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J Therm Anal Calorim (2013) 113:1511–1519 DOI 10.1007/s10973-012-2900-7

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 Akade´miai 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- fied 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-modified 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 finding 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 modifi- cations of SiO 2 . It was attributed to the confinement 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

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

zero growth rate coincided with end-to-end distance of matrix iPP chain.

Keywords

Crystallization

Polypropylene Nanocomposites Silica

Introduction

Thermoplastic polymers such as iPP are often reinforced by inorganic fillers 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 filled 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 influence on the polymer-nanoparticle composites. It has been reported that the large specific area of the fillers 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,

123

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Y. Fukuyama et al.

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

2 i 1 =2 . It demonstrates that the crystal

matrix polymer, hr

0

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 modification 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 modification 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 modification. 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

123

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 filler.

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 flow 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 filtration 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 specific 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.

Crystallization behavior of isotactic polypropylene

1513

Thermogravimetry

The mass loss of SiO 2 particles was measured by means of Thermogravimetry–Differential 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 films 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 films 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 5–6 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

101 600 100 500 99 n -SiO 2 400 98 300 97 200 96 95
101
600
100
500
99
n
-SiO 2
400
98
300
97
200
96
95
g
-SiO 2
100
94
0
Mass/%
Temperature/°C

0

5

10

15

20

Time/min

25

30

Fig. 1 TG curves of n-SiO 2 and g-SiO 2 particle during heat treatment. The temperature is also indicated in the figure

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 ¼ W N A q f r 10 21 3 M n W f

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 ¼ 0 : 022 M

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

ð

1 Þ

0

:56

w

ð

2 Þ

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Y. Fukuyama et al.

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

00

c

E

¼ 1 :2 % =E

00 Interfacial layer thickness h/nm

0

0.03

6.5

7.1

1.27

21

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

00 measured at room temperature as follows

composite E

and the

00

E

0

c

[4, 27]:

E

00

c

1 / f Þ B

00

0

E

ð1

¼

ð 3a Þ

B ¼ 1 þ Dr

r

3

ð

3b Þ

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

iPP (60 chains/particle) SiO 2 SiO 2 26 (nm) h = 21 (nm) S b
iPP (60 chains/particle)
SiO 2
SiO 2
26 (nm)
h = 21 (nm)
S b = 6.5 (nm)
236 (nm)

Fig. 2 Schematic illustration of the hierarchical structure of g-SiO 2 in the matrix iPP

(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 modifications, it seems to be the characteristics of the crystallization of polymer with high contents of fillers, which is to be discussed later.

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

of iPP/ n -SiO 2 ( a ) and iPP/ g -SiO 2 ( b ).

123

Crystallization behavior of isotactic polypropylene

1515

Fig. 4 DSC curves of iPP/n- SiO 2 (a) and iPP/g-SiO 2 /iPP

(b) during isothermal

crystallization at 128 C

(a) (b) g -SiO 2 n -SiO 2 0 % 0 % 0.06 % 0.09
(a)
(b)
g
-SiO 2
n
-SiO 2
0 %
0 %
0.06
%
0.09
%
0.12
%
0.18
%
0.9
%
1.2
%
1.8
%
2.3
%
12.9
%
14.6
%
Exothermic
Exothermic

0

0.5

12341.5

2.5

3.5

Time/min

0

0.5

12341.5

2.5

3.5

Time/min

0.02 0.018 0.016 iPP 0.014 0.012 iPP/ n -SiO 2 iPP/ g -SiO 2 0.01
0.02
0.018
0.016
iPP
0.014
0.012
iPP/
n
-SiO
2
iPP/
g
-SiO
2
0.01
V /sec –1

0.01

0.1

SiO 2

1

10

content/vol.%

100

Fig. 5 Plots of the crystallization rate of the composites against the SiO 2 content. The crystallization temperature is 128 C

The isothermal crystallization kinetics are analyzed by well known Avrami equation [31, 32]:

ð 4 Þ

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

X c ðÞ¼t

1 exp k ð t s Þ

½

n

parameters. X c (t) is equal to the ratio of the heat generated at time t to the heat generated at infinite time according to:

