
which is to be discussed later.
Table 1 Structural characteristics of grafted iPP chains
Number density r/chains nm
-2
Interchain distance S
b
/nm Radius of gyration R
g
/nm E
00
c
1:2 %=E
00
0
Interfacial layer thickness h/nm
0.03 6.5 7.1 1.27 21
h = 21 (nm)
26 (nm)

2
3
6

(
n
m
)
iPP (60 chains/particle)

S
b

=

6
.
5

(
n
m
)
SiO
2
SiO
2
Fig. 2 Schematic illustration of the hierarchical structure of g-SiO
2
in the matrix iPP
Fig. 3 TEM micrographs of
iPP/n-SiO
2
(a) and iPP/g-SiO
2
(b). The black sphere indicates
the aggregated SiO
2
particle
1514 Y. Fukuyama et al.
123
The isothermal crystallization kinetics are analyzed by
well known Avrami equation [31, 32]:
X
c
t 1 exp k t s
n
4
where X
c
(t) is relative the crystallinity at time (t), n is the
Avrami exponent whose value depends on the mechanism
of nucleation and on the dimension of crystal growth, and
k is a rate constant containing the nucleation and growth
parameters. X
c
(t) is equal to the ratio of the heat generated
at time t to the heat generated at innite time according to:
X t
Q
t
=
Q
1

_
t
0
dH=dt dt
_
_
1
0
dH=dt dt 5
where dH/dt is the rate of heat evolution. Eq. (4) can be
changed to
log ln 1 X t n logt s log k 6
The crystallization rate constant k and Avrami exponent
n can be determined fromthe intercept and slope in the plot of
log[-ln(1 - X(t))] versus log(t - s), respectively. Here, s is
the inductiontime for the crystallization. s was adjustedsothat
the data in the shorter time range shows the straight line in
Avrami plot. The Avrami plots are shown in Fig. 6 for iPP/n-
SiO
2
and iPP/g-SiO
2
. The Avrami exponents are ranging
between 3 and 4, suggesting heterogeneous and homogeneous
nucleation for the three dimensional spherical growth. The
summary of the Avrami analysis is listed in Table 2. The
Avrami exponent decreases slightly with increasing n-SiO
2
.
Considering that the spherulite morphologies are observed in
all samples, the decrease is attributed to the change in the
nucleation process. The increase in the particle shall enhance
the nucleationprobabilityat the interface althoughthe effect is
quite limited. The same trend is observed for iPP/g-SiO
2
,
0 0.5 1.5 1 2 3 4 2.5 3.5 0 0.5 1.5 1 2 3 4 2.5 3.5
Time/min Time/min
E
x
o
t
h
e
r
m
i
c
0 %
0.09 %
0.18 %
0.9 %
1.8 %
14.6 %
0 %
0.06 %
0.12 %
1.2 %
2.3 %
12.9 %
n-SiO
2
g-SiO
2
E
x
o
t
h
e
r
m
i
c
(a) (b)
Fig. 4 DSC curves of iPP/n-
SiO
2
(a) and iPP/g-SiO
2
/iPP
(b) during isothermal
crystallization at 128 C
content/vol.%
V
/
s
e
c

1
SiO
2
g-SiO
2
n-SiO
2
iPP/
iPP/
0.02
0.01 0.1 1 10 100
iPP
0.018
0.016
0.014
0.012
0.01
Fig. 5 Plots of the crystallization rate of the composites against the
SiO
2
content. The crystallization temperature is 128 C
1
0 %
1.8 %
14.6 %
0 %
1.2 %
2.3 %
12.9 %
(a) (b)
0.5
0
0.5
1.5
1
2
2.5
1
0.5
0
0.5
1.5
1
2
2.5
log (t ) log (t )
3.5 4 4.5 5 3.6 3.8 4 4.2 4.4
l
o
g