X

ðÞ¼t

Q t = Q 1 ¼ Z ð dH = dt Þ dt , Z ð dH = dt Þ dt

0

0

t

1

ð

5 Þ

where dH/dt is the rate of heat evolution. Eq. (4) can be changed to

log ½ ln ð 1 X ð t Þ Þ ¼ n logð t s Þ þ log k

The crystallization rate constant k and Avrami exponent

n can be determined from the intercept and slope in the plot of

log [-ln (1 - X(t))] versus log (t - s), respectively. Here, s is the induction time for the crystallization. s was adjusted so that

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 nucleation probability at the interface although the effect is quite limited. The same trend is observed for iPP/g-SiO 2 ,

ð 6 Þ

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

(a) (b) 1 1 0.5 0.5 0 0 –0.5 –0.5 –1 –1 0 % –1.5
(a)
(b)
1
1
0.5
0.5
0
0
–0.5
–0.5
–1
–1
0 %
–1.5
–1.5
0 %
1.2
%
1.8 %
2.3
%
–2
–2
14.6 %
12.9 %
–2.5
–2.5
log [–In (1– X t )]
log [–In (1– X t )]

3.5

4

4.5

log (tτ )

5

3.6

3.8

4

log (tτ )

4.2

4.4

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Y. Fukuyama et al.

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

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 very early stage 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

250 iPP/ n -SiO 2 iPP/ g -SiO 200 2 150 iPP 100 50 0
250
iPP/
n
-SiO
2
iPP/
g
-SiO
200
2
150
iPP
100
50
0
Spherulite number density/mm –3

0.01

0.1

SiO 2

1

content/vol%

10

100

Fig. 8 Plots of the spherulite number density as a function of SiO 2 content. The crystallization temperature is 135 C

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

followed by the steep reduction. This decelerating effect is Fig. 7 Polarized optical microscope of iPP

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

123

Crystallization behavior of isotactic polypropylene

1517

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

(a)

15 0 % 1.8 % 7.1 % 14.6 % 10 5 0 Spherulite radius/μm
15
0 %
1.8
%
7.1
%
14.6 %
10
5
0
Spherulite radius/μm

0

50

100

150

200

Time/sec

250

300

(b)

15 0 % 2.3 % 5.6 % 12.9 % 10 5 0 Spherulite radius/μm
15
0 %
2.3
%
5.6
%
12.9 %
10
5
0
Spherulite radius/μm

0

50

100

150

200

Time/sec

250

300

0.07 0.06 0.05 0.04 0.03 0.02 iPP/ n -SiO 2 0.01 iPP/ g -SiO 2
0.07
0.06
0.05
0.04
0.03
0.02
iPP/
n
-SiO
2
0.01
iPP/
g
-SiO
2
0
Spherulite growth rate/µ m/sec

0.01

0.1

SiO 2

1

10

content/vol%

100

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 fitted curve of Eqs. 7 and 8 assuming the particle radius of 143 nm, respectively

well explained by the model of the confinement 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

¼

2

4

4p

p

ffiffiffi

2

3u f

1=3

3

2 5 r

ð 7 Þ

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

1

c ¼ G k d

ð 8 Þ

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

2 i 1= 2 , of matrix iPP chains. Our

the end-to-end distance, hr

0

results in Fig. 10 qualitatively agreed with their results. With an assumption that the radius r equals to 26 nm, fitting 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]:

2

0

r

M w

1=2 ¼ 0 : 83

ð

9 Þ

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

2 i 1= 2 . The fitted curve is shown in

assuming d c ¼ h r

h

r 0 2

0

Fig. 10 with bold line, implying that it fits 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 confinement effect of matrix polymer chains, which was discussed above. The acceleration effect, on the other hand, in the middle content range seems

123

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Y. Fukuyama et al.

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

¼ G 0 exp

U

R ð

T

c

T

1

Þ

exp

K g T c DTf

ð 10 Þ

where G 0 is the coefficient 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 defined as DT ¼ T m T c , K g is

the

. 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 form semi-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 from the 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.

nucleation

T c þ T

constant and f is corrective factor,

m

f

¼ 2T c

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 primary structure for the matrix and

123

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 confirmed 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 modifications. It was concluded that the confinement 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 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.

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