[

I
n

(
1

X
t
)
]
l
o
g

[

I
n

(
1

X
t
)
]
Fig. 6 Avrami plots of iPP with
various contents of n-SiO
2
(a) and g-SiO
2
(b). The
crystallization temperature is
128 C
Crystallization behavior of isotactic polypropylene 1515
123
showing the nucleating ability of g-SiO
2
. The value of s stays
almost constant for entire samples. The small values of s,
compared to the time required for the completion of the
crystallization, indicates that the s has negligible effect for the
Avrami exponent except for veryearlystage of crystallization.
In order to understand the acceleration effect in the
crystallization process of iPP/SiO
2
composite, polarized
optical microscopy was utilized during isothermal crystal-
lization from the melt. Figure 7 shows the optical micro-
graphs of iPP (a), iPP/n-SiO
2
(1.8 vol%) (b), and iPP/
g-SiO
2
(1.2 vol%) (c) during the isothermal crystallization
at 135 C after the elapsed time of 155 s. No particular
difference in the number of spherulite, i.e. nucleation
density, is observed between iPP and iPP/n-SiO
2
, indicat-
ing that the non-treated surface of SiO
2
has poor effect on
the nucleation of iPP. While for iPP/g-SiO
2
, one can see
clearly that the number of spherulite is greatly enhanced. It
should be noted that the nucleation of matrix iPP took place
within a limited range of time, so no further spherulite was
appeared after 155 s. Considering that the dispersibility of
SiO
2
in matrix iPP does not show much difference between
n-SiO
2
and g-SiO
2
system as shown in Fig. 3, grafted iPP
chains on the surface of SiO
2
have a particular effect on the
nucleation of iPP. The number density of spherulites
formed during the isothermal crystallization at 135 C is
plotted in Fig. 8 against the content of SiO
2
. Although data
shows some variations, the number density for nucleation
is not affected by the addition of n-SiO
2
. While for iPP/
g-SiO
2
composite, the density increases with SiO
2
contents
up to 2.3 vol%. It demonstrates the effectiveness of grafted
iPP chains on the SiO
2
surface in the nucleation process. It
is interesting that the nucleation density showed maximum
at 2.3 vol%, followed by steep decrease with increasing
SiO
2
. It suggests that the g-SiO
2
has incremental and
decremental effects in the nucleation process of matrix iPP,
which is to be discussed together with the growth rate
analysis.
Figure 9 shows the change in the spherulite size during
the isothermal crystallization at 135 C. It is well known
that the spherulite grows linearly with time when the
polymer is subjected to the isothermal crystallization. No
non-linear growth, as is often seen in the crystallization of
polymer/plasticizer, is observed [33]. Although the induc-
tion time for crystallization is not much differed in each
sample, the gradient of linear radial growth, which corre-
sponds to the growth rate of iPP crystal, shows the sample
dependence. The spherulite growth rates of the composites
are plotted in Fig. 10 against the logarithmic SiO
2
content.
The dotted line indicates the growth rate of iPP without
SiO
2
particle. It is clearly seen in iPP/n-SiO
2
composites
that the growth rate stays almost constant up to 0.9 vol%,
followed by the steep reduction. This decelerating effect is
Table 2 Summary of Avrami analysis for iPP/n-SiO
2
and iPP/g-SiO
2
SiO
2
/vol% s/s n k/s
n
iPP 0 3.5 3.38 6.81 9 10
-7
iPP/n-SiO
2
1.8 3.0 3.21 1.53 9 10
-6
iPP/n-SiO
2
14.6 3.5 3.08 5.25 9 10
-7
iPP/g-SiO
2
1.2 2.5 3.31 1.49 9 10
-6
iPP/g-SiO
2
2.3 3.0 3.25 2.28 9 10
-6
iPP/g-SiO
2
12.9 3.5 3.54 2.74 9 10
-7
Fig. 7 Polarized optical microscope of iPP (a), iPP/n-SiO
2
(b), and iPP/g-SiO
2
(c) at the elapsed time of 155 s during the isothermal
crystallization at 135 C
250
content/vol%
S
p
h
e
r
u
l
i
t
e

n
u
m
b
e
r

d
e
n
s
i
t
y
/
m
m

3

SiO
2
g-SiO
2
n-SiO
2
iPP/
iPP/
200
150
100
50
0
0.01 0.1 1 10 100
iPP
Fig. 8 Plots of the spherulite number density as a function of SiO
2
content. The crystallization temperature is 135 C
1516 Y. Fukuyama et al.
123
well explained by the model of the connement of the
matrix chains due to the reduction in the inter-particle
distance of SiO
2
. The distance between the surfaces of
adjacent particles d can be estimated by the following
[6, 34]:
d
4p

2
p
3u
f
_ _1=3
2
_
_
_
_
r 7
where /
f
and r are the volume fraction and the radius of the
particle or aggregate, respectively. Nitta et al. [6] have
reported that the growth rate of iPP approached to zero
with increasing SiO
2
content as following:
G
c
G k
1
d
8
where G
c
and G are the spherulite growth rate of the
composite and homopolymer, respectively. k is the
constant that has no molecular mass dependence, and
d the inter-particle distance. They have also concluded that
the critical distance which G
c
become zero coincides with
the end-to-end distance, hr
2
0
i
1=2
, of matrix iPP chains. Our
results in Fig. 10 qualitatively agreed with their results.
With an assumption that the radius r equals to 26 nm,
tting of Eq. (7) to our data leads to obtain the critical
distance as 2 nm, which is much smaller than the end-to-
end distance of polymer. The end-to-end distance of iPP
is reported to have the molecular mass dependence as
follows [35]:
r
2
0
_
_
M
w
_ _
1=2
0:83 9
hr
2
0
i
1=2
of matrix iPP used in this study is estimated to
be 41.5 nm. The difference between the evaluated critical
distance and the end-to-end distance of iPP strongly
suggests the aggregation of the SiO
2
particles. Here, we
tried to estimate the effective radius of aggregation by
assuming d
c
hr
2
0
i
1=2
. The tted curve is shown in
Fig. 10 with bold line, implying that it ts well with the
data of n-SiO
2
composites. The radius of the aggregates of
n-SiO
2
was then estimated as 143 nm, which shows good
agreement with the radius directly observed by TEM
(118 nm). It is important to note that the method described
above enable us to evaluate the average aggregation size of
the particle in semi-crystalline polymer matrix.
The composite with g-SiO
2
, on the other hand, shows
peculiar content dependence in the spherulite growth rate
as seen in Fig. 10. The growth rate starts to increase at
2.3 vol%, reaches to the maximum at 5.6 vol%, and then
starts to decelerate. It indicates that iPP/g-SiO
2
composites
have reciprocal effects on the crystallization of matrix iPP
chains. The deceleration effect at higher content range is
attributed to the connement effect of matrix polymer
chains, which was discussed above. The acceleration
effect, on the other hand, in the middle content range seems
Time/sec
0 50 100 150 200 250 300
Time/sec
0 50 100 150 200 250 300
S
p
h
e
r
u
l
i
t
e

r
a
d
i
u
s
/

m
S
p
h
e
r
u
l
i
t
e

r
a
d
i
u
s
/

m
15
10
5
0
15
10
5
0
0 %
1.8 %
7.1 %
14.6 %
0 %
2.3 %
5.6 %
12.9 %
(a) (b)
Fig. 9 Changes in the radius of
spherulite of iPP/n-SiO
2
(a)
and iPP/g-SiO
2
composites
(b) during the crystallization
at 135 C
0.01
content/vol%
S
p
h
e
r
u
l
i
t
e

g
r
o
w
t
h

r
a
t
e
/

m
/
s
e
c
SiO
2
g-SiO
2
0.1 1 10 100
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
n-SiO
2
iPP/
iPP/
Fig. 10 Plots of spherulite growth rate of iPP/SiO
2
composites as a
function of SiO
2
content. The crystallization temperature is 135 C.
The broken and bold line indicates the growth rate of iPP and the
tted curve of Eqs. 7 and 8 assuming the particle radius of 143 nm,
respectively
Crystallization behavior of isotactic polypropylene 1517
123
to originate in iPP chains grafted onto nano-SiO
2
surface
since n-SiO
2
composite shows no acceleration effect.
It is well accepted that the growth rate of polymer is
depending on its molecular mass. The spherulite growth
rate (G) of polymer spherulite is written as follows [36]:
G G
0
exp
U

R T
c
T
1

_ _
exp
K
g
T
c
DTf
_ _
10
where G
0
is the coefcient and dependent on the molecular
mass, U* is the effective activation energy related to chain
motion, R is the gas constant, T
c
is the crystallization tem-
perature, T
?
is the temperature at which chain motion cea-
ses, DT is the supercooling dened as DT T

m
T
c
, K
g
is
the nucleation constant and f is corrective factor,
f 2T
c
_
T
c
T

m
_ _
. G
0
has been recognized to have a
molecular mass dependence as G
0
* M
-0.5
[37]. It
demonstrates that shorter grafted iPP chains have higher
growth rate during the crystallization except at high T
c
. Thus,
the increase in the growth rate with increasing g-SiO
2
content
in Fig. 10 is attributed to the increase of shorter iPP chains at
the interface of iPP/g-SiO
2
composite. As already mentioned
in this manuscript, grafted iPP chains formsemi-dilute brush
structure at the interfacial region with the thickness of
21 nm. iPP chains of matrix might be able to enter the
interfacial region since the density at the interfacial layer is
extremely small. The grafted chain reduced the chain
entanglements and allows iPP crystal to grow faster. The
higher mobility of grafted chain also helps to nucleate at the
interface, resulting in the increase in the nucleation rate as
well as the nucleation density at the early stage of crystalli-
zation process. Moreover, the co-crystallization of matrix
and grafted chains could be occurring due the same primary
structure, as proposed in the previous paper [18]. It is rea-
sonable that the grafted iPP accelerates the crystal growth by
acting as plasticizer, and then it is packed in same crystalline
lamellae. This might be the characteristic of the crystalli-
zation of composites that the chemical structure of grafted
chains and matrix are the same. If they have different
chemical structures, the grafted chains have to be extracted
fromthe surface of growing crystal yielding to the very weak
interaction with the matrix polymer, i.e. forming very soft
interface. The increase in crystal which includes both matrix
and graft chains should increase the mechanical, thermal,
and electrical properties of the interfacial layer.
Conclusions
The effect of the addition of iPP/SiO
2
nanocomposite on the
crystallization behavior of iPP was investigated by means of
DSC and polarized optical microscopy. In this study, iPP/SiO
2
composite having the same primarystructure for the matrix and
grafted chain was synthesized. No acceleration effect was
observed for the crystallization of non-surface treated SiO
2
/iPP
composite, suggesting the weak nucleation ability of SiO
2
surface. While large acceleration effect was observed for iPP-
grafted SiO
2
/iPP composite. The acceleration of spherulite
growth rate of iPP conrmed that the grafted iPP acted as a
plasticizer. At SiO
2
contents higher than 5.6 vol%, steep
decrease in the crystallization rate were seen regardless of the
surface modications. It was concluded that the connement of
matrix chain took place according to the decrease in the inter-
particle distance with increasing SiO
2
content. Moreover, the
average size of SiO
2
aggregationiniPPmatrixwas successfully
evaluated by analyzing the contents dependence of the growth
rate, assuming that the inter-particle distance with zero growth
rate coincided with end-to-end distance of matrix iPP chain.
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Crystallization behavior of isotactic polypropylene 1519
